Study of dithiol monolayer as the interface for controlled deposition of gold nanoparticles

International Nuclear Information System (INIS)

Cichomski, M.; Tomaszewska, E.; Kosla, K.; Kozlowski, W.; Kowalczyk, P.J.; Grobelny, J.

2011-01-01

Self-assembled monolayer of dithiol molecules, deposited on polycrystalline Au (111), prepared at room atmosphere, was studied using scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). Dithiols were used as interface, which chemically bonds to the deposited gold nanoparticles through strong covalent bonds. The size and size distribution of the deposited nanoparticles were measured using dynamic light scattering (DLS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The AFM results showed that nanoparticles are immobilized and stable during scanning procedure and do not contaminate the AFM tip. The size of monodisperse nanoparticles obtained from the DLS measurements is slightly higher than that obtained from the AFM and SEM measurements. This is due to the fact that the DLS measures the hydrodynamic radius, dependent on the protective chemical layer on nanoparticles. - Research Highlights: → Dithiols molecules create chemically bounded layers on a Au (111) surface. → Gold nanoparticles can be chemically bounded to a self-assembled monolayer. → Nanoparticles are stable during AFM probe interactions.

From atoms to layers: in situ gold cluster growth kinetics during sputter deposition

Science.gov (United States)

Schwartzkopf, Matthias; Buffet, Adeline; Körstgens, Volker; Metwalli, Ezzeldin; Schlage, Kai; Benecke, Gunthard; Perlich, Jan; Rawolle, Monika; Rothkirch, André; Heidmann, Berit; Herzog, Gerd; Müller-Buschbaum, Peter; Röhlsberger, Ralf; Gehrke, Rainer; Stribeck, Norbert; Roth, Stephan V.

2013-05-01

The adjustment of size-dependent catalytic, electrical and optical properties of gold cluster assemblies is a very significant issue in modern applied nanotechnology. We present a real-time investigation of the growth kinetics of gold nanostructures from small nuclei to a complete gold layer during magnetron sputter deposition with high time resolution by means of in situ microbeam grazing incidence small-angle X-ray scattering (μGISAXS). We specify the four-stage growth including their thresholds with sub-monolayer resolution and identify phase transitions monitored in Yoneda intensity as a material-specific characteristic. An innovative and flexible geometrical model enables the extraction of morphological real space parameters, such as cluster size and shape, correlation distance, layer porosity and surface coverage, directly from reciprocal space scattering data. This approach enables a large variety of future investigations of the influence of different process parameters on the thin metal film morphology. Furthermore, our study allows for deducing the wetting behavior of gold cluster films on solid substrates and provides a better understanding of the growth kinetics in general, which is essential for optimization of manufacturing parameters, saving energy and resources.The adjustment of size-dependent catalytic, electrical and optical properties of gold cluster assemblies is a very significant issue in modern applied nanotechnology. We present a real-time investigation of the growth kinetics of gold nanostructures from small nuclei to a complete gold layer during magnetron sputter deposition with high time resolution by means of in situ microbeam grazing incidence small-angle X-ray scattering (μGISAXS). We specify the four-stage growth including their thresholds with sub-monolayer resolution and identify phase transitions monitored in Yoneda intensity as a material-specific characteristic. An innovative and flexible geometrical model enables the extraction

Temperature-dependent surface density of alkylthiol monolayers on gold nanocrystals

Science.gov (United States)

Liu, Xuepeng; Lu, Pin; Zhai, Hua; Wu, Yucheng

2018-03-01

Atomistic molecular dynamics (MD) simulations are performed to study the surface density of passivating monolayers of alkylthiol chains on gold nanocrystals at temperatures ranging from 1 to 800 K. The results show that the surface density of alkylthiol monolayer reaches a maximum value at near room temperature (200-300 K), while significantly decreases with increasing temperature in the higher temperature region (> 300 {{K}}), and slightly decreases with decreasing temperature at low temperature (< 200 {{K}}). We find that the temperature dependence of surface ligand density in the higher temperature region is attributed to the substantial ligand desorption induced by the thermal fluctuation, while that at low temperature results from the reduction in entropy caused by the change in the ordering of passivating monolayer. These results are expected helpful to understand the temperature-dependent surface coverage of gold nanocrystals.

Formation and optical characterisation of colloidal gold monolayers

NARCIS (Netherlands)

Kooij, Ernst S.; Brouwer, E.A.M.; Wormeester, Herbert; Poelsema, Bene

2003-01-01

We study the deposition of charge-stabilised gold nanocolloids on silicon substrates, which have been derivatised with (aminopropyl)triethoxysilane. Atomic force microscopy (AFM) and spectroscopic ellipsometry are employed to investigate the nanocrystal monolayers ex situ. Analysis of AFM images

Photo-induced transformation process at gold clusters-semiconductor interface: Implications for the complexity of gold clusters-based photocatalysis

Science.gov (United States)

Liu, Siqi; Xu, Yi-Jun

2016-03-01

The recent thrust in utilizing atomically precise organic ligands protected gold clusters (Au clusters) as photosensitizer coupled with semiconductors for nano-catalysts has led to the claims of improved efficiency in photocatalysis. Nonetheless, the influence of photo-stability of organic ligands protected-Au clusters at the Au/semiconductor interface on the photocatalytic properties remains rather elusive. Taking Au clusters-TiO2 composites as a prototype, we for the first time demonstrate the photo-induced transformation of small molecular-like Au clusters to larger metallic Au nanoparticles under different illumination conditions, which leads to the diverse photocatalytic reaction mechanism. This transformation process undergoes a diffusion/aggregation mechanism accompanied with the onslaught of Au clusters by active oxygen species and holes resulting from photo-excited TiO2 and Au clusters. However, such Au clusters aggregation can be efficiently inhibited by tuning reaction conditions. This work would trigger rational structural design and fine condition control of organic ligands protected-metal clusters-semiconductor composites for diverse photocatalytic applications with long-term photo-stability.

High-Yield Excited Triplet States in Pentacene Self-Assembled Monolayers on Gold Nanoparticles through Singlet Exciton Fission.

Science.gov (United States)

Kato, Daiki; Sakai, Hayato; Tkachenko, Nikolai V; Hasobe, Taku

2016-04-18

One of the major drawbacks of organic-dye-modified self-assembled monolayers on metal nanoparticles when employed for efficient use of light energy is the fact that singlet excited states on dye molecules can be easily deactivated by means of energy transfer to the metal surface. In this study, a series of 6,13-bis(triisopropylsilylethynyl)pentacene-alkanethiolate monolayer protected gold nanoparticles with different particle sizes and alkane chain lengths were successfully synthesized and were employed for the efficient generation of excited triplet states of the pentacene derivatives by singlet fission. Time-resolved transient absorption measurements revealed the formation of excited triplet states in high yield (172±26 %) by suppressing energy transfer to the gold surface. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mixed carboranethiol self-assembled monolayers on gold surfaces

Energy Technology Data Exchange (ETDEWEB)

Yavuz, Adem [Micro and Nanotechnology Department, Graduate School of Natural and Applied Science, Middle East Technical University, Ankara 06800 (Turkey); Sohrabnia, Nima [Department of Chemistry, Middle East Technical University, Ankara 06800 (Turkey); Yilmaz, Ayşen [Micro and Nanotechnology Department, Graduate School of Natural and Applied Science, Middle East Technical University, Ankara 06800 (Turkey); Department of Chemistry, Middle East Technical University, Ankara 06800 (Turkey); Danışman, M. Fatih, E-mail: danisman@metu.edu.tr [Micro and Nanotechnology Department, Graduate School of Natural and Applied Science, Middle East Technical University, Ankara 06800 (Turkey); Department of Chemistry, Middle East Technical University, Ankara 06800 (Turkey)

2017-08-15

Highlights: • M1 binds to the gold surface preferentially when co-deposited with M9 or O1. • Contact angles show similar trends regardless of the gold substrate roughness. • Contact angles were lower, with higher hysteresis, on template stripped gold. • Mixed carboranethiol SAMs have similar morphological properties regardless of mixing ratio. - Abstract: Carboranethiol self-assembled monolayers on metal surfaces have been shown to be very convenient systems for surface engineering. Here we have studied pure and mixed self-assembled monolayers (SAMs) of three different carboranethiol (CT) isomers on gold surfaces. The isomers were chosen with dipole moments pointing parallel to (m-1-carboranethiol, M1), out of (m-9-carboranethiol, M9) and into (o-1-carboranethiol, O1) the surface plane, in order to investigate the effect of dipole moment orientation on the film properties. In addition, influence of the substrate surface morphology on the film properties was also studied by using flame annealed (FA) and template stripped (TS) gold surfaces. Contact angle measurements indicate that in M1/M9 and M1/O1 mixed SAMs, M1 is the dominant species on the surface even for low M1 ratio in the growth solution. Whereas for O1/M9 mixed SAMs no clear evidence could be observed indicating dominance of one of the species over the other one. Though contact angle values were lower and hysteresis values were higher for SAMs grown on TS gold surfaces, the trends in the behavior of the contact angles with changing mixing ratio were identical for SAMs grown on both substrates. Atomic force microscopy images of the SAMs on TS gold surfaces indicate that the films have similar morphological properties regardless of mixing ratio.

Mixed carboranethiol self-assembled monolayers on gold surfaces

Science.gov (United States)

Yavuz, Adem; Sohrabnia, Nima; Yilmaz, Ayşen; Danışman, M. Fatih

2017-08-01

Carboranethiol self-assembled monolayers on metal surfaces have been shown to be very convenient systems for surface engineering. Here we have studied pure and mixed self-assembled monolayers (SAMs) of three different carboranethiol (CT) isomers on gold surfaces. The isomers were chosen with dipole moments pointing parallel to (m-1-carboranethiol, M1), out of (m-9-carboranethiol, M9) and into (o-1-carboranethiol, O1) the surface plane, in order to investigate the effect of dipole moment orientation on the film properties. In addition, influence of the substrate surface morphology on the film properties was also studied by using flame annealed (FA) and template stripped (TS) gold surfaces. Contact angle measurements indicate that in M1/M9 and M1/O1 mixed SAMs, M1 is the dominant species on the surface even for low M1 ratio in the growth solution. Whereas for O1/M9 mixed SAMs no clear evidence could be observed indicating dominance of one of the species over the other one. Though contact angle values were lower and hysteresis values were higher for SAMs grown on TS gold surfaces, the trends in the behavior of the contact angles with changing mixing ratio were identical for SAMs grown on both substrates. Atomic force microscopy images of the SAMs on TS gold surfaces indicate that the films have similar morphological properties regardless of mixing ratio.

Synthesis and stability of monolayer-protected Au38 clusters

NARCIS (Netherlands)

Toikkanen, O.; Ruiz, V.; Rönnholm, G.; Kalkkinen, N.; Liljeroth, P.W.; Quinn, B.M.

2008-01-01

A synthesis strategy to obtain monodisperse hexanethiolate-protected Au38 clusters based on their resistance to etching upon exposure to a hyperexcess of thiol is reported. The reduction time in the standard Brust−Schiffrin two-phase synthesis was optimized such that Au38 were the only clusters that

Near-Edge X-ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

Energy Technology Data Exchange (ETDEWEB)

Willey, T M; Fabbri, J; Lee, J I; Schreiner, P; Fokin, A A; Tkachenko, B A; Fokina, N A; Dahl, J; Carlson, B; Vance, A L; Yang, W; Terminello, L J; van Buuren, T; Melosh, N

2007-11-27

Diamondoids, hydrocarbon molecules with cubic-diamond-cage structures, have unique properties with potential value for nanotechnology. The availability and ability to selectively functionalize this special class of nanodiamond materials opens new possibilities for surface-modification, for high-efficiency field emitters in molecular electronics, as seed crystals for diamond growth, or as robust mechanical coatings. The properties of self-assembled monolayers (SAMs) of diamondoids are thus of fundamental interest for a variety of emerging applications. This paper presents the effects of thiol substitution position and polymantane order on diamondoid SAMs on gold using near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and X-ray photoelectron spectroscopy (XPS). A framework to determine both molecular tilt and twist through NEXAFS is presented and reveals highly ordered diamondoid SAMs, with the molecular orientation controlled by the thiol location. C 1s and S 2p binding energies are lower in adamantane thiol than alkane thiols on gold by 0.67 {+-} 0.05 eV and 0.16 {+-} 0.04 eV respectively. These binding energies vary with diamondoid monolayer structure and thiol substitution position, consistent with different amounts of steric strain and electronic interaction with the substrate. This work demonstrates control over the assembly, in particular the orientational and electronic structure, providing a flexible design of surface properties with this exciting new class of diamond clusters.

Electrochemical immobilization of biomolecules on gold surface modified with monolayered L-cysteine

Energy Technology Data Exchange (ETDEWEB)

Honda, Mitsunori, E-mail: honda.mitsunori@jaea.go.jp; Baba, Yuji; Sekiguchi, Tetsuhiro; Shimoyama, Iwao; Hirao, Norie

2014-04-01

Immobilization of organic molecules on the top of a metal surface is not easy because of lattice mismatch between organic and metal crystals. Gold atoms bind to thiol groups through strong chemical bonds, and a self-assembled monolayer of sulfur-terminated organic molecules is formed on the gold surface. Herein, we suggested that a monolayer of L-cysteine deposited on a gold surface can act as a buffer layer to immobilize biomolecules on the metal surface. We selected lactic acid as the immobilized biomolecule because it is one of the simplest carboxyl-containing biomolecules. The immobilization of lactic acid on the metal surface was carried out by an electrochemical method in an aqueous environment under the potential range varying from − 0.6 to + 0.8 V. The surface chemical states before and after the electrochemical reaction were characterized using X-ray photoelectron spectroscopy (XPS). The N 1s and C 1s XPS spectra showed that the L-cysteine-modified gold surface can immobilize lactic acid via peptide bonds. This technique might enable the immobilization of large organic molecules and biomolecules. - Highlights: • Monolayer l-cysteine deposited on Au surface as a buffer layer to immobilize biomolecules. • Lactic acid as the immobilized biomolecule as it is simple carboxyl-containing biomolecule. • X-ray photoelectron spectroscopy (XPS) of surface chemical states, before and after. • L-cysteine-modified Au surface can immobilize lactic acid via peptide bonds.

Electrochemical immobilization of biomolecules on gold surface modified with monolayered L-cysteine

International Nuclear Information System (INIS)

Honda, Mitsunori; Baba, Yuji; Sekiguchi, Tetsuhiro; Shimoyama, Iwao; Hirao, Norie

2014-01-01

Immobilization of organic molecules on the top of a metal surface is not easy because of lattice mismatch between organic and metal crystals. Gold atoms bind to thiol groups through strong chemical bonds, and a self-assembled monolayer of sulfur-terminated organic molecules is formed on the gold surface. Herein, we suggested that a monolayer of L-cysteine deposited on a gold surface can act as a buffer layer to immobilize biomolecules on the metal surface. We selected lactic acid as the immobilized biomolecule because it is one of the simplest carboxyl-containing biomolecules. The immobilization of lactic acid on the metal surface was carried out by an electrochemical method in an aqueous environment under the potential range varying from − 0.6 to + 0.8 V. The surface chemical states before and after the electrochemical reaction were characterized using X-ray photoelectron spectroscopy (XPS). The N 1s and C 1s XPS spectra showed that the L-cysteine-modified gold surface can immobilize lactic acid via peptide bonds. This technique might enable the immobilization of large organic molecules and biomolecules. - Highlights: • Monolayer l-cysteine deposited on Au surface as a buffer layer to immobilize biomolecules. • Lactic acid as the immobilized biomolecule as it is simple carboxyl-containing biomolecule. • X-ray photoelectron spectroscopy (XPS) of surface chemical states, before and after. • L-cysteine-modified Au surface can immobilize lactic acid via peptide bonds

Metal ion interaction with phosphorylated tyrosine analogue monolayers on gold.

Science.gov (United States)

Petoral, Rodrigo M; Björefors, Fredrik; Uvdal, Kajsa

2006-11-23

Phosphorylated tyrosine analogue molecules (pTyr-PT) were assembled onto gold substrates, and the resulting monolayers were used for metal ion interaction studies. The monolayers were characterized by X-ray photoelectron spectroscopy (XPS), infrared reflection-absorption spectroscopy (IRAS), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS), both prior to and after exposure to metal ions. XPS verified the elemental composition of the molecular adsorbate and the presence of metal ions coordinated to the phosphate groups. Both the angle-dependent XPS and IRAS results were consistent with the change in the structural orientation of the pTyr-PT monolayer upon exposure to metal ions. The differential capacitance of the monolayers upon coordination of the metal ions was evaluated using EIS. These metal ions were found to significantly change the capacitance of the pTyr-PT monolayers in contrast to the nonphosphorylated tyrosine analogue (TPT). CV results showed reduced electrochemical blocking capabilities of the phosphorylated analogue monolayer when exposed to metal ions, supporting the change in the structure of the monolayer observed by XPS and IRAS. The largest change in the structure and interfacial capacitance was observed for aluminum ions, compared to calcium, magnesium, and chromium ions. This type of monolayer shows an excellent capability to coordinate metal ions and has a high potential for use as sensing layers in biochip applications to monitor the presence of metal ions.

Small gold clusters on graphene, their mobility and clustering: a DFT study

International Nuclear Information System (INIS)

Amft, Martin; Sanyal, Biplab; Eriksson, Olle; Skorodumova, Natalia V

2011-01-01

Motivated by the experimentally observed high mobility of gold atoms on graphene and their tendency to form nanometer-sized clusters, we present a density functional theory study of the ground state structures of small gold clusters on graphene, their mobility and clustering. Our detailed analysis of the electronic structures identifies the opportunity to form strong gold-gold bonds and the graphene-mediated interaction of the pre-adsorbed fragments as the driving forces behind gold's tendency to aggregate on graphene. While clusters containing up to three gold atoms have one unambiguous ground state structure, both gas phase isomers of a cluster with four gold atoms can be found on graphene. In the gas phase the diamond-shaped Au 4 D cluster is the ground state structure, whereas the Y-shaped Au 4 Y becomes the actual ground state when adsorbed on graphene. As we show, both clusters can be produced on graphene by two distinct clustering processes. We also studied in detail the stepwise formation of a gold dimer out of two pre-adsorbed adatoms, as well as the formation of Au 3 . All reactions are exothermic and no further activation barriers, apart from the diffusion barriers, were found. The diffusion barriers of all studied clusters range from 4 to 36 meV only, and are substantially exceeded by the adsorption energies of - 0.1 to - 0.59 eV. This explains the high mobility of Au 1-4 on graphene along the C-C bonds.

Organic vapor discrimination with chemiresistor arrays of temperature modulated tin-oxide nanowires and thiolate-monolayer-protected gold nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Scholten, K; Bohrer, F I; Dattoli, E; Lu, W; Zellers, E T, E-mail: ezellers@umich.edu [Center for Wireless Integrated Microsystems, University of Michigan, Ann Arbor, MI 48109-2122 (United States)

2011-03-25

This paper explores the discrimination of organic vapors with arrays of chemiresistors (CRs) employing interface layers of tin-oxide nanowires (NWs) and thiolate-monolayer-protected gold nanoparticles (MPNs). The former devices use contact-printed mats of NWs on micro-hotplate membranes to bridge a pair of metal electrodes. Oxidation at the NW surface causes changes in charge transport, the temperature dependence of which differs among different vapors, permitting vapor discrimination. The latter devices use solvent cast films of MPNs on interdigital electrodes operated at room temperature. Sorption into the organic monolayers causes changes in film tunneling resistance that differ among different vapors and MPN structures, permitting vapor discrimination. Here, we compare the performance and assess the 'complementarity' of these two types of sensors. Calibrated responses from an NW CR operated at two different temperatures and from a set of four different MPN CRs were generated for three test vapors: n-hexane, toluene, and nitromethane. This pooled data set was then analyzed using principal components regression classification models with varying degrees of random error superimposed on the responses via Monte Carlo simulation in order to estimate the rates of recognition/discrimination for arrays comprising different combinations of sensors. Results indicate that the diversity of most of the dual MPN-CR arrays exceeds that of the dual NW-CR array. Additionally, in assessing all possible arrays of 4-6 CR sensors, the recognition rates of the hybrid arrays (i.e. MPN + NW) were no better than that of the 4-sensor array containing only MPN CRs.

Formation of high-quality self-assembled monolayers of conjugated dithiols on gold: base matters.

Science.gov (United States)

Valkenier, Hennie; Huisman, Everardus H; van Hal, Paul A; de Leeuw, Dago M; Chiechi, Ryan C; Hummelen, Jan C

2011-04-06

This Article reports a systematic study on the formation of self-assembled monolayers (SAMs) of conjugated molecules for molecular electronic (ME) devices. We monitored the deprotection reaction of acetyl protected dithiols of oligophenylene ethynylenes (OPEs) in solution using two different bases and studied the quality of the resulting SAMs on gold. We found that the optimal conditions to reproducibly form dense, high-quality monolayers are 9-15% triethylamine (Et(3)N) in THF. The deprotection base tetrabutylammonium hydroxide (Bu(4)NOH) leads to less dense SAMs and the incorporation of Bu(4)N into the monolayer. Furthermore, our results show the importance of the equilibrium concentrations of (di)thiolate in solution on the quality of the SAM. To demonstrate the relevance of these results for molecular electronics applications, large-area molecular junctions were fabricated using no base, Et(3)N, and Bu(4)NOH. The magnitude of the current-densities in these devices is highly dependent on the base. A value of β=0.15 Å(-1) for the exponential decay of the current-density of OPEs of varying length formed using Et(3)N was obtained. © 2011 American Chemical Society

Site-Specific Biomolecule Labeling with Gold Clusters

OpenAIRE

Ackerson, Christopher J.; Powell, Richard D.; Hainfeld, James F.

2010-01-01

Site-specific labeling of biomolecules in vitro with gold clusters can enhance the information content of electron cryomicroscopy experiments. This chapter provides a practical overview of well-established techniques for forming biomolecule/gold cluster conjugates. Three bioconjugation chemistries are covered: Linker-mediated bioconjugation, direct gold–biomolecule bonding, and coordination-mediated bonding of nickel(II) nitrilotriacetic acid (NTA)-derivatized gold clusters to polyhistidine (...

Site-Specific Biomolecule Labeling with Gold Clusters

Science.gov (United States)

Ackerson, Christopher J.; Powell, Richard D.; Hainfeld, James F.

2013-01-01

Site-specific labeling of biomolecules in vitro with gold clusters can enhance the information content of electron cryomicroscopy experiments. This chapter provides a practical overview of well-established techniques for forming biomolecule/gold cluster conjugates. Three bioconjugation chemistries are covered: Linker-mediated bioconjugation, direct gold–biomolecule bonding, and coordination-mediated bonding of nickel(II) nitrilotriacetic acid (NTA)-derivatized gold clusters to polyhistidine (His)-tagged proteins. PMID:20887859

Gold Nanoparticles Protected with Thiol-Derivatized Amphiphilic Poly( -caprolactone)-b-poly(acrylic acid)

DEFF Research Database (Denmark)

Javakhishvili, Irakli; Hvilsted, Søren

2008-01-01

Amphiphilic poly(c-caprolactone)-b-poly(acrylic acid) (HS-PCL-b-PAA) bearing thiol functionality at the PCL terminal has been synthesized by a combination of ring-opening polymerization (ROP) of c-caprolactone (c-CL), esterification of hydroxy chain end with protected mercaptoacetic acid, subsequ....... As a result stable, aggregation-free nanopaticles with moderate dispersity as estimated from UV-visible spectroscopy and transmission electron microscopy (TEM) data were obtained....... chromatography (SEC), nuclear magnetic resonance eR NMR) and infrared (FT IR) spectroscopy. The capacity of the resulting block copolymer in preparation of monolayer-protected gold nanoparticles has been examined by reduction of a gold salt in the presence of this macroligand under thiol-deficient conditions...

A grand unified model for liganded gold clusters

Science.gov (United States)

Xu, Wen Wu; Zhu, Beien; Zeng, Xiao Cheng; Gao, Yi

2016-12-01

A grand unified model (GUM) is developed to achieve fundamental understanding of rich structures of all 71 liganded gold clusters reported to date. Inspired by the quark model by which composite particles (for example, protons and neutrons) are formed by combining three quarks (or flavours), here gold atoms are assigned three `flavours' (namely, bottom, middle and top) to represent three possible valence states. The `composite particles' in GUM are categorized into two groups: variants of triangular elementary block Au3(2e) and tetrahedral elementary block Au4(2e), all satisfying the duet rule (2e) of the valence shell, akin to the octet rule in general chemistry. The elementary blocks, when packed together, form the cores of liganded gold clusters. With the GUM, structures of 71 liganded gold clusters and their growth mechanism can be deciphered altogether. Although GUM is a predictive heuristic and may not be necessarily reflective of the actual electronic structure, several highly stable liganded gold clusters are predicted, thereby offering GUM-guided synthesis of liganded gold clusters by design.

Tribology of monolayer films: comparison between n-alkanethiols on gold and n-alkyl trichlorosilanes on silicon.

Science.gov (United States)

Booth, Brandon D; Vilt, Steven G; McCabe, Clare; Jennings, G Kane

2009-09-01

This Article presents a quantitative comparison of the frictional performance for monolayers derived from n-alkanethiolates on gold and n-alkyl trichlorosilanes on silicon. Monolayers were characterized by pin-on-disk tribometry, contact angle analysis, ellipsometry, and electrochemical impedance spectroscopy (EIS). Pin-on-disk microtribometry provided frictional analysis at applied normal loads from 10 to 1000 mN at a speed of 0.1 mm/s. At low loads (10 mN), methyl-terminated n-alkanethiolate self-assembled monolayers (SAMs) exhibited a 3-fold improvement in coefficient of friction over SAMs with hydroxyl- or carboxylic-acid-terminated surfaces. For monolayers prepared from both n-alkanethiols on gold and n-alkyl trichlorosilanes on silicon, a critical chain length of at least eight carbons is required for beneficial tribological performance at an applied load of 9.8 mN. Evidence for disruption of chemisorbed alkanethiolate SAMs with chain lengths n tribology wear tracks. The direct comparison between the tribological stability of alkanethiolate and silane monolayers shows that monolayers prepared from n-octadecyl dimethylchlorosilane and n-octadecyl trichlorosilane withstood normal loads at least 30 times larger than those that damaged octadecanethiolate SAMs. Collectively, our results show that the tribological properties of monolayer films are dependent on their internal stabilities, which are influenced by cohesive chain interactions (van der Waals) and the adsorbate-substrate bond.

Hole mobility enhancement and p-doping in monolayer WSe2 by gold decoration

KAUST Repository

Chen, Chang-Hsiao

2014-10-28

Tungsten diselenide (WSe2) is an attractive transition metal dichalcogenide material, since its Fermi energy close to the mid gap makes it an excellent candidate for realizing p-n junction devices and complementary digital logic applications. Doping is one of the most important technologies for controlling the Fermi energy in semiconductors, including 2D materials. Here we present a simple, stable and controllable p-doping technique on a WSe2 monolayer, where a more p-typed WSe2 field effect transistor is realized by electron transfer from the WSe2 to the gold (Au) decorated on the WSe2 surfaces. Related changes in Raman spectroscopy are also reported. The p-doping caused by Au on WSe2 monolayers lowers the channel resistance by orders of magnitude. The effective hole mobility is ~100 (cm2/Vs) and the near ideal subthreshold swing of ~60 mV/decade and high on/off current ratio of >106 are observed. The Au deposited on the WSe2 also serves as a protection layer to prevent a reaction between the WSe2 and the environment, making the doping stable and promising for future scalable fabrication.

Electrodeposition of gold templated by patterned thiol monolayers

Energy Technology Data Exchange (ETDEWEB)

She, Zhe [EaStCHEM School of Chemistry, University of St. Andrews, KY16 9ST (United Kingdom); Di Falco, Andrea [SUPA, School of Physics and Astronomy, University of St. Andrews, KY16 9SS (United Kingdom); Hähner, Georg [EaStCHEM School of Chemistry, University of St. Andrews, KY16 9ST (United Kingdom); Buck, Manfred, E-mail: mb45@st-andrews.ac.uk [EaStCHEM School of Chemistry, University of St. Andrews, KY16 9ST (United Kingdom)

2016-06-15

Graphical abstract: - Highlights: • First demonstration of electrodeposition/lift-off of gold using thiol monolayers. • Microelectrode structures with large length to width ratio were generated. • Performance of two different patterning techniques was investigated. • Conditions for achieving good contrast in the electrodeposition were established. - Abstract: The electrochemical deposition of Au onto Au substrates modified by self-assembled monolayers (SAMs) was studied by linear sweep voltammetry (LSV), atomic force microscopy (AFM) and scanning electron microscopy (SEM). Patterned SAMs exhibiting electrochemical contrast were prepared by two different methods. One used microcontact printing (μCP) to generate a binary SAM of ω-(4′-methyl-biphenyl-4-yl)-propane thiol (CH{sub 3}-C{sub 6}H{sub 4}-C{sub 6}H{sub 4}-(CH{sub 2}){sub 3}-SH, MBP3) and octadecane thiol (CH{sub 3}(CH{sub 2}){sub 17}SH, ODT). Templated by the SAM, a gold microelectrode structure was electrodeposited featuring a line 15 μm wide and 3 mm long. After transfer to an epoxy substrate the structure proved to be electrically conductive across the full length. The other patterning method applied electron beam lithography (EBL) where electrochemical contrast was achieved by crosslinking molecules in a single component SAM of MBP3. An electron dose above 250 mC/cm{sup 2} results in a high deposition contrast. The choice of parameters for the deposition/lift-off process is found to be more critical for Au compared to Cu studied previously. The origin of the differences and implications for nanoscale patterning are discussed.

GOLD CLUSTER LABELS AND RELATED TECHNOLOGIES IN MOLECULAR MORPHOLOGY.

Energy Technology Data Exchange (ETDEWEB)

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

2004-02-04

Although intensely colored, even the largest colloidal gold particles are not, on their own, sufficiently colored for routine use as a light microscopy stain: only with very abundant antigens or with specialized illumination methods can bound gold be seen. Colloidal gold probes were developed primarily as markers for electron microscopy, for which their very high electron density and selectivity for narrow size distributions when prepared in different ways rendered them highly suited. The widespread use of gold labeling for light microscopy was made possible by the introduction of autometallographic enhancement methods. In these processes, the bound gold particles are exposed to a solution containing metal ions and a reducing agent; they catalyze the reduction of the ions, resulting in the deposition of additional metal selectively onto the particles. On the molecular level, the gold particles are enlarged up to 30-100 nm in diameter; on the macroscale level, this results in the formation of a dark stain in regions containing bound gold particles, greatly increasing visibility and contrast. The applications of colloidal gold have been described elsewhere in this chapter, we will focus on the use of covalently linked cluster complexes of gold and other metals. A gold cluster complex is a discrete molecular coordination compound comprising a central core, or ''cluster'' of electron-dense metal atoms, ligated by a shell of small organic molecules (ligands), which are linked to the metal atoms on the surface of the core. This structure gives clusters several important advantages as labels. The capping of the metal surface by ligands prevents non-specific binding to cell and tissue components, which can occur with colloidal gold. Cluster compounds are more stable and may be used under a wider range of conditions. Unlike colloidal gold, clusters do not require additional macromolecules such as bovine serum albumin or polyethylene glycol for

Structures of 38-atom gold-platinum nanoalloy clusters

Energy Technology Data Exchange (ETDEWEB)

Ong, Yee Pin; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

2015-04-24

Bimetallic nanoclusters, such as gold-platinum nanoclusters, are nanomaterials promising wide range of applications. We perform a numerical study of 38-atom gold-platinum nanoalloy clusters, Au{sub n}Pt{sub 38−n} (0 ≤ n ≤ 38), to elucidate the geometrical structures of these clusters. The lowest-energy structures of these bimetallic nanoclusters at the semi-empirical level are obtained via a global-minimum search algorithm known as parallel tempering multi-canonical basin hopping plus genetic algorithm (PTMBHGA), in which empirical Gupta many-body potential is used to describe the inter-atomic interactions among the constituent atoms. The structures of gold-platinum nanoalloy clusters are predicted to be core-shell segregated nanoclusters. Gold atoms are observed to preferentially occupy the surface of the clusters, while platinum atoms tend to occupy the core due to the slightly smaller atomic radius of platinum as compared to gold’s. The evolution of the geometrical structure of 38-atom Au-Pt clusters displays striking similarity with that of 38-atom Au-Cu nanoalloy clusters as reported in the literature.

Self-Assembled Monolayers on Gold of β-Cyclodextrin Adsorbates with Different Anchoring Groups

NARCIS (Netherlands)

Méndez Ardoy, Alejandro; Steentjes, Tom; Kudernac, Tibor; Huskens, Jurriaan

2014-01-01

We designed multivalent β-cyclodextrin-based adsorbates bearing different anchoring groups aiming to yield stable monolayers with improved packing and close contact of the cavity to the gold surface. Toward this end the primary rim of the β-cyclodextrin was decorated with several functional groups,

Ethylene glycol monolayer protected nanoparticles: synthesis, characterization, and interactions with biological molecules.

Science.gov (United States)

Zheng, Ming; Li, Zhigang; Huang, Xueying

2004-05-11

The usefulness of the hybrid materials of nanoparticles and biological molecules on many occasions depends on how well one can achieve a rational design based on specific binding and programmable assembly. Nonspecific binding between nanoparticles and biomolecules is one of the major barriers for achieving their utilities in a biological system. In this paper, we demonstrate a new approach to eliminate nonspecific interactions between nanoparticles and biological molecules by shielding the nanoparticle with a monolayer of ethylene glycol. A direct synthesis of di-, tri-, and tetra(ethylene glycol)-protected gold nanoparticles (Au-S-EGn, n = 2, 3, and 4) was achieved under the condition that the water content was optimized in the range of 9-18% in the reaction mixture. With controlled ratio of [HAuCl4]/[EGn-SH] at 2, the synthesized particles have an average diameter of 3.5 nm and a surface plasma resonance band around 510 nm. Their surface structures were confirmed by 1H NMR spectra. These gold nanoparticles are bonded with a uniform monolayer with defined lengths of 0.8, 1.2, and 1.6 nm for Au-S-EG2, Au-S-EG3, and Au-S-EG4, respectively. They have great stabilities in aqueous solutions with a high concentration of electrolytes as well as in organic solvents. Thermogravimetric analysis revealed that the ethylene glycol monolayer coating is ca. 14% of the total nanoparticle weight. Biological binding tests by using ion-exchange chromatography and gel electrophoresis demonstrated that these Au-S-EGn (n = 2, 3, or 4) nanoparticles are free of any nonspecific bindings with various proteins, DNA, and RNA. These types of nanoparticles provide a fundamental starting material for designing hybrid materials composed of metallic nanoparticles and biomolecules.

Hole mobility enhancement and p -doping in monolayer WSe2 by gold decoration

International Nuclear Information System (INIS)

Chen, Chang-Hsiao; Wu, Chun-Lan; Kumar, Pushpendra; Pu, Jiang; Takenobu, Taishi; Chiu, Ming-Hui; Li, Lain-Jong

2014-01-01

Tungsten diselenide (WSe 2 ) is an attractive transition metal dichalcogenide material, since its Fermi energy close to the mid gap makes it an excellent candidate for realizing p–n junction devices and complementary digital logic applications. Doping is one of the most important technologies for controlling the Fermi energy in semiconductors, including 2D materials. Here we present a simple, stable and controllable p-doping technique on a WSe 2 monolayer, where a more p-typed WSe 2 field effect transistor is realized by electron transfer from the WSe 2 to the gold (Au) decorated on the WSe 2 surfaces. Related changes in Raman spectroscopy are also reported. The p-doping caused by Au on WSe 2 monolayers lowers the channel resistance by orders of magnitude. The effective hole mobility is ∼100 (cm 2 /Vs) and the near ideal subthreshold swing of ∼60 mV/decade and high on/off current ratio of >10 6 are observed. The Au deposited on the WSe 2 also serves as a protection layer to prevent a reaction between the WSe 2 and the environment, making the doping stable and promising for future scalable fabrication. (paper)

Surface chemistry and electrocatalytic behaviour of tetra-carboxy substituted iron, cobalt and manganese phthalocyanine monolayers on gold electrode

International Nuclear Information System (INIS)

Mashazi, Philani N.; Westbroek, Philippe; Ozoemena, Kenneth I.; Nyokong, Tebello

2007-01-01

Surface chemistry and electrocatalytic properties of self-assembled monolayers of metal tetra-carboxylic acid phthalocyanine complexes with cobalt (Co), iron (Fe) and manganese (Mn) as central metal ions have been studied. These phthalocyanine molecules are immobilized on gold electrode via the coupling reaction between the ring substituents and pre-formed mercaptoethanol self-assembled monolayer (Au-ME SAM). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy confirmed chemisorption of mercaptoethanol via sulfur group on gold electrode and also coupling reaction between phthalocyanines and Au-ME SAM. Electrochemical parameters of the immobilized molecules show that these molecules are densely packed with a perpendicular orientation. The potential applications of the gold modified electrodes were investigated towards L-cysteine detection and the analysis at phthalocyanine SAMs. Cobalt and iron tetra-carboxylic acid phthalocyanine monolayers showed good oxidation peak for L-cysteine at potentials where metal oxidation (M III /M II ) takes place and this metal oxidation mediates the catalytic oxidation of L-cysteine. Manganese tetra-carboxylic acid phthalocyanine monolayer also exhibited a good catalytic oxidation peak towards L-cysteine at potentials where Mn IV /Mn III redox peak occurs and this redox peak mediates L-cysteine oxidation. The analysis of cysteine at phthalocyanine monolayers displayed good analytical parameters with good detection limits of the orders of 10 -7 mol L -1 and good linearity for a studied concentration range up to 60 μmol L -1

Immobilization of rhodium complexes at thiolate monolayers on gold surfaces : Catalytic and structural studies

NARCIS (Netherlands)

Belser, T; Stöhr, Meike; Pfaltz, A

2005-01-01

Chiral rhodium-diphosphine complexes have been incorporated into self-assembled thiolate monolayers (SAMS) on gold colloids. Catalysts of this type are of interest because they combine properties of homogeneous and heterogeneous systems. In addition, it should be possible to influence the catalytic

Structural, electronic, and magnetic properties of 3D metal trioxide and tetraoxide superhalogen cluster-doped monolayer BN

International Nuclear Information System (INIS)

Meng, Jingjing; Li, Dan; Niu, Yuan; Zhao, Hongmin; Liang, Chunjun; He, Zhiqun

2016-01-01

The structural, electronic, and magnetic properties of monolayer BN doped with 3D metal trioxide and tetraoxide superhalogen clusters are investigated using first-principle calculations. TMO_3_(_4_)-doped monolayer BN exhibits a low negative formation energy, whereas TM atoms embedded in monolayer BN show a high positive formation energy. TMO_3_(_4_) clusters are embedded more easily in monolayer BN than TM atoms. Compared with TMO_3-doped structures, TMO_4-doped structures have a higher structural stability because of their higher binding energies. Given their low negative formation energies, TMO_4-doped structures are more favored for specific applications than TMO_3-doped structures and TM atom-doped structures. Large magnetic moments per supercell and significant ferromagnetic couplings between a TM atom and neighboring B and N atoms on the BN layer were observed in all TMO_4-doped structures, except for TiO_4-doped structures. - Highlights: • TMO_3_(_4_) superhalogen clusters incorporated into monolayer BN were investigated. • TMO_3_(_4_) clusters are embedded more easily in monolayer BN than TM atoms. • TMO_4-doped structures are more favored for specific applications. • Large magnetic moments were observed in TMO_4-doped structures. • The band gap was sensitively dependent on the doped clusters.

Binding motif of terminal alkynes on gold clusters.

Science.gov (United States)

Maity, Prasenjit; Takano, Shinjiro; Yamazoe, Seiji; Wakabayashi, Tomonari; Tsukuda, Tatsuya

2013-06-26

Gold clusters protected by terminal alkynes (1-octyne (OC-H), phenylacetylene (PA-H) and 9-ethynyl-phenanthrene (EPT-H)) were prepared by the ligand exchange of small (diameter alkynes on Au clusters was investigated using various spectroscopic methods. FTIR and Raman spectroscopy revealed that terminal hydrogen is lost during the ligand exchange and that the C≡C bond of the alkynyl group is weakened upon attachment to the Au clusters. Acidification of the water phase after the ligand exchange indicated that the ligation of alkynyl groups to the Au clusters proceeds via deprotonation of the alkynes. A series of precisely defined Au clusters, Au34(PA)16, Au54(PA)26, Au30(EPT)13, Au35(EPT)18, and Au(41-43)(EPT)(21-23), were synthesized and characterized in detail to obtain further insight into the interfacial structures. Careful mass analysis confirmed the ligation of the alkynes in the dehydrogenated form. An upright configuration of the alkynes on Au clusters was suggested from the Au to alkyne ratios and photoluminescence from the excimer of the EPT ligands. EXAFS analysis implied that the alkynyl carbon is bound to bridged or hollow sites on the cluster surface.

Scanning tunneling microscopy studies of glucose oxidase on gold surface

International Nuclear Information System (INIS)

Losic, D.; Shapter, J.G.; Gooding, J.J.

2002-01-01

Full text: Three immobilization methods have been used for scanning tunneling microscopy (STM) studies of glucose oxidase (GOD) on gold. They are based on a) physical adsorption from solution, b) microcontact printing and c) covalent bonding onto self-assembled monolayers (SAM) of 3-mercaptopropionic acid (MPA). The STM images are used to provide information about the organization of individual GOD molecules and more densely packed monolayers of GOD on electrode surfaces, thus providing information of the role of interfacial structure on biosensor performance. The use of atomically flat gold substrates enables easy distinction of deposited enzyme features from the flat gold substrate. Microcontact printing is found to be a more reliable method than adsorption from solution for preparing individual GOD molecules on the gold surface STM images of printed samples reveal two different shapes of native GOD molecules. One is a butterfly shape with dimensions of 10 ± 1 nm x 6 ± 1 nm, assigned to the lying position of molecule while the second is an approximately spherical shape with dimensions of 6.5 ± 1 nm x 5 ± 1nm assigned to a standing position. Isolated clusters of 5 to 6 GOD molecules are also observed. With monolayer coverage, GOD molecules exhibit a tendency to organize themselves into a two dimensional array with adequate sample stability to obtain high-resolution STM images. Within these two-dimensional arrays are clearly seen repeating clusters of five to six enzyme molecules in a unit STM imaging of GOD monolayers covalently immobilized onto SAM (MPA) are considerably more difficult than when the enzyme is adsorbed directly onto the metal. Cluster structures are observed both high and low coverage despite the fact that native GOD is a negatively charged molecule. Copyright (2002) Australian Society for Electron Microscopy Inc

sp magnetism in clusters of gold thiolates

International Nuclear Information System (INIS)

Ayuela, A; Hernando, A; Echenique, P M; Crespo, P; García, M A

2012-01-01

Using first-principles calculations, we consider the bond between thiolate and small Au clusters, with particular emphasis on the resulting magnetic moment. The moment of pure gold clusters is 1 μ B for clusters with an odd number of Au atoms and zero for those with an even number. The addition of the thiolate, having an odd number of electrons itself, shifts the phase of the odd-even oscillations so that particles with an even number of Au atoms now have unit moment. Surprisingly, gold thiolate exhibits a dramatic and non-intuitive distribution of charge and spin moment. Our results show that the S-Au bond is such that sulfur does not get charge and an electron is transferred to the Au cluster. This extra electron is mainly sp in character and resides in an electronic shell below the Au surface. The calculations suggest that any thiolate-induced magnetism occurs in the gold nanoparticle and not the thiolate, and can be controlled by modifying the thiolate coverage. (paper)

Molecular tilt on monolayer-protected nanoparticles

KAUST Repository

Giomi, L.

2012-02-01

The structure of the tilted phase of monolayer-protected nanoparticles is investigated by means of a simple Ginzburg-Landau model. The theory contains two dimensionless parameters representing the preferential tilt angle and the ratio ε between the energy cost due to spatial variations in the tilt of the coating molecules and that of the van der Waals interactions which favors the preferential tilt. We analyze the model for both spherical and octahedral particles. On spherical particles, we find a transition from a tilted phase, at small ε, to a phase where the molecules spontaneously align along the surface normal and tilt disappears. Octahedral particles have an additional phase at small ε characterized by the presence of six topological defects. These defective configurations provide preferred sites for the chemical functionalization of monolayer-protected nanoparticles via place-exchange reactions and their consequent linking to form molecules and bulk materials. Copyright © EPLA, 2012.

Molecular tilt on monolayer-protected nanoparticles

KAUST Repository

Giomi, L.; Bowick, M. J.; Ma, X.; Majumdar, A.

2012-01-01

The structure of the tilted phase of monolayer-protected nanoparticles is investigated by means of a simple Ginzburg-Landau model. The theory contains two dimensionless parameters representing the preferential tilt angle and the ratio ε between the energy cost due to spatial variations in the tilt of the coating molecules and that of the van der Waals interactions which favors the preferential tilt. We analyze the model for both spherical and octahedral particles. On spherical particles, we find a transition from a tilted phase, at small ε, to a phase where the molecules spontaneously align along the surface normal and tilt disappears. Octahedral particles have an additional phase at small ε characterized by the presence of six topological defects. These defective configurations provide preferred sites for the chemical functionalization of monolayer-protected nanoparticles via place-exchange reactions and their consequent linking to form molecules and bulk materials. Copyright © EPLA, 2012.

Ultrafast, 2 min synthesis of monolayer-protected gold nanoclusters (d < 2 nm)

Science.gov (United States)

Martin, Matthew N.; Li, Dawei; Dass, Amala; Eah, Sang-Kee

2012-06-01

An ultrafast synthesis method is presented for hexanethiolate-coated gold nanoclusters (d gold nanoclusters are separated from the reaction byproducts fast and easily without any need for post-synthesis cleaning.An ultrafast synthesis method is presented for hexanethiolate-coated gold nanoclusters (d gold nanoclusters are separated from the reaction byproducts fast and easily without any need for post-synthesis cleaning. Electronic supplementary information (ESI) available: Experimental details of gold nanocluster synthesis and mass-spectrometry. See DOI: 10.1039/c2nr30890h

Photoemission on gold-55-clusters derived from gold-phosphine AuP(C6H5)3Cl

International Nuclear Information System (INIS)

Quinten, M.; Sander, I.; Steiner, P.; Kreibig, U.; Fauth, K.; Schmid, G.

1991-01-01

We measured XPS and UPS spectra of gold clusters with 55 atoms, embedded in an electrically isolating phosphine matrix, and of gold-phosphine, from which the clusters were chemically derived. Compared to the spectra of bulk gold the valence band spectrum and the core level spectra of the clusters showed shifts of the peaks and the fermi level to higher binding energies. The shift of the peaks could qualitatively be interpreted by a final state effect. We succeeded in a separation of bulk and surface contributions to the core level spectra and in a reasonable quantitative analysis of the valence band spectrum of the clusters. The Au 4f core level spectrum of gold-phosphine showed two peaks at 1.5 eV higher binding energies than the corresponding peaks of the clusters. (orig.)

Monolayers of gold nanostars with two Near-IR LSPR capable of additive photothermal response

KAUST Repository

Pallavicini, Piersandro

2015-07-06

Monolayers of photothermally responsive gold nanostars on PEI-coated surfaces display two Localized Surface Plasmon Resonances (LSPR) in the near-IR region that can be laser-irradiated either separately, obtaining two different T jumps, or simultaneously, obtaining a T jump equal to the sum of what obtained with separate irradiations

Monolayers of gold nanostars with two Near-IR LSPR capable of additive photothermal response

KAUST Repository

Pallavicini, Piersandro; Basile, Simone; Chirico, Giuseppe; Dacarro, Giacomo; D'Alfonso, Laura; Donà , Alice; Patrini, Maddalena; Falqui, Andrea; Sironi, Laura; Taglietti, Angelo

2015-01-01

Monolayers of photothermally responsive gold nanostars on PEI-coated surfaces display two Localized Surface Plasmon Resonances (LSPR) in the near-IR region that can be laser-irradiated either separately, obtaining two different T jumps, or simultaneously, obtaining a T jump equal to the sum of what obtained with separate irradiations

Lanthanide-based NMR: a tool to investigate component distribution in mixed-monolayer-protected nanoparticles.

Science.gov (United States)

Guarino, Gaetano; Rastrelli, Federico; Scrimin, Paolo; Mancin, Fabrizio

2012-05-02

Gd(3+) ions, once bound to the monolayer of organic molecules coating the surface of gold nanoparticles, produce a paramagnetic relaxation enhancement (PRE) that broadens and eventually cancels the signals of the nuclear spins located nearby (within 1.6 nm distance). In the case of nanoparticles coated with mixed monolayers, the signals arising from the different coating molecules experience different PRE, depending on their distance from the binding site. As a consequence, observation of the signal broadening patterns provides direct information on the monolayer organization. © 2012 American Chemical Society

Density functional study of structural and electronic properties of bimetallic silver-gold clusters: Comparison with pure gold and silver clusters

Science.gov (United States)

Bonacic-Koutecky, Vlasta; Burda, Jaroslav; Mitric, Roland; Ge, Maofa; Zampella, Giuseppe; Fantucci, Piercarlo

2002-08-01

Bimetallic silver-gold clusters offer an excellent opportunity to study changes in metallic versus "ionic" properties involving charge transfer as a function of the size and the composition, particularly when compared to pure silver and gold clusters. We have determined structures, ionization potentials, and vertical detachment energies for neutral and charged bimetallic AgmAun 3[less-than-or-equal](m+n)[less-than-or-equal]5 clusters. Calculated VDE values compare well with available experimental data. In the stable structures of these clusters Au atoms assume positions which favor the charge transfer from Ag atoms. Heteronuclear bonding is usually preferred to homonuclear bonding in clusters with equal numbers of hetero atoms. In fact, stable structures of neutral Ag2Au2, Ag3Au3, and Ag4Au4 clusters are characterized by the maximum number of hetero bonds and peripheral positions of Au atoms. Bimetallic tetramer as well as hexamer are planar and have common structural properties with corresponding one-component systems, while Ag4Au4 and Ag8 have 3D forms in contrast to Au8 which assumes planar structure. At the density functional level of theory we have shown that this is due to participation of d electrons in bonding of pure Aun clusters while s electrons dominate bonding in pure Agm as well as in bimetallic clusters. In fact, Aun clusters remain planar for larger sizes than Agm and AgnAun clusters. Segregation between two components in bimetallic systems is not favorable, as shown in the example of Ag5Au5 cluster. We have found that the structures of bimetallic clusters with 20 atoms Ag10Au10 and Ag12Au8 are characterized by negatively charged Au subunits embedded in Ag environment. In the latter case, the shape of Au8 is related to a pentagonal bipyramid capped by one atom and contains three exposed negatively charged Au atoms. They might be suitable for activating reactions relevant to catalysis. According to our findings the charge transfer in bimetallic

Determination of low levels of cadmium ions by the under potential deposition on a self-assembled monolayer on gold electrode

Energy Technology Data Exchange (ETDEWEB)

Noyhouzer, Tomer [Institute of Chemistry, Hebrew University of Jerusalem, Jerusalem 91904 (Israel); Mandler, Daniel, E-mail: mandler@vms.huji.ac.il [Institute of Chemistry, Hebrew University of Jerusalem, Jerusalem 91904 (Israel)

2011-01-17

The electrochemical determination of low levels of Cd using a self-assembled monolayer (SAM) modified Au electrode is reported. Determination was based on the stripping of Cd, which was deposited by under potential deposition (UPD). A series of short alkanethiol SAMs bearing different end groups, i.e., sulfonate, carboxylate and ammonium, were examined. Lowest level of detection (ca. 50 ng L{sup -1}) was achieved with a 3-mercaptopropionic acid (MPA) monolayer using subtractive anodic square wave voltammetry (SASV). Additional surface methods, namely, reductive desorption and X-ray photoelectron spectroscopy, were applied to determine the interfacial structure of the electrodeposited Cd on the modified electrodes. We conclude that the deposited Cd forms a monoatomic layer, which bridges between the gold surface and the alkanethiol monolayer associating with both the gold and the sulfur atoms.

Electronic and magnetic properties of 3d-metal trioxides superhalogen cluster-doped monolayer MoS2: A first-principles study

International Nuclear Information System (INIS)

Li, Dan; Niu, Yuan; Zhao, Hongmin; Liang, Chunjun; He, Zhiqun

2014-01-01

Utilizing first-principle calculations, the structural, electronic, and magnetic properties of monolayer MoS 2 doped with 3d transition-metal (TM) atoms and 3d-metal trioxides (TMO 3 ) superhalogen clusters are investigated. 3d-metal TMO 3 superhalogen cluster-doped monolayers MoS 2 almost have negative formation energies except CoO 3 and NiO 3 doped monolayer MoS 2 , which are much lower than those of 3d TM-doped structures. 3d-metal TMO 3 superhalogen clusters are more easily embedded in monolayer MoS 2 than 3d-metal atoms. MnO 3 , FeO 3 , CoO 3 , and NiO 3 incorporated into monolayer MoS 2 are magnetic, and the total magnetic moments are approximately 1.0, 2.0, 3.0, and 4.0 μB per supercell, respectively. MnO 3 and FeO 3 incorporated into monolayer MoS 2 become semiconductors, whereas CoO 3 and NiO 3 incorporated into monolayer MoS 2 become half-metallic. Our studies demonstrate that the half-metallic ferromagnetic nature of 3d-metal TMO 3 superhalogen clusters-doped monolayer MoS 2 has a great potential for MoS 2 -based spintronic device applications. -- Highlights: •TMO 3 superhalogen clusters incorporated into monolayer MoS 2 were investigated. •TMO 3 doped structures have much lower formation energies than TM doped structures. •TMO 3 cluster-doped MoS 2 are thermodynamically favored. •Significant charge transfers between O atoms and Mo atoms in TMO 3 doped structures. •MnO 3 , FeO 3 , CoO 3 , and NiO 3 incorporated into monolayer MoS 2 are magnetic.

Permanent magnetism in phosphine- and chlorine-capped gold: from clusters to nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Munoz-Marquez, Miguel A., E-mail: miguel.angel@icmse.csic.es; Guerrero, Estefania; Fernandez, Asuncion [Instituto de Ciencia de Materiales de Sevilla (CSIC-US) (Spain); Crespo, Patricia; Hernando, Antonio [Instituto de Magnetismo Aplicado (UCM-ADIF-CSIC) (Spain); Lucena, Raquel; Conesa, Jose C. [Instituto de Catalisis y Petroleoquimica (CSIC) (Spain)

2010-05-15

Magnetometry results have shown that gold NPs ({approx}2 nm in size) protected with phosphine and chlorine ligands exhibit permanent magnetism. When the NPs size decreases down to the subnanometric size range, e.g. undecagold atom clusters, the permanent magnetism disappears. The near edge structure of the X-ray absorption spectroscopy data points out that charge transfer between gold and the capping system occurs in both cases. These results strongly suggest that nearly metallic Au bonds are also required for the induction of a magnetic response. Electron paramagnetic resonance observations indicate that the contribution to magnetism from eventual iron impurities can be disregarded.

A low voltage programmable unipolar inverter with a gold nanoparticle monolayer on plastic.

Science.gov (United States)

Zhou, Ye; Han, Su-Ting; Huang, Long-Biao; Huang, Jing; Yan, Yan; Zhou, Li; Roy, V A L

2013-05-24

A programmable low voltage unipolar inverter with saturated-load configuration has been demonstrated on a plastic substrate. A self-assembled monolayer of gold (Au) nanoparticles was inserted into the dielectric layer acting as a charge trapping layer. The inverter operated well with supply voltages of inverter. Furthermore, the programmable behavior was maintained well at various bending states, demonstrating the adequate flexibility of our devices.

Multidentate-Protected Colloidal Gold Nanocrystals: pH Control of Cooperative Precipitation and Surface Layer Shedding

Science.gov (United States)

Kairdolf, Brad A.; Nie, Shuming

2011-01-01

Colloidal gold nanocrystals with broad size tunability and unusual pH-sensitive properties have been synthesized by using multidentate polymer ligands. Containing both carboxylic functional groups and sterically hindered aliphatic chains, the multidentate ligands are able to both reduce gold precursors and to stabilize gold nanoclusters during nucleation and growth. The “as-synthesized” nanocrystals are protected by an inner coordinating layer and an outer polymer layer, and are soluble in water and polar solvents. When the solution pH is lowered by just 0.6 units (from pH 4.85 to 4.25), the particles undergo a dramatic cooperative transition from being soluble to insoluble, allowing rapid isolation, purification, and redispersion of the multidentate-protected nanocrystals. A surprise finding is that when a portion of the surface carboxylate groups is neutralized by protonation, the particles irreversibly shed their outer polymer layer and become soluble in nonpolar organic solvents. Further, the multidentate polymer coatings are permeable to small organic molecules, in contrast to tightly packed self-assembled monolayers of alkanethiols on gold. These insights are important towards the design of “smart” imaging and therapeutic nanoparticles that are activated by small pH changes in the tumor interstitial space or endocytic organelles. PMID:21510704

Self-assembled monolayers of a disulphide-derivatised cobalt-porphyrin on gold

International Nuclear Information System (INIS)

Viana, A.S.; Leupold, S.; Montforts, F.-P.; Abrantes, L.M.

2005-01-01

A self-assembled monolayer (SAM) of a novel cobalt(II)porphyrin disulphide derivative was prepared on flat gold(1 1 1) electrode. Evidence for surface modification was provided by electrochemical reductive desorption of the monolayer and ellipsometry, consistent with a coverage of 2.5 x 10 -10 mol cm -2 and a thickness of 13 A, respectively. Both results support the presence of SAMs where the molecules share an intermediate position between perpendicular and flat orientation. Scanning tunnelling microscopy have also proven the formation of CoPSS SAMs, however high-resolution images could only be obtained when the CoPSS molecules were diluted in an hexanethiol SAM. The electrocatalytic activity of the surface confined Co-porphyrin was evaluated for the oxygen reduction. Voltammetric data indicate that reaction involves two electrons consistent with the formation of hydrogen peroxide. Under similar experimental conditions the data obtained for an iron-porphyrin analogue points for a full reduction of dioxygen to water

Inkjet-printed gold nanoparticle surfaces for the detection of low molecular weight biomolecules by laser desorption/ionization mass spectrometry.

Science.gov (United States)

Marsico, Alyssa L M; Creran, Brian; Duncan, Bradley; Elci, S Gokhan; Jiang, Ying; Onasch, Timothy B; Wormhoudt, Joda; Rotello, Vincent M; Vachet, Richard W

2015-11-01

Effective detection of low molecular weight compounds in matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) is often hindered by matrix interferences in the low m/z region of the mass spectrum. Here, we show that monolayer-protected gold nanoparticles (AuNPs) can serve as alternate matrices for the very sensitive detection of low molecular weight compounds such as amino acids. Amino acids can be detected at low fmol levels with minimal interferences by properly choosing the AuNP deposition method, density, size, and monolayer surface chemistry. By inkjet-printing AuNPs at various densities, we find that AuNP clusters are essential for obtaining the greatest sensitivity. Graphical Abstract ᅟ.

Gold cluster carbonyls: saturated adsorption of CO on gold cluster cations, vibrational spectroscopy, and implications for their structures.

Science.gov (United States)

Fielicke, André; von Helden, Gert; Meijer, Gerard; Pedersen, David B; Simard, Benoit; Rayner, David M

2005-06-15

We report on the interaction of carbon monoxide with cationic gold clusters in the gas phase. Successive adsorption of CO molecules on the Au(n)(+) clusters proceeds until a cluster size specific saturation coverage is reached. Structural information for the bare gold clusters is obtained by comparing the saturation stoichiometry with the number of available equivalent sites presented by candidate structures of Au(n)(+). Our findings are in agreement with the planar structures of the Au(n)(+) cluster cations with n < or = 7 that are suggested by ion mobility experiments [Gilb, S.; Weis, P.; Furche, F.; Ahlrichs, R.; Kappes, M. M. J. Chem. Phys. 2001, 116, 4094]. By inference we also establish the structure of the saturated Au(n)(CO)(m)(+) complexes. In certain cases we find evidence suggesting that successive adsorption of CO can distort the metal cluster framework. In addition, the vibrational spectra of the Au(n)(CO)(m)(+) complexes in both the CO stretching region and in the region of the Au-C stretch and the Au-C-O bend are measured using infrared photodepletion spectroscopy. The spectra further aid in the structure determination of Au(n)(+), provide information on the structure of the Au(n)(+)-CO complexes, and can be compared with spectra of CO adsorbates on deposited clusters or surfaces.

The nature and role of the gold-krypton interactions in small neutral gold clusters.

Science.gov (United States)

Mancera, Luis A; Benoit, David M

2015-03-26

We investigate the nature and role of krypton embedding in small neutral gold clusters. For some of these clusters, we observe a particular site-dependent character of the Kr binding that does not completely follow the criterion of binding at low-coordinated sites, widely accepted for interaction of a noble gas with closed-shell metal systems such as metal surfaces. We aim at understanding the effect of low dimensionality and open-shell electronic structure of the odd-numbered clusters on the noble gas-metal cluster interaction. First, we investigate the role of attractive and repulsive forces, and the frontier molecular orbitals. Second, we investigate the Au-Kr interaction in terms of reactivity and bonding character. We use a reactivity index derived from Fukui formalism, and criteria provided by the electron localization function (ELF), in order to classify the type of bonding. We carry out this study on the minimum energy structures of neutral gold clusters, as obtained using pseudo potential plane-wave density functional theory (DFT). A model is proposed that includes the effect of attractive electrostatic, van der Waals and repulsive forces, together with effects originating from orbital overlap. This satisfactorily explains minimum configurations of the noble gas-gold cluster systems, the site preference of the noble gas atoms, and changes in electronic properties.

Thiol-ene immobilisation of carbohydrates onto glass slides as a simple alternative to gold-thiol monolayers, amines or lipid binding.

Science.gov (United States)

Biggs, Caroline I; Edmondson, Steve; Gibson, Matthew I

2015-01-01

Carbohydrate arrays are a vital tool in studying infection, probing the mechanisms of bacterial, viral and toxin adhesion and the development of new treatments, by mimicking the structure of the glycocalyx. Current methods rely on the formation of monolayers of carbohydrates that have been chemically modified with a linker to enable interaction with a functionalised surface. This includes amines, biotin, lipids or thiols. Thiol-addition to gold to form self-assembled monolayers is perhaps the simplest method for immobilisation as thiolated glycans are readily accessible from reducing carbohydrates in a single step, but are limited to gold surfaces. Here we have developed a quick and versatile methodology which enables the use of thiolated carbohydrates to be immobilised as monolayers directly onto acrylate-functional glass slides via a 'thiol-ene'/Michael-type reaction. By combining the ease of thiol chemistry with glass slides, which are compatible with microarray scanners this offers a cost effective, but also useful method to assemble arrays.

Melting behaviour of gold-platinum nanoalloy clusters by molecular dynamics simulations

Energy Technology Data Exchange (ETDEWEB)

Ong, Yee Pin; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

2015-04-24

The melting behavior of bimetallic gold-platinum nanoclusters is studied by applying Brownian-type isothermal molecular dynamics (MD) simulation, a program modified from the cubic coupling scheme (CCS). The process begins with the ground-state structures obtained from global minimum search algorithm and proceeds with the investigation of the effect of temperature on the thermal properties of gold-platinum nanoalloy clusters. N-body Gupta potential has been employed in order to account for the interactions between gold and platinum atoms. The ground states of the nanoalloy clusters, which are core-shell segregated, are heated until they become thermally segregated. The detailed melting mechanism of the nanoalloy clusters is studied via this approach to provide insight into the thermal stability of the nanoalloy clusters.

Structural properties of gold clusters at different temperatures

CSIR Research Space (South Africa)

Mahladisa, MA

2005-09-01

Full Text Available A series of gold clusters consisting of aggregates of from 13 to 147 atoms was studied using the Sutton-Chen type many-body potential in molecular dynamics simulations. The properties of these clusters at temperatures from 10 K to 1000 K were...

Chemically induced magnetism in atomically precise gold clusters.

Science.gov (United States)

Krishna, Katla Sai; Tarakeshwar, Pilarisetty; Mujica, Vladimiro; Kumar, Challa S S R

2014-03-12

Comparative theoretical and experimental investigations are reported into chemically induced magnetism in atomically-precise, ligand-stabilized gold clusters Au25 , Au38 and Au55 . The results indicate that [Au25 (PPh3 )10 (SC12 H25 )5 Cl2 ](2+) and Au38 (SC12 H25 )24 are diamagnetic, Au25 (SC2 H4 Ph)18 is paramagnetic, and Au55 (PPh3 )12 Cl6 , is ferromagnetic at room temperature. Understanding the magnetic properties resulting from quantum size effects in such atomically precise gold clusters could lead to new fundamental discoveries and applications. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biomimetic nanoparticles with polynucleotide and PEG mixed-monolayers enhance calcium phosphate mineralization

Science.gov (United States)

Vasconcellos, Kayla B.; McHugh, Sean M.; Dapsis, Katherine J.; Petty, Alexander R.; Gerdon, Aren E.

2013-09-01

Biomineralization of hydroxyapatite (Ca10(PO4)6(OH)2) is of significant importance in biomedical applications such as bone and dental repair, and biomimetic control of mineral formation may lead to more effective restorative procedures. Gold nanoparticles are functional scaffolds on which to assemble multi-component monolayers capable of mimicking protein activity in the templated synthesis of calcium phosphate. The goal of this research was to explore nanoparticle templates with mixed-monolayers of uncharged polar polyethylene glycol (PEG) molecules and highly charged polynucleotide and amino acid molecules in their ability to influence mineralization rates and mineral particle size and morphology. This research demonstrates through time-resolved optical density and dynamic light scattering measurements that the combination of tiopronin, PEG, and DNA presented on a nanoparticle surface decreases nanoparticle aggregation from 59 to 21 nm solvated radius, increases mineralization kinetics from 1.5 × 10-3 to 3.1 × 10-3 OD/min, and decreases mineral particle size from 685 to 442 nm average radius. FT-IR and TEM data demonstrate that mineralized material, while initially amorphous, transforms to a semi-crystalline material when guided by template interactions. This demonstrates that surface-tailored monolayer protected cluster scaffolds are successful and controllable mineralization templates with further potential for biomedical applications involving calcium phosphate and other biomaterials.

Biomimetic nanoparticles with polynucleotide and PEG mixed-monolayers enhance calcium phosphate mineralization

Energy Technology Data Exchange (ETDEWEB)

Vasconcellos, Kayla B.; McHugh, Sean M.; Dapsis, Katherine J.; Petty, Alexander R.; Gerdon, Aren E., E-mail: gerdoar@emmanuel.edu [Emmanuel College (United States)

2013-09-15

Biomineralization of hydroxyapatite (Ca{sub 10}(PO{sub 4}){sub 6}(OH){sub 2}) is of significant importance in biomedical applications such as bone and dental repair, and biomimetic control of mineral formation may lead to more effective restorative procedures. Gold nanoparticles are functional scaffolds on which to assemble multi-component monolayers capable of mimicking protein activity in the templated synthesis of calcium phosphate. The goal of this research was to explore nanoparticle templates with mixed-monolayers of uncharged polar polyethylene glycol (PEG) molecules and highly charged polynucleotide and amino acid molecules in their ability to influence mineralization rates and mineral particle size and morphology. This research demonstrates through time-resolved optical density and dynamic light scattering measurements that the combination of tiopronin, PEG, and DNA presented on a nanoparticle surface decreases nanoparticle aggregation from 59 to 21 nm solvated radius, increases mineralization kinetics from 1.5 Multiplication-Sign 10{sup -3} to 3.1 Multiplication-Sign 10{sup -3} OD/min, and decreases mineral particle size from 685 to 442 nm average radius. FT-IR and TEM data demonstrate that mineralized material, while initially amorphous, transforms to a semi-crystalline material when guided by template interactions. This demonstrates that surface-tailored monolayer protected cluster scaffolds are successful and controllable mineralization templates with further potential for biomedical applications involving calcium phosphate and other biomaterials.

Scanning tunneling microscope observation of the phosphatidylserine domains in the phosphatidylcholine monolayer.

Science.gov (United States)

Matsunaga, Soichiro; Yamada, Taro; Kobayashi, Toshihide; Kawai, Maki

2015-05-19

A mixed monolayer of 1,2-dihexanoyl-sn-glycero-3-phospho-l-serine (DHPS) and 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC) on an 1-octanethiol-modified gold substrate was visualized on the nanometer scale using in situ scanning tunneling microscopy (STM) in aqueous solution. DHPS clusters were evident as spotty domains. STM enabled us to distinguish DHPS molecules from DHPC molecules depending on their electronic structures. The signal of the DHPS domains was abolished by neutralization with Ca(2+). The addition of the PS + Ca(2+)-binding protein of annexin V to the Ca(2+)-treated monolayer gave a number of spots corresponding to a single annexin V molecule.

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

International Nuclear Information System (INIS)

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

2017-01-01

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

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

Energy Technology Data Exchange (ETDEWEB)

Berlanga, Isadora [Departamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Av. Blanco Encalada 2008, Santiago (Chile); Etcheverry-Berríos, Álvaro; Mella, Andy; Jullian, Domingo [Departamento de Ciencia de los Materiales, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Beaucheff 851, Santiago (Chile); Gómez, Victoria Alejandra [Departamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Av. Blanco Encalada 2008, Santiago (Chile); Aliaga-Alcalde, Núria [ICREA (Institució Catalana de Recerca i Estudis Avançats), Passeig Lluís Companys, 23, 08018, Barcelona (Spain); CSIC-ICMAB (Institut de Ciència dels Materials de Barcelona), Campus de la Universitat Autònoma de Barcelona, 08193 Bellaterra (Spain); Fuenzalida, Victor [Departamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Av. Blanco Encalada 2008, Santiago (Chile); Flores, Marcos, E-mail: mflorescarra@ing.uchile.cl [Departamento de Física, Facultad de Ciencias Físicas y Matemáticas, Universidad de Chile, Av. Blanco Encalada 2008, Santiago (Chile); and others

2017-01-15

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

Structures, stabilities, and electronic properties for rare-earth lanthanum doped gold clusters

International Nuclear Information System (INIS)

Zhao, Ya-Ru

2015-01-01

The structures, stabilities, and electronic properties of rare-earth lanthanum doped gold La 2 Au n (n = 1-9) and pure gold Au n (n ≤ 11) clusters have been investigated by using density functional theory. The optimized geometries show that the lowest energy structures of La 2 Au n clusters favour the 3D structure at n ≥ 3. The lanthanum atoms can strongly enhance the stabilities of gold clusters and tend to occupy the most highly coordinated position. By analysing the gap, vertical ionization potential, and chemical hardness, it is found that the La 2 Au 6 isomer possesses higher stability for small-sized La 2 Au n clusters (n = 1-9). The charges in the La 2 Au n clusters transfer from La atoms to the Au n host. In addition, Wiberg bond indices analysis reveals that the intensity of different bonds of La 2 Au n clusters exhibits a sequence of La-La bond > La-Au bond > Au-Au bond.

Fabrication of P3HT/gold nanoparticle LB films by P3HT templating Langmuir monolayer

International Nuclear Information System (INIS)

Chen, Liang-Huei; Hsu, Wen-Ping; Chan, Han-Wen; Lee, Yuh-Lang

2014-01-01

Highlights: • Addition of ODA into the P3HT monolayer can significantly improve the dispersion ability of P3HT molecules. • The adsorption ability of the P3HT monolayer to the dispersed AuNPs can also be enhanced by the presence of ODA. - Abstract: Regioregular poly(3-hexyl thiophene) (rr-P3HT) and mixed P3HT/octadecyl amine (ODA) were used as template monolayers to adsorb the gold nanoparticles (AuNPs) dispersed in subphase. The behaviors of P3HT and P3HT/ODA monolayers were investigated by surface pressure area per molecule (π–A) isotherms, transmission electron microscopy (TEM) and atomic force microscopy (AFM). The experimental results show that P3HT does not form a homogeneous film and tends to aggregate at the air/water interface. Meanwhile, the amount of AuNPs adsorbed by the P3HT monolayers is low, attributable to the weak interaction between AuNPs and P3HT. By introduction of ODA molecules into the P3HT monolayer, the spreading of P3HT molecules at the air/water interface is improved and the aggregation of P3HT is significantly inhibited. A nearly uniform and homogeneously mixed P3HT/ODA monolayer can be obtained when 50% of ODA is introduced. It is also found that the introduction of ODA can significantly increase the adsorption of AuNPs. For the mixed monolayer with low ratio of ODA (P3HT/ODA = 1/0.2), a higher concentration of adsorbed AuNPs was observed on the corresponding monolayer. However, when the ODA/P3HT ratio increases to 1/1, the AuNPs tend to form three-dimensional (3D) aggregates and the AuNPs cannot distribute well as a homogeneous monolayer. This result is ascribed to the increasing hydrophobicity of the adsorbed AuNPs because of capping of more ODA molecules

Morphology and magnetism of Fe monolayers and small Fen clusters (n 2-19) supported on the Ni(111) surface

International Nuclear Information System (INIS)

Longo, R C; MartInez, E; Dieguez, O; Vega, A; Gallego, L J

2007-01-01

Using the modified embedded atom model in conjunction with a self-consistent tight-binding method, we investigated the lowest-energy structures of Fe monolayers and isolated Fe n clusters (n = 2-19) supported on the Ni(111) surface. In keeping with experimental findings, our calculations predict that the atoms of the monolayer occupy face-centred cubic (fcc) rather than hexagonal close-packed (hcp) sites. Likewise in agreement with experiment we found that Fe layers stack with a pseudomorphic fcc structure up to two monolayers, beyond which they stack as bcc(110). The structures of supported Fe clusters are predicted to be two-dimensional islands maximizing the number of nearest-neighbour bonds among the adsorbed Fe atoms, and their average magnetic moments per atom decrease towards that of the supported Fe monolayer almost monotonically as n increases. Finally, a pair of Fe 3 clusters on Ni(111) were found to exhibit virtually no interaction with each other even when separated by only one atomic row, i.e. so long as they do not coalesce they retain their individual magnetic properties

Oxidation of ligand-protected aluminum clusters: An ab initio molecular dynamics study

International Nuclear Information System (INIS)

Alnemrat, Sufian; Hooper, Joseph P.

2014-01-01

We report Car-Parrinello molecular dynamics simulations of the oxidation of ligand-protected aluminum clusters that form a prototypical cluster-assembled material. These clusters contain a small aluminum core surrounded by a monolayer of organic ligand. The aromatic cyclopentadienyl ligands form a strong bond with surface Al atoms, giving rise to an organometallic cluster that crystallizes into a low-symmetry solid and is briefly stable in air before oxidizing. Our calculations of isolated aluminum/cyclopentadienyl clusters reacting with oxygen show minimal reaction between the ligand and O 2 molecules at simulation temperatures of 500 and 1000 K. In all cases, the reaction pathway involves O 2 diffusing through the ligand barrier, splitting into atomic oxygen upon contact with the aluminum, and forming an oxide cluster with aluminum/ligand bonds still largely intact. Loss of individual aluminum-ligand units, as expected from unimolecular decomposition calculations, is not observed except following significant oxidation. These calculations highlight the role of the ligand in providing a steric barrier against oxidizers and in maintaining the large aluminum surface area of the solid-state cluster material

Raman spectra of zinc phthalocyanine monolayers absorbed on glassy carbon and gold electrodes by application of a confocal Raman microspectrometer

NARCIS (Netherlands)

Palys-Staron, B.J.; Palys, B.J.; Puppels, G.J.; Puppels, G.J.; van den Ham, D.M.W.; van den Ham, D.M.W.; Feil, D.; Feil, D.

1992-01-01

Raman spectra of zinc phthalocyanine monolayers, adsorbed on gold and on glassy carbon surfaces (electrodes), are presented. These spectra have been recorded with the electrodes inside and outside an electrochemical cell filled with an aqueous electrolyte. A confocal Raman microspectrometer was

PEGylation on mixed monolayer gold nanoparticles: Effect of grafting density, chain length, and surface curvature.

Science.gov (United States)

Lin, Jiaqi; Zhang, Heng; Morovati, Vahid; Dargazany, Roozbeh

2017-10-15

PEGylation on nanoparticles (NPs) is widely used to prevent aggregation and to mask NPs from the fast clearance system in the body. Understanding the molecular details of the PEG layer could facilitate rational design of PEGylated NPs that maximize their solubility and stealth ability without significantly compromising the targeting efficiency and cellular uptake. Here, we use molecular dynamics (MD) simulation to understand the structural and dynamic the PEG coating of mixed monolayer gold NPs. Specifically, we modeled gold NPs with PEG grafting densities ranging from 0-2.76chain/nm 2 , chain length with 0-10 PEG monomers, NP core diameter from 5nm to 500nm. It is found that the area accessed by individual PEG chains gradually transits from a "mushroom" to a "brush" conformation as NP surface curvature become flatter, whereas such a transition is not evident on small NPs when grafting density increases. It is shown that moderate grafting density (∼1.0chain/nm 2 ) and short chain length are sufficient enough to prevent NPs from aggregating in an aqueous medium. The effect of grafting density on solubility is also validated by dynamic light scattering measurements of PEGylated 5nm gold NPs. With respect to the shielding ability, simulations predict that increase either grafting density, chain length, or NP diameter will reduce the accessibility of the protected content to a certain size molecule. Interestingly, reducing NP surface curvature is estimated to be most effective in promoting shielding ability. For shielding against small molecules, increasing PEG grafting density is more effective than increasing chain length. A simple model that includes these three investigated parameters is developed based on the simulations to roughly estimate the shielding ability of the PEG layer with respect to molecules of different sizes. The findings can help expand our current understanding of the PEG layer and guide rational design of PEGylated gold NPs for a particular

The adsorption of helium atoms on small cationic gold clusters.

Science.gov (United States)

Goulart, Marcelo; Gatchell, Michael; Kranabetter, Lorenz; Kuhn, Martin; Martini, Paul; Gitzl, Norbert; Rainer, Manuel; Postler, Johannes; Scheier, Paul; Ellis, Andrew M

2018-04-04

Adducts formed between small gold cluster cations and helium atoms are reported for the first time. These binary ions, Aun+Hem, were produced by electron ionization of helium nanodroplets doped with neutral gold clusters and were detected using mass spectrometry. For a given value of n, the distribution of ions as a function of the number of added helium atoms, m, has been recorded. Peaks with anomalously high intensities, corresponding to so-called magic number ions, are identified and interpreted in terms of the geometric structures of the underlying Aun+ ions. These features can be accounted for by planar structures for Aun+ ions with n ≤ 7, with the addition of helium having no significant effect on the structures of the underlying gold cluster ions. According to ion mobility studies and some theoretical predictions, a 3-D structure is expected for Au8+. However, the findings for Au8+ in this work are more consistent with a planar structure.

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

Science.gov (United States)

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

2018-05-01

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

Scanning probe microscopy investigation of gold clusters deposited on atomically flat substrates

International Nuclear Information System (INIS)

Vandamme, N; Janssens, E; Vanhoutte, F; Lievens, P; Haesendonck, C van

2003-01-01

We systematically studied the influence of the substrate on the shape, mobility, and stability of deposited gold clusters. The Au n clusters were produced in a laser vaporization source and deposited with low kinetic energy (∼0.4 eV/atom) on atomically flat substrates (graphite, mica, and gold and silver films on mica) under UHV conditions. Their size distribution is probed with time-of-flight mass spectrometry and ranges from dimers to several hundreds of atoms. Scanning probe microscopy is used to characterize the deposited clusters and the formation of islands by cluster aggregation. On all substrates, Au n islands can be clearly distinguished and the islands are flattened despite the small impact energy. The shape and size of the island configurations are strongly system dependent. Gold clusters deposited on Au(111) and Ag(111) films grown on mica do not aggregate, but deform due to strong cluster-substrate interactions. The clusters tend to grow epitaxially on these surfaces. On graphite and on mica, deposited clusters do diffuse and aggregate. On the graphite surface, large ramified islands are formed by juxtaposition of small islands and trapping of the clusters at the step edges. On the other hand, the diffusion of the clusters on mica results in a total coalescence of the Au n clusters into compact islands

Gold clusters sliding on graphite: a possible quartz crystal microbalance experiment?

International Nuclear Information System (INIS)

Pisov, S; Tosatti, E; Tartaglino, U; Vanossi, A

2007-01-01

A large measured two-dimensional (2D) diffusion coefficient of gold nanoclusters on graphite has been known experimentally and theoretically for about a decade. When subjected to a lateral force, these clusters should slide with an amount of friction that can be measured. We examine the hypothetical possibility of measuring by quartz crystal microbalance (QCM) the phononic sliding friction of gold clusters in the size range around 250 atoms on a graphite substrate between 300 and 600 K. Assuming the validity of Einstein's relations of ordinary Brownian motion and making use of the experimentally available activated behaviour of the diffusion coefficients, we can predict the sliding friction and slip times as a function of temperature. It is found that a prototypical deposited gold cluster could yield slip times at the standard measurable size of 10 -9 s for temperatures around 450-500 K, or 200 0 C. Since gold nanoclusters may also melt at around these temperatures, QCM could offer the additional chance of observing this phenomenon through a frictional change

Simulation studies on structural and thermal properties of alkane thiol capped gold nanoparticles.

Science.gov (United States)

Devi, J Meena

2017-06-01

The structural and thermal properties of the passivated gold nanoparticles were explored employing molecular dynamics simulation for the different surface coverage densities of the self-assembled monolayer (SAM) of alkane thiol. The structural properties of the monolayer protected gold nanoparticles such us overall shape, organization and conformation of the capping alkane thiol chains were found to be influenced by the capping density. The structural order of the thiol capped gold nanoparticles enhances with the increase in the surface coverage density. The specific heat capacity of the alkane thiol capped gold nanoparticles was found to increase linearly with the thiol coverage density. This may be attributed to the enhancement in the lattice vibrational energy. The present simulation results suggest, that the structural and thermal properties of the alkane thiol capped gold nanoparticles may be modified by the suitable selection of the SAM coverage density. Copyright © 2017 Elsevier Inc. All rights reserved.

Influence of Structure and Charge State on the Mechanism of CO Oxidation on Gold Clusters

Science.gov (United States)

Johnson, Grant; Burgel, Christian; Reilly, Nelly; Mitric, Roland; Kimble, Michele; Tyo, Eric; Castleman, A. W.; Bonacic-Koutecky, Vlasta

2008-05-01

Gas-phase reactivity experiments and high level theoretical calculations have been employed to study the interaction of both positively and negatively charged gold oxide clusters with carbon monoxide (CO). We demonstrate that for negatively charged clusters CO is oxidized to CO2 by an Eley-Ridel-like (ER-) mechanism involving the attack of CO on oxygen rather than gold. In contrast, for positively charged clusters, the oxidation reaction may also occur by a Langmuir-Hinshelwood-like (LH-) mechanism involving the initial binding of CO to a gold atom followed by subsequent migration to an oxygen site. The LH mechanism is made possible through the large energy gain associated with the adsorption of two CO molecules onto cationic gold clusters. Structure-reactivity relationships are also established which demonstrate that terminally bound oxygen atoms are the most active sites for CO oxidation. Bridge bonded oxygen atoms and molecularly bound O2 units are shown to be inert. We also establish an inverse relationship between the binding energy of CO to gold clusters and the energy of the clusters lowest unoccupied molecular orbital (LUMO).

Formation of Underbrushes on thiolated Poly (ethylene glycol) PEG monolayers by Oligoethylene glycol (OEG) terminated Alkane Thiols on Gold

DEFF Research Database (Denmark)

Lokanathan, Arcot R.

2011-01-01

Adding underbrushes of oligoethylene glycol (OEG) to monolayers of long chain PEG molecules on a surface is one of the strategies [1] in designing a suitable platform for antifouling purpose, where it is possible to have high graft density and molecular conformational freedom[4] simultaneously......, there by maximal retention of activity of covalently immobilised antifouling enzyme [2] on PEG surfaces along with resistance to protein adsorption[3]. Here we present some our studies on the addition of OEG thiol molecules over a self assembled monolayer of PEG thiol on gold. The kinetics of addition of OEG thiol...

Nanoparticle-Mediated Rescue of p53 Through Targeted Degradation of MDM2

National Research Council Canada - National Science Library

Fischer, Nicholas; Rotello, Vincent M

2004-01-01

.... By incorporating traditional peptide inhibitors of mdm2 with mixed monolayer protected gold cluster nanoparticles, we hope to effect mdm2 denaturation on the nanoparticle surface, increase peptide...

Water-Soluble Phosphine-Protected Au₁₁ Clusters: Synthesis, Electronic Structure, and Chiral Phase Transfer in a Synergistic Fashion.

Science.gov (United States)

Yao, Hiroshi; Iwatsu, Mana

2016-04-05

Synthesis of atomically precise, water-soluble phosphine-protected gold clusters is still currently limited probably due to a stability issue. We here present the synthesis, magic-number isolation, and exploration of the electronic structures as well as the asymmetric conversion of triphenylphosphine monosulfonate (TPPS)-protected gold clusters. Electrospray ionization mass spectrometry and elemental analysis result in the primary formation of Au11(TPPS)9Cl undecagold cluster compound. Magnetic circular dichroism (MCD) spectroscopy clarifies that extremely weak transitions are present in the low-energy region unresolved in the UV-vis absorption, which can be due to the Faraday B-terms based on the magnetically allowed transitions in the cluster. Asymmetric conversion without changing the nuclearity is remarkable by the chiral phase transfer in a synergistic fashion, which yields a rather small anisotropy factor (g-factor) of at most (2.5-7.0) × 10(-5). Quantum chemical calculations for model undecagold cluster compounds are then used to evaluate the optical and chiroptical responses induced by the chiral phase transfer. On this basis, we find that the Au core distortion is ignorable, and the chiral ion-pairing causes a slight increase in the CD response of the Au11 cluster.

A theoretical study on interaction of proline with gold cluster

Indian Academy of Sciences (India)

with Au3 (Pakiari and Jamshidi 2007) and interaction of. ∗. Author for correspondence (harjinder.singh@iiit.ac.in) small gold clusters with xDNA base pairs (Sharma et al. 2009) have motivated us to carry out a theoretical study on interaction of proline with gold nanoparticles. Proline is unique among the natural amino acids ...

IMPACT OF POLYCYCLIC AROMATIC HYDROCARBONS OF THE ELECTROCHEMICAL RESPONSES OF A FERRICYNIDE PROBE AT TEMPLATE-MODIFIED SELF ASSEMBLED MONOLAYERS ON GOLD ELECTRODES

Science.gov (United States)

The impact of pyrene on the electrochemical response of the ferricyanide probe using Self Assembled Monolayer (SAM)-modified gold electrodes was investigated using Cyclic Voltammetry (CV) and Square Wave Voltammetry (SWV). These results suggest the feasibility of using SAMs, par...

Deposition of metal Islands, metal clusters and metal containing single molecules on self-assembled monolayers

NARCIS (Netherlands)

Speets, Emiel Adrianus

2005-01-01

The central topic of this thesis is the deposition of metals on Self-Assembled Monolayers (SAMs). Metals are deposited in the form of submicron scale islands, nanometer scale clusters, and as supramolecular, organometallic coordination cages. Several SAMs on various substrates were prepared and

Formation of high-quality self-assembled monolayers of conjugated dithiols on gold : Base matters

NARCIS (Netherlands)

Valkenier, Hennie; Huisman, Everardus H.; Hal, Paul A. van; de Leeuw, Dagobert; Chiechi, Ryan C.; Hummelen, Jan C.

2011-01-01

This Article reports a systematic study on the formation of self-assembled monolayers (SAMs) of conjugated molecules for molecular electronic (ME) devices. We monitored the deprotection reaction of acetyl protected dithiols of oligophenylene ethynylenes (OPEs) in solution using two different bases

Cyanide leaching of Au/CeO2: highly active gold clusters for 1,3-butadiene hydrogenation.

Science.gov (United States)

Guan, Y; Hensen, E J M

2009-11-07

Ceria-supported gold catalysts before and after leaching by NaCN were investigated by X-ray absorption spectroscopy at the Au L(III) edge. After gold leaching, isolated gold cations remain in close interaction with the support. These ions form an ideal precursor to very small clusters of a few gold atoms upon reduction. The resulting gold clusters exhibit a very high intrinsic activity in the hydrogenation of 1,3-butadiene, which is at least one order of magnitude higher than that of the nanometre-sized gold particles in the non-leached parent catalyst. These findings point to a very strong structure sensitivity of the gold-catalyzed hydrogenation of dienes.

A critical size for emergence of nonbulk electronic and geometric structures in dodecanethiolate-protected Au clusters.

Science.gov (United States)

Negishi, Yuichi; Nakazaki, Tafu; Malola, Sami; Takano, Shinjiro; Niihori, Yoshiki; Kurashige, Wataru; Yamazoe, Seiji; Tsukuda, Tatsuya; Häkkinen, Hannu

2015-01-28

We report on how the transition from the bulk structure to the cluster-specific structure occurs in n-dodecanethiolate-protected gold clusters, Au(n)(SC12)m. To elucidate this transition, we isolated a series of Au(n)(SC12)m in the n range from 38 to ∼520, containing five newly identified or newly isolated clusters, Au104(SC12)45, Au(∼226)(SC12)(∼76), Au(∼253)(SC12)(∼90), Au(∼356)(SC12)(∼112), and Au(∼520)(SC12)(∼130), using reverse-phase high-performance liquid chromatography. Low-temperature optical absorption spectroscopy, powder X-ray diffractometry, and density functional theory (DFT) calculations revealed that the Au cores of Au144(SC12)60 and smaller clusters have molecular-like electronic structures and non-fcc geometric structures, whereas the structures of the Au cores of larger clusters resemble those of the bulk gold. A new structure model is proposed for Au104(SC12)45 based on combined approach between experiments and DFT calculations.

Detection of gold cluster ions by ion-to-ion conversion using a CsI-converter

International Nuclear Information System (INIS)

Nguyen, V.-T.; Novilkov, A.C.; Obnorskii, V.V.

1997-01-01

Gold cluster ions in the m/z range of 10 4 -2 x 10 6 u were produced by bombarding a thin film of gold with 252 Cf-fission fragments. The gold covering a C-Al substrate formed islets having a mean diameter of 44 A. Their size- and mass-distribution was determined by means of electron microscopy. The main task was to measure the m/z distribution of the cluster ions ejected from the sample surface. For this purpose we built a time-of-flight (TOF) mass spectrometer, which could be used as a linear TOF instrument or, alternatively, as a tandem-TOF instrument being equipped with an ion-to-ion converter. Combining the results obtained in both modes, it turned out that the linear TOF instrument equipped with micro-channel plates had a mean detection efficiency for 20 keV cluster ions of about 40%. In the tandem mode, the cluster ions hit a CsI converter with energies of 40z keV (z = charge state), from where secondary ions - mainly Cs + and (CsI) n Cs + cluster ions - were ejected. These ions were used to measure the TOF spectrum of the gold cluster ions. The detection efficiency of the cluster ions was found to vary in the available mass range from 99.7% to 96.5%. The complete mass distribution between 4 x 10 4 and 4 x 10 6 u was determined and compared with the corresponding mass distribution of the gold islets covering the substrate. (orig.)

Impact of slow gold clusters on various solids

International Nuclear Information System (INIS)

Benguerba, M.; Brunelle, A.; Della-Negra, S.; Depauw, J.; Joret, H.; Beyec, Y. Le; Schweikert, E.A.; Assayag, G.B.; Sudraud, P.

1991-01-01

A liquid metal ion source has been installed on a pulsed ion gun. The time of flight (TOF) spectra of the pulsed beam were recorded. With the gold source several cluster ions (up to 10 atoms in the cluster) and doubly charged ions were identified in the ion beam TOF spectra. With a second pulsation, single cluster ions can be selected as projectiles for secondary ion TOF mass spectrometry. The secondary ion emission induced by cluster impact from a variety of targets (organic, CsI, metallic) was studied. A large enhancement of yield is observed by comparison to single atomic ion impact (e.g., a factor of 30 between Au 3 + and Au + ). The secondary ion yields increase nonlinearly with the number of constituents in the cluster. A comparison with other types of clusters and also fission fragments of 252 Cf has been performed. The rate of secondary emission stimulated by cluster is similar to the secondary ion yield induced by fission fragments. (author) 47 refs., 18 figs., 5 tabs

Plasmon-enhanced photocurrent generation from self-assembled monolayers of phthalocyanine by using gold nanoparticle films.

Science.gov (United States)

Sugawa, Kosuke; Akiyama, Tsuyoshi; Kawazumi, Hirofumi; Yamada, Sunao

2009-04-09

The effect of localized electric fields on the photocurrent responses of phthalocyanine that was self-assembled on a gold nanoparticle film was investigated by comparing the conventional and the total internal reflection (TIR) experimental systems. In the case of photocurrent measurements, self-assembled monolayers (SAMs) of a thiol derivative of palladium phthalocyanine (PdPc) were prepared on the surface of gold-nanoparticle film that was fixed on the surface of indium-tin-oxide (ITO) substrate via a polyion (PdPc/AuP/polyion/ITO) or on the ITO surface (PdPc/ITO). Photocurrent action spectra from the two samples were compared by using the conventional spectrometer, and were found that PdPc/AuP/polyion/ITO gave considerably larger photocurrent signals than PdPc/ITO under the identical concentration of PdPc. In the case of the TIR experiments for the PdPc/AuP/polyion/ITO and the PdPc/AuP/Glass systems, incident-angle profiles of photocurrent and emission signals were correlated with each other, and they were different from that of the PdPc/ITO system. Accordingly, it was demonstrated that the photocurrent signals were certainly enhanced by the localized electric fields of the gold-nanoparticle film.

Self-Assembled Gold Nano-Ripple Formation by Gas Cluster Ion Beam Bombardment.

Science.gov (United States)

Tilakaratne, Buddhi P; Chen, Quark Y; Chu, Wei-Kan

2017-09-08

In this study, we used a 30 keV argon cluster ion beam bombardment to investigate the dynamic processes during nano-ripple formation on gold surfaces. Atomic force microscope analysis shows that the gold surface has maximum roughness at an incident angle of 60° from the surface normal; moreover, at this angle, and for an applied fluence of 3 × 10 16 clusters/cm², the aspect ratio of the nano-ripple pattern is in the range of ~50%. Rutherford backscattering spectrometry analysis reveals a formation of a surface gradient due to prolonged gas cluster ion bombardment, although the surface roughness remains consistent throughout the bombarded surface area. As a result, significant mass redistribution is triggered by gas cluster ion beam bombardment at room temperature. Where mass redistribution is responsible for nano-ripple formation, the surface erosion process refines the formed nano-ripple structures.

Molecular dynamics simulation of gold cluster growth during sputter deposition

Energy Technology Data Exchange (ETDEWEB)

Abraham, J. W., E-mail: abraham@theo-physik.uni-kiel.de; Bonitz, M., E-mail: bonitz@theo-physik.uni-kiel.de [Institut für Theoretische Physik und Astrophysik, Christian-Albrechts-Universität zu Kiel, Leibnizstraße 15, D-24098 Kiel (Germany); Strunskus, T.; Faupel, F. [Institut für Materialwissenschaft, Lehrstuhl für Materialverbunde, Christian-Albrechts-Universität zu Kiel, Kaiserstraße 2, D-24143 Kiel (Germany)

2016-05-14

We present a molecular dynamics simulation scheme that we apply to study the time evolution of the self-organized growth process of metal cluster assemblies formed by sputter-deposited gold atoms on a planar surface. The simulation model incorporates the characteristics of the plasma-assisted deposition process and allows for an investigation over a wide range of deposition parameters. It is used to obtain data for the cluster properties which can directly be compared with recently published experimental data for gold on polystyrene [M. Schwartzkopf et al., ACS Appl. Mater. Interfaces 7, 13547 (2015)]. While good agreement is found between the two, the simulations additionally provide valuable time-dependent real-space data of the surface morphology, some of whose details are hidden in the reciprocal-space scattering images that were used for the experimental analysis.

Ligand-free gold atom clusters adsorbed on graphene nano sheets generated by oxidative laser fragmentation in water

Science.gov (United States)

Lau, Marcus; Haxhiaj, Ina; Wagener, Philipp; Intartaglia, Romuald; Brandi, Fernando; Nakamura, Junji; Barcikowski, Stephan

2014-08-01

Over three decades after the first synthesis of stabilized Au55-clusters many scientific questions about gold cluster properties are still unsolved and ligand-free colloidal clusters are difficult to fabricate. Here we present a novel route to produce ultra-small gold particles by using a green technique, the laser ablation and fragmentation in water, without using reductive or stabilizing agents at any step of the synthesis. For fabrication only a pulsed laser, a gold-target, pure water, sodium hydroxide and hydrogen peroxide are deployed. The particles are exemplarily hybridized to graphene supports showing that these carbon-free colloidal clusters might serve as versatile building blocks.

DNA biosensor for detection of Salmonella typhi from blood sample of typhoid fever patient using gold electrode modified by self-assembled monolayers of thiols

Science.gov (United States)

Suryapratiwi, Windha Novita; Paat, Vlagia Indira; Gaffar, Shabarni; Hartati, Yeni Wahyuni

2017-05-01

Electrochemical biosensors are currently being developed in order to handle various clinical problems in diagnosing infectious diseases caused by pathogenic bacteria, or viruses. On this research, voltammetric DNA biosensor using gold electrode modified by thiols with self-assembled monolayers had been developed to detect a certain sequence of Salmonella typhi DNA from blood sample of typhoid fever patient. Thiol groups of cysteamines (Cys) and aldehyde groups from glutaraldehydes (Glu) were used as a link to increase the performance of gold electrode in detecting guanine oxidation signal of hybridized S. typhi DNA and ssDNA probe. Standard calibration method was used to determine analytical parameters from the measurements. The result shown that, the detection of S. typhi DNA from blood sample of typhoid fever patient can be carried out by voltammetry using gold electrode modified by self-assembled monolayers of thiols. A characteristic oxidation potential of guanine using Au/Cys/Gluwas obtained at +0.17 until +0.20 V. Limit of detection and limit of quantification from this measurements were 1.91μg mL-1 and 6.35 μg mL-1. The concentration of complement DNA from sample was 6.96 μg mL-1.

Theory of lithium islands and monolayers: Electronic structure and stability

International Nuclear Information System (INIS)

Quassowski, S.; Hermann, K.

1995-01-01

Systematic calculations on planar clusters and monolayers of lithium are performed to study geometries and stabilities of the clusters as well as their convergence behavior with increasing cluster size. The calculations are based on ab initio methods using density-functional theory within the local-spin-density approximation for exchange and correlation. The optimized nearest-neighbor distances d NN of the Li n clusters, n=1,...,25, of both hexagonal and square geometry increase with cluster size, converging quite rapidly towards the monolayer results. Further, the cluster cohesive energies E c increase with cluster size and converge towards the respective monolayer values that form upper bounds. Clusters of hexagonal geometry are found to be more stable than square clusters of comparable size, consistent with the monolayer results. The size dependence of the cluster cohesive energies can be described approximately by a coordination model based on the concept of pairwise additive nearest-neighbor binding. This indicates that the average binding in the Li n clusters and their relative stabilities can be explained by simple geometric effects which derive from the nearest-neighbor coordination

Plasmonic Gold Nanorods Coverage Influence on Enhancement of the Photoluminescence of Two-Dimensional MoS2 Monolayer

KAUST Repository

Lee, Kevin C. J.

2015-11-17

The 2-D transition metal dichalcogenide (TMD) semiconductors, has received great attention due to its excellent optical and electronic properties and potential applications in field-effect transistors, light emitting and sensing devices. Recently surface plasmon enhanced photoluminescence (PL) of the weak 2-D TMD atomic layers was developed to realize the potential optoelectronic devices. However, we noticed that the enhancement would not increase monotonically with increasing of metal plasmonic objects and the emission drop after the certain coverage. This study presents the optimized PL enhancement of a monolayer MoS2 in the presence of gold (Au) nanorods. A localized surface plasmon wave of Au nanorods that generated around the monolayer MoS2 can provide resonance wavelength overlapping with that of the MoS2 gain spectrum. These spatial and spectral overlapping between the localized surface plasmon polariton waves and that from MoS2 emission drastically enhanced the light emission from the MoS2 monolayer. We gave a simple model and physical interpretations to explain the phenomena. The plasmonic Au nanostructures approach provides a valuable avenue to enhancing the emitting efficiency of the 2-D nano-materials and their devices for the future optoelectronic devices and systems.

Plasmonic Gold Nanorods Coverage Influence on Enhancement of the Photoluminescence of Two-Dimensional MoS2 Monolayer

KAUST Repository

Lee, Kevin C. J.; Chen, Yi-Huan; Lin, Hsiang-Yu; Cheng, Chia-Chin; Chen, Pei-Ying; Wu, Ting-Yi; Shih, Min-Hsiung; Wei, Kung-Hwa; Li, Lain-Jong; Chang, Chien-Wen

2015-01-01

The 2-D transition metal dichalcogenide (TMD) semiconductors, has received great attention due to its excellent optical and electronic properties and potential applications in field-effect transistors, light emitting and sensing devices. Recently surface plasmon enhanced photoluminescence (PL) of the weak 2-D TMD atomic layers was developed to realize the potential optoelectronic devices. However, we noticed that the enhancement would not increase monotonically with increasing of metal plasmonic objects and the emission drop after the certain coverage. This study presents the optimized PL enhancement of a monolayer MoS2 in the presence of gold (Au) nanorods. A localized surface plasmon wave of Au nanorods that generated around the monolayer MoS2 can provide resonance wavelength overlapping with that of the MoS2 gain spectrum. These spatial and spectral overlapping between the localized surface plasmon polariton waves and that from MoS2 emission drastically enhanced the light emission from the MoS2 monolayer. We gave a simple model and physical interpretations to explain the phenomena. The plasmonic Au nanostructures approach provides a valuable avenue to enhancing the emitting efficiency of the 2-D nano-materials and their devices for the future optoelectronic devices and systems.

Electrochemical detection of Cd2+ ions by a self-assembled monolayer of 1,9-nonanedithiol on gold

International Nuclear Information System (INIS)

Malel, Esteban; Sinha, Jatin K.; Zawisza, Izabella; Wittstock, Gunther; Mandler, Daniel

2008-01-01

The application of 1,9-nonanedithiol (NDT) self-assembled monolayer (SAM) on gold for the electrochemical determination of Cd 2+ was studied. Interestingly, we found that a NDT SAM strongly affects the stripping wave of Cd, resulting in a sharp peak that was used for electroanalytical determination of Cd 2+ in aqueous solutions. The different parameters, such as potential and time of deposition of Cd, were examined. Furthermore, polarization-modulated infrared reflection absorption spectroscopy (PM IRRAS) and X-ray photoelectron spectroscopy (XPS) were used for exploring the interaction between the deposited Cd and the thiol groups on Au. FTIR measurements clearly indicate that NDT is assembled in a disordered liquid type monolayer interacting with the Au electrode via both thiol moieties. XPS reveals that Cd is stripped at two different potentials and that the signal of sulfur is almost unchanged by deposition and desorption of Cd. All these finding allude to the interesting conclusion that Cd is deposited on Au lifting to some extent the thiol groups

Aqueous gold nanosols stabilized by electrostatic protection generated by X-ray irradiation assisted radical reduction

International Nuclear Information System (INIS)

Wang, C.-H.; Hua, Tzu-En; Chien, C.-C.; Yu, Y.-L.; Yang, T.-Y.; Liu, C.-J.; Leng, W.-H.; Hwu, Y.; Yang, Y.-C.; Kim, Chong-Cook; Je, Jung-Ho; Chen, C.-H.; Lin, H.-M.; Margaritondo, G.

2007-01-01

Reductant, stabilizer-free colloidal gold solutions were fabricated by a new room-temperature synchrotron X-ray irradiation method. The influence of process parameters such as the pH value and the exposure time on the structure of gold nanoparticles was investigated. The mechanisms underlying the X-ray-triggered reduction of gold ions and the formation of gold clusters are discussed in detail. The X-ray irradiation derived highly concentrated gold nanoparticles are readily to be re-dispersed and possess suitable colloidal stability within cellular environment. The characterization included a study of the possible cytotoxicity for the EMT-6 tumor cell line: the negative results indicate that the gold clusters produced with our approach are biocompatible

Observing the real time formation of phosphine-ligated gold clusters by electrospray ionization mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Ligare, Marshall R.; Johnson, Grant E.; Laskin, Julia

2017-01-01

Early stages of the reduction and nucleation of solution-phase gold clusters are largely unknown. This is due, in part, to the high reaction rates and the complexity of the cluster synthesis process. Through the addition of a diphosphine ligand, 1-4,Bis(diphenylphosphino)butane (L4) to the gold precursor, chloro(triphenylphosphine) gold(I) (Au(PPh3)Cl), in methanol organometallic complexes of the type, [Au(L4)x(L4O)y(PPh3)z]+, are formed. These complexes lower the rate of reduction so that the reaction can be directly monitored from 1 min to over an hour using on-line electrospray ionization mass spectrometry (ESI-MS). Our results indicate that the formation of Au8(L4)42+, Au9(L4)4H2+ and Au10(L4)52+ cationic clusters occurs through different reaction pathways that may be kinetically controlled either through the reducing agent concentration or the extent of oxidation of L4. Through comparison of selected ion chronograms our results indicate that Au2(L4)2H+ may be an intermediate in the formation of Au8(L4)42+and Au10(L4)52+ while a variety of chlorinated clusters are involved in the formation of Au9(L4)4H2+. Additionally, high-resolution mass spectrometry was employed to identify 53 gold containing species produced under highly oxidative conditions. New intermediate species are identified which help understand how different gold cluster nuclearities can be stabilized during the growth process.

Phosphate-mediated electrochemical adsorption of cisplatin on gold electrodes

International Nuclear Information System (INIS)

Kolodziej, Adam; Figueiredo, Marta C.; Koper, Marc T.M.; Fernandez-Trillo, Francisco; Rodriguez, Paramaconi

2017-01-01

Highlights: •The potential-dependent adsorption and deposition of cisplatin on polycrystalline gold electrode is mediated by the adsorption of phosphate anions on gold electrode. •Quantitative analysis suggests that the stoichiometry of the phosphate species and the cisplatin adsorbed was 1:1. •Upon reduction of the phosphate-mediated cisplatin adsorption, the platinum deposits are formed by 3D nanoclusters -- Abstract: This manuscript reports the potential-dependent adsorption and deposition of cisplatin on polycrystalline gold electrode. It was found that this process is mediated by the adsorption of phosphate anions on the gold electrode and that the maximum coverage of Pt adsorbed is given by the maximum coverage of phosphate adsorbed at a given potential. The interaction of cisplatin with the phosphate groups was confirmed by in situ FTIR spectroscopy under external reflexion configuration. Quantitative analysis suggests that the stoichiometry of the phosphate species and the cisplatin adsorbed was 1:1. Moreover, the relationship between the charge of the Pt deposited and the charge of the electrochemical surface area of the Pt deposited on the gold electrodes indicates that 3D nanoclusters of a few atoms of Pt were formed over the gold electrode upon the electrochemical reduction of the adsorbed cisplatin. The Pt nanoclusters formed under these conditions were later evaluated for the oxidation of a monolayer of carbon monoxide. The Pt nanoclusters showed a high overpotential for the oxidation of the carbon monoxide monolayer and the high oxidation overpotential was attributed to the absence of adsorption sites for OH species on the Pt clusters: only at potentials where the OH species are adsorbed at the edge between the Pt nanocluster and the gold support, the oxidation of the carbon monoxide on the Pt nanoparticles takes place.

Cyanide leaching of Au/CeO2: highly active gold clusters for 1,3-butadiene hydrogenation

NARCIS (Netherlands)

Guan, Y.; Hensen, E.J.M.

2009-01-01

Ceria-supported gold catalysts before and after leaching by NaCN were investigated by X-ray absorption spectroscopy at the Au LIII edge. After gold leaching, isolated gold cations remain in close interaction with the support. These ions form an ideal precursor to very small clusters of a few gold

Fluorescence Imaging Assisted Photodynamic Therapy Using Photosensitizer-Linked Gold Quantum Clusters.

Science.gov (United States)

Nair, Lakshmi V; Nazeer, Shaiju S; Jayasree, Ramapurath S; Ajayaghosh, Ayyappanpillai

2015-06-23

Fluorescence imaging assisted photodynamic therapy (PDT) is a viable two-in-one clinical tool for cancer treatment and follow-up. While the surface plasmon effect of gold nanorods and nanoparticles has been effective for cancer therapy, their emission properties when compared to gold nanoclusters are weak for fluorescence imaging guided PDT. In order to address the above issues, we have synthesized a near-infrared-emitting gold quantum cluster capped with lipoic acid (L-AuC with (Au)18(L)14) based nanoplatform with excellent tumor reduction property by incorporating a tumor-targeting agent (folic acid) and a photosensitizer (protoporphyrin IX), for selective PDT. The synthesized quantum cluster based photosensitizer PFL-AuC showed 80% triplet quantum yield when compared to that of the photosensitizer alone (63%). PFL-AuC having 60 μg (0.136 mM) of protoporphyrin IX was sufficient to kill 50% of the tumor cell population. Effective destruction of tumor cells was evident from the histopathology and fluorescence imaging, which confirm the in vivo PDT efficacy of PFL-AuC.

Combined atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and quartz crystal microbalance (QCM) studies of glucose oxidase (GOx) immobilised onto self-assembled monolayer on the gold film

International Nuclear Information System (INIS)

Losic, D.; Shapter, J.; Gooding, J.; Erokin, P.; Short, K.

1999-01-01

In fabrication of biosensors, self-assembled monolayers (SAM) are an attractive method of immobilising enzymes at electrode surface since it allows precise control over the amount and spatial distribution of the immobilized enzyme. The covalent attachment of glucose oxidase (GOx) to a carboxylic terminated SAM chemisorbed onto gold films was achieved via carbodiimide activation of the carboxylic acids to a reactive intermediate susceptible to nucleophilic attack by amines on free lysine chains of the enzyme. Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and quartz crystal microbalance (QCM) measurements were used for characterisation of GOx modified gold surfaces. Tapping mode AFM studies have revealed that GOx molecules form slightly disordered arrays of pentagonal or hexagonal clusters. Observed features of immobilised GOx are distributed as a submonolayer on the SAM surface which has allowed visualisation of native and unfolded enzyme structure. The presence of the SAM and enzyme on the gold surface was detected by XPS spectroscopy. Spectra show typical peaks for the C 1s, O 1s and N 1s regions. A kinetic study of the adsorption of GOx onto activated SAM using in-situ QCM allowed determination the amount of immobilised GOx on the layer and consequently the optimal immobilisation conditions. Performance parameters of the biosensor such as sensitivity to glucose concentration as a function of enzyme loading were evaluated amperometrically using the redox mediator p-benzoquinone

Complexes of DNA bases and Watson-Crick base pairs with small neutral gold clusters.

Science.gov (United States)

Kryachko, E S; Remacle, F

2005-12-08

The nature of the DNA-gold interaction determines and differentiates the affinity of the nucleobases (adenine, thymine, guanine, and cytosine) to gold. Our preliminary computational study [Kryachko, E. S.; Remacle, F. Nano Lett. 2005, 5, 735] demonstrates that two major bonding factors govern this interaction: the anchoring, either of the Au-N or Au-O type, and the nonconventional N-H...Au hydrogen bonding. In this paper, we offer insight into the nature of nucleobase-gold interactions and provide a detailed characterization of their different facets, i.e., geometrical, energetic, and spectroscopic aspects; the gold cluster size and gold coordination effects; proton affinity; and deprotonation energy. We then investigate how the Watson-Crick DNA pairing patterns are modulated by the nucleobase-gold interaction. We do so in terms of the proton affinities and deprotonation energies of those proton acceptors and proton donors which are involved in the interbase hydrogen bondings. A variety of properties of the most stable Watson-Crick [A x T]-Au3 and [G x C]-Au3 hybridized complexes are described and compared with the isolated Watson-Crick A x T and G x C ones. It is shown that enlarging the gold cluster size to Au6 results in a rather short gold-gold bond in the Watson-Crick interbase region of the [G x C]-Au6 complex that bridges the G x C pair and thus leads to a significant strengthening of G x C pairing.

Gold Cluster Diffusion Kinetics on Stoichiometric and Reduced Surfaces of Rutile TiO ₂ (110)

Energy Technology Data Exchange (ETDEWEB)

Goldman, Nir; Browning, Nigel D.

2011-06-16

Gold clusters on rutile TiO₂ are known to serve as efficient oxidation catalysts for pollutants and environmental contaminants. However, the mechanism by which highly mobile small clusters migrate and aggregate into larger species relevant to gold’s catalytic activity remains unresolved. We report herein on ab initio simulations of the diffusion of atomic gold clusters up to the trimer on rutile TiO₂(110) surfaces. We show that, on the stoichiometric surface, both the dimer and the trimer can exhibit relatively low surface mobility due to high energetic barriers for diffusion out of their energetic minima coupled with low barriers for the reverse motion. On the reduced surface, these clusters can diffuse relatively quickly between energetic minima within the oxygen vacancy site due to the large degree of vibrational entropy in their transition states. Our computed diffusion times provide a point of comparison for future experiments and will aid in development of models of gold cluster island sintering.

Far-infrared spectra of yttrium-doped gold clusters Au(n)Y (n=1-9).

Science.gov (United States)

Lin, Ling; Claes, Pieterjan; Gruene, Philipp; Meijer, Gerard; Fielicke, André; Nguyen, Minh Tho; Lievens, Peter

2010-06-21

The geometric, spectroscopic, and electronic properties of neutral yttrium-doped gold clusters Au(n)Y (n=1-9) are studied by far-infrared multiple photon dissociation (FIR-MPD) spectroscopy and quantum chemical calculations. Comparison of the observed and calculated vibrational spectra allows the structures of the isomers present in the molecular beam to be determined. Most of the isomers for which the IR spectra agree best with experiment are calculated to be the energetically most stable ones. Attachment of xenon to the Au(n)Y cluster can cause changes in the IR spectra, which involve band shifts and band splittings. In some cases symmetry changes, as a result of the attachment of xenon atoms, were also observed. All the Au(n)Y clusters considered prefer a low spin state. In contrast to pure gold clusters, which exhibit exclusively planar lowest-energy structures for small sizes, several of the studied species are three-dimensional. This is particularly the case for Au(4)Y and Au(9)Y, while for some other sizes (n=5, 8) the 3D structures have an energy similar to that of their 2D counterparts. Several of the lowest-energy structures are quasi-2D, that is, slightly distorted from planar shapes. For all the studied species the Y atom prefers high coordination, which is different from other metal dopants in gold clusters.

Moessbauer studies of non-linear excitations and gold cluster compounds

International Nuclear Information System (INIS)

Smit, H.H.A.

1988-01-01

Moessbauer effect spectroscopy has been applied to the study of three polynuclear gold cluster compounds. The resulting information on the local vibrational density of states has been compared to several models which take the finite size of the particles into consideration. 188 refs.; 34 figs.; 103 schemes; 8 tabs

Binding energy and preferred adsorption sites of CO on gold and silver-gold cluster cations: adsorption kinetics and quantum chemical calculations.

Science.gov (United States)

Neumaier, Marco; Weigend, Florian; Hampe, Oliver; Kappes, Manfred M

2008-01-01

We revisit the reactivity of trapped pure gold (Au(n)+, n cations (Ag(m)Au(n)+, m + n carbon monoxide as studied in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. The experimental results are discussed in terms of ab initio computations which provide a comprehensive picture of the chemical binding behaviour (like binding energy, adsorption sites, associated vibrational frequencies) of CO to the noble metal as a function of cluster size and composition. Starting from results for pure gold cluster cations for which an overall decrease of CO binding energy with increasing cluster size was experimentally observed--from about 1.09 +/- 0.1 eV (for n = 6) to below 0.65 +/- 0.1 eV (for n > 26) we demonstrate that metal--CO bond energies correlate with the total electron density and with the energy of the lowest unoccupied molecular orbital (LUMO) on the bare metal cluster cation as obtained by density functional theory (DFT) computations. This is a consequence of the predominantly sigma-donating character of the CO-M bond. Further support for this concept is found by contrasting the predictions of binding energies to the experimental results for small alloy cluster cations (Ag(m)Au(n)+, 4 < m + n < 7) as a function of composition. Here, binding energy drops with increasing silver content, while CO still binds always in a head-on fashion to a gold atom. Finally we show how the CO stretch frequency of Ag(m)Au(n)CO+ may be used to identify possible adsorption sites and pre-screen favorable isomers.

Controlled Clustering of Gold Nanoparticles using Solid-support for Surface-enhanced Raman Spectroscopic Probes

International Nuclear Information System (INIS)

Chang, Hyejin; Chae, Jinjoo; Jeong, Hong; Kang, Homan; Lee, Yoonsik

2014-01-01

We fabricated small clusters of gold nanoparticles by using solid-supported aggregation of gold nanoparticles. The fabricated Au nanoclusters consisting mainly of dimers showed homogeneous characteristics in cluster size and SERS intensity. The SERS enhancement of 4-ABT molecules in an effective area within 2-nm gap appeared to be approximately 10. Detachment process by ultrasonication was successively carried out in order to use the nanoclusters as SERS probes. The possibility of these clusters as SERS probe was proved in terms of signal and cluster size. Single molecule-level sensitivity of surface-enhanced Raman scattering (SERS) was known approximately fifteen years ago. Ever since there have been many different applications benefiting from the ultra-high sensitivity such as single molecule detection, chemical sensing and bio-molecular probes. Especially, SERS has drawn much attention in bio-multiplexing probes owing to its unique optical characteristics claiming extremely narrow bandwidth, high sensitivity of light signals, and non-bleaching feature

Controlled Clustering of Gold Nanoparticles using Solid-support for Surface-enhanced Raman Spectroscopic Probes

Energy Technology Data Exchange (ETDEWEB)

Chang, Hyejin; Chae, Jinjoo; Jeong, Hong [Department of Chemistry Education, Seoul (Korea, Republic of); Kang, Homan; Lee, Yoonsik [Interdisciplinary Program in Nano-Science and Technology, Pohang (Korea, Republic of)

2014-03-15

We fabricated small clusters of gold nanoparticles by using solid-supported aggregation of gold nanoparticles. The fabricated Au nanoclusters consisting mainly of dimers showed homogeneous characteristics in cluster size and SERS intensity. The SERS enhancement of 4-ABT molecules in an effective area within 2-nm gap appeared to be approximately 10. Detachment process by ultrasonication was successively carried out in order to use the nanoclusters as SERS probes. The possibility of these clusters as SERS probe was proved in terms of signal and cluster size. Single molecule-level sensitivity of surface-enhanced Raman scattering (SERS) was known approximately fifteen years ago. Ever since there have been many different applications benefiting from the ultra-high sensitivity such as single molecule detection, chemical sensing and bio-molecular probes. Especially, SERS has drawn much attention in bio-multiplexing probes owing to its unique optical characteristics claiming extremely narrow bandwidth, high sensitivity of light signals, and non-bleaching feature.

Non-linear sputtering effects induced by MeV energy gold clusters

International Nuclear Information System (INIS)

Boussofiane-Baudin, K.; Brunelle, A.; Chaurand, P.; Della-Negra, S.; Depauw, J.; Le Beyec, Y.; Hakansson, P.

1993-09-01

Gold clusters Au n + with 1 < n ≤ 4, accelerated to MeV energies at the Orsay tandem accelerator, have been used to induce secondary ion emission from the surface of thin organic and inorganic films. A non-linear enhancement of the secondary ion yields is observed when cluster impacts are compared to single atom impacts at the same velocity. It has been shown that the collective effects propagate in the solid over a depth larger than 2000 A. The equilibrium charge state of cluster constituents after their passage through a thin carbon foil (1000 A) has been measured. The mean value for the cluster constituents is the same as for single atoms at the same velocity. (authors). 41 refs., 8 figs., 1 tab

Optical Properties of Linoleic Acid Protected Gold Nanoparticles

Directory of Open Access Journals (Sweden)

Ratan Das

2011-01-01

Full Text Available Linoleic acid-protected gold nanoparticles have been synthesized through the chemical reduction of tetrachloroaurate ions by ethanol in presence of sodium linoleate. The structure of these nanoparticles is investigated using transmission electron microscopy, which shows that the Au nanoparticles are spherical in shape with a narrow size distribution which ranges from 8 to 15 nm. Colloidal dispersion of gold nanoparticles in cyclohexane exhibits absorption bands in the ultraviolet-visible range due to surface plasmon resonance, with absorption maximum at 530 nm. Fluorescence spectra of gold nanoparticles also show an emission peak at 610 nm when illuminated at 450 nm. UV-Vis spectroscopy reveals that these nanoparticles remain stable for 10 days.

Influence of the photothermal effect of a gold nanorod cluster on biofilm disinfection

International Nuclear Information System (INIS)

Jo, Wonjin; Kim, Min Jun

2013-01-01

We evaluate a method for biofilm disinfection by raising biofilm temperature using the photothermal effect of a gold nanorod cluster. Gold nanorods (GNRs) are capable of generating enough heat to lyse bacteria by heating biofilm via laser irradiation. To test this, GNRs are synthesized using wet chemistry and a single GNR cluster is fabricated using photo-lithography technique. The GNR cluster is directly applied to the biofilm and its effects on bacteria are measured before and after laser irradiation. The photothermal effect of GNRs on the biofilm structure results in a considerable reduction of cell viability and biofilm thickness. Several quantitative measurements of bacterial mortality and biofilm destruction show an increase in efficacy with increasing durations of laser irradiation. Scanning electron microscopy images of the irradiated bacteria show obvious morphological damage such as rupture or collapse of the bacterial cell membrane in the biofilm. These results indicate that GNRs are useful and a potential material for use in photothermal treatments, particularly biofilm disinfection. (paper)

Ligand induced structural isomerism in phosphine coordinated gold clusters revealed by ion mobility mass spectrometry

Energy Technology Data Exchange (ETDEWEB)

Ligare, Marshall R.; Baker, Erin M.; Laskin, Julia; Johnson, Grant E.

2017-01-01

Structural isomerism in ligated gold clusters is revealed using electrospray ionization ion mobility spectrometry mass spectrometry. Phosphine ligated Au8 clusters are shown to adopt more “extended” type structures with increasing exchange of methyldiphenylphosphine (MePPh2) for triphenylphosphine (PPh3). These ligand-dependant structure-property relationships are critical to applications of clusters in catalysis.

Macrocluster desorption effect caused by single MCI: charges of gold clusters (2-20 nm) desorbed due to electronic processes induced by fission fragment bombardment in nanodispersed gold targets

International Nuclear Information System (INIS)

Baranov, I.; Jarmiychuk, S.; Kirillov, S.; Novikov, A.; Obnorskii, V.; Pchelintsev, A.; Wien, K.; Reimann, C.

1999-01-01

In this work the charge state of the negatively charged gold nanocluster ions (2-20 nm) that were desorbed from nanodispersed gold islet targets by 252 Cf fission fragments via electronic processes is studied. Mean cluster charge was calculated as a ratio of mean cluster mass to mean mass-to-charge ratio . Cluster masses were measured by means of a collector technique employing transmission electron microscopy and scanning force microscopy, while m/q was measured by means of a tandem TOF-spectrometer. It is shown that the nanocluster ions are mostly multiply charged (2-16e) and the charge increases non-linearly with the cluster size. The results are discussed

Supramolecular domains in mixed peptide self-assembled monolayers on gold nanoparticles.

Science.gov (United States)

Duchesne, Laurence; Wells, Geoff; Fernig, David G; Harris, Sarah A; Lévy, Raphaël

2008-09-01

Self-organization in mixed self-assembled monolayers of small molecules provides a route towards nanoparticles with complex molecular structures. Inspired by structural biology, a strategy based on chemical cross-linking is introduced to probe proximity between functional peptides embedded in a mixed self-assembled monolayer at the surface of a nanoparticle. The physical basis of the proximity measurement is a transition from intramolecular to intermolecular cross-linking as the functional peptides get closer. Experimental investigations of a binary peptide self-assembled monolayer show that this transition happens at an extremely low molar ratio of the functional versus matrix peptide. Molecular dynamics simulations of the peptide self-assembled monolayer are used to calculate the volume explored by the reactive groups. Comparison of the experimental results with a probabilistic model demonstrates that the peptides are not randomly distributed at the surface of the nanoparticle, but rather self-organize into supramolecular domains.

Direct patterning of negative nanostructures on self-assembled monolayers of 16-mercaptohexadecanoic acid on Au(111) substrate via dip-pen nanolithography

International Nuclear Information System (INIS)

Zheng Zhikun; Yang Menglong; Liu Yaqing; Zhang Bailin

2006-01-01

Both bare and self-assembled monolayer (SAM) protected gold substrate could be etched by allyl bromide according to atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometric (ICPMS) analysis results. With this allyl bromide ink material, negative nanopatterns could be fabricated directly by dip-pen nanolithography (DPN) on SAMs of 16-mercaptohexadecanoic acid (MHA) on Au(111) substrate. A tip-promoted etching mechanism was proposed where the gold-reactive ink could penetrate the MHA resist film through tip-induced defects resulting in local corrosive removal of the gold substrate. The fabrication mechanism was also confirmed by electrochemical characterization, energy dispersive spectroscopy (EDS) analysis and fabrication of positive nanopatterns via a used DPN tip

Direct patterning of negative nanostructures on self-assembled monolayers of 16-mercaptohexadecanoic acid on Au(111) substrate via dip-pen nanolithography

Science.gov (United States)

Zheng, Zhikun; Yang, Menglong; Liu, Yaqing; Zhang, Bailin

2006-11-01

Both bare and self-assembled monolayer (SAM) protected gold substrate could be etched by allyl bromide according to atomic force microscopy (AFM), x-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometric (ICPMS) analysis results. With this allyl bromide ink material, negative nanopatterns could be fabricated directly by dip-pen nanolithography (DPN) on SAMs of 16-mercaptohexadecanoic acid (MHA) on Au(111) substrate. A tip-promoted etching mechanism was proposed where the gold-reactive ink could penetrate the MHA resist film through tip-induced defects resulting in local corrosive removal of the gold substrate. The fabrication mechanism was also confirmed by electrochemical characterization, energy dispersive spectroscopy (EDS) analysis and fabrication of positive nanopatterns via a used DPN tip.

Comparing the performances of electrochemical sensors using p-aminophenol redox cycling by different reductants on gold electrodes modified with self-assembled monolayers

International Nuclear Information System (INIS)

Xia, Ning; Ma, Fengji; Zhao, Feng; He, Qige; Du, Jimin; Li, Sujuan; Chen, Jing; Liu, Lin

2013-01-01

Highlights: • Performances of p-AP redox cycling using different reductants on gold surface are compared. • Background current decreases in order of hydrazine, Na 2 SO 3 , NaBH 4 , NADH, cysteamine, and TCEP. • Chemical reaction rate with QI increases in order of NADH, TCEP, and cysteamine. • NADH, TCEP and cysteamine are suitable for p-AP redox cycling on gold electrode. -- Abstract: p-Aminophenol (p-AP) redox cycling using chemical reductants is one strategy for developing sensitive electrochemical sensors. However, most of the reported reductants are only used on indium-tin oxide (ITO) electrodes but not gold electrodes due to the high background current caused by the oxidation reaction of the reductants on the highly electrocatalytic gold electrodes. Therefore, new strategies and/or reductants are in demand for expanding the application of p-AP redox cycling on gold electrodes. In this work, we compared the performances of several reductants in p-AP redox cycling on self-assembled monolayers (SAMs)-modified gold electrodes. Among the tested reagents, nicotinamide adenine dinucleotide (NADH), tris(2-carboxyethyl)phosphine (TCEP) and cysteamine were demonstrated to be suitable for p-AP redox cycling on the alkanethiol-modified gold electrodes because of their low background current. The rate of chemical reaction between reductants and p-quinone imine (QI, the electrochemically oxidized product of p-AP) increases in the order of NADH −1 was achieved. We believe that our work will be valuable for the development of electrochemical sensors using p-AP redox cycling on gold electrodes

Influence of dielectric protective layer on laser damage resistance of gold coated gratings

Science.gov (United States)

Wu, Kepeng; Ma, Ping; Pu, Yunti; Xia, Zhilin

2016-03-01

Aiming at the problem that the damage threshold of gold coated grating is relatively low, a dielectric film is considered on the gold coated gratings as a protective layer. The thickness range of the protective layer is determined under the prerequisite that the diffraction efficiency of the gold coated grating is reduced to an acceptable degree. In this paper, the electromagnetic field, the temperature field and the stress field distribution in the grating are calculated when the silica and hafnium oxide are used as protective layers, under the preconditions of the electromagnetic field distribution of the gratings known. The results show that the addition of the protective layer changes the distribution of the electromagnetic field, temperature field and stress field in the grating, and the protective layer with an appropriate thickness can improve the laser damage resistance of the grating.

Fullerene monolayer formation by spray coating

Czech Academy of Sciences Publication Activity Database

Červenka, Jiří; Flipse, C.F.J.

2010-01-01

Roč. 21, č. 6 (2010), 065302/1-065302/7 ISSN 0957-4484 Institutional research plan: CEZ:AV0Z10100521 Keywords : monolayer * spray coating * fullerene * atomic force microscopy * scanning tunnelling microscopy * electronic structure * graphite * gold Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.644, year: 2010

Composition dependent selectivity in the coadsorption of H2O and CO on pure and binary silver-gold clusters

Science.gov (United States)

Fleischer, Irene; Popolan, Denisia M.; Krstić, Marjan; Bonačić-Koutecký, Vlasta; Bernhardt, Thorsten M.

2013-04-01

Small cationic gold clusters exhibit a strong affinity toward carbon monoxide. This prevents the coadsorption of water which would be the first step of a catalytic water gas shift chemistry on these clusters. In a gas phase ion trap experiment with mass selected AgnAum+ it was however possible to demonstrate that the replacement of gold by silver atoms in triatomic cluster ions liberates sites for H2O adsorption. The resulting observed coadsorption effect occurs at a cross-over in the molecular binding energies of carbon monoxide and water to these clusters determined by reaction kinetics measurements and first principles calculations.

Gold atomic cluster mediated electrochemical aptasensor for the detection of lipopolysaccharide.

Science.gov (United States)

Posha, Biyas; Nambiar, Sindhu R; Sandhyarani, N

2018-03-15

We have constructed an aptamer immobilized gold atomic cluster mediated, ultrasensitive electrochemical biosensor (Apt/AuAC/Au) for LPS detection without any additional signal amplification strategy. The aptamer self-assemble onto the gold atomic clusters makes Apt/AuAC/Au an excellent platform for the LPS detection. Differential pulse voltammetry and EIS were used for the quantitative LPS detection. The Apt/AuAC/Au sensor offers an ultrasensitive and selective detection of LPS down to 7.94 × 10 -21 M level with a wide dynamic range from 0.01 attomolar to 1pM. The sensor exhibited excellent selectivity and stability. The real sample analysis was performed by spiking the diluted insulin sample with various concentration of LPS and obtained recovery within 2% error value. The sensor is found to be more sensitive than most of the literature reports. The simple and easy way of construction of this sensor provides an efficient and promising detection of an even trace amount of LPS. Copyright © 2017 Elsevier B.V. All rights reserved.

Highly Sensitive Aluminium(III) Ion Sensor Based on a Self-assembled Monolayer on a Gold Nanoparticles Modified Screen-printed Carbon Electrode.

Science.gov (United States)

See, Wong Pooi; Heng, Lee Yook; Nathan, Sheila

2015-01-01

A new approach for the development of a highly sensitive aluminium(III) ion sensor via the preconcentration of aluminium(III) ion with a self-assembled monolayer on a gold nanoparticles modified screen-printed carbon electrode and current mediation by potassium ferricyanide redox behavior during aluminium(III) ion binding has been attempted. A monolayer of mercaptosuccinic acid served as an effective complexation ligand for the preconcentration of trace aluminium; this led to an enhancement of aluminium(III) ion capture and thus improved the sensitivity of the sensor with a detection limit of down to the ppb level. Under the optimum experimental conditions, the sensor exhibited a wide linear dynamic range from 0.041 to 12.4 μM. The lower detection limit of the developed sensor was 0.037 μM (8.90 ppb) using a 10 min preconcentration time. The sensor showed excellent selectivity towards aluminium(III) ion over other interference ions.

Shadow mask evaporation through monolayer modified nanostencils

NARCIS (Netherlands)

Kolbel, M.; Tjerkstra, R.W.; Brugger, J.P.; van Rijn, C.J.M.; Nijdam, W.; Huskens, Jurriaan; Reinhoudt, David

2002-01-01

Gradual clogging of the apertures of nanostencils used as miniature shadow masks in metal evaporations can be reduced by coating the stencil with self-assembled monolayers (SAM). This is quantified by the dimensions (height and volume) of gold features obtained by nanostencil evaporation as measured

Controlled electrodeposition of Au monolayer film on ionic liquid

Energy Technology Data Exchange (ETDEWEB)

Ma, Qiang; Pang, Liuqing; Li, Man; Zhang, Yunxia; Ren, Xianpei [Key Laboratory of Applied Surface and Colloid Chemistry, National Ministry of Education, Shaanxi Engineering Lab for Advanced Energy Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710062 (China); Liu, Shengzhong Frank, E-mail: szliu@dicp.ac.cn [Key Laboratory of Applied Surface and Colloid Chemistry, National Ministry of Education, Shaanxi Engineering Lab for Advanced Energy Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710062 (China); Dalian Institute of Chemical Physics, Dalian National Laboratory for Clean Energy, Chinese Academy of Sciences, Dalian 116023 (China)

2016-05-15

Highlights: • We fabricate Au monolayer film on Ionic liquid substrate using an electrochemical deposition technique. • Au monolayer film was deposited on a “soft substrate” for the first time. • Au monolayer film can contribute extra Raman enhancement. - Abstract: Gold (Au) nanoparticles have been attractive for centuries for their vibrant appearance enhanced by their interaction with sunlight. Nowadays, there have been tremendous research efforts to develop them for high-tech applications including therapeutic agents, sensors, organic photovoltaics, medical applications, electronics and catalysis. However, there remains to be a challenge to fabricate a monolayer Au coating with complete coverage in controlled fashion. Here we present a facile method to deposit a uniform Au monolayer (ML) film on the [BMIM][PF{sub 6}] ionic liquid substrate using an electrochemical deposition process. It demonstrates that it is feasible to prepare a solid phase coating on the liquid-based substrate. Moreover, the thickness of the monolayer coating can be controlled to a layer-by-layer accuracy.

Self-assembling monolayers of helical oligopeptides with applications in molecular electronics

International Nuclear Information System (INIS)

Strong, A.E.

1997-01-01

The aim of this project was to develop a generic method of preparing a 'molecular architecture' containing functional groups on a surface at predetermined relative positions several nm apart. This would be of great utility in molecular electronics, chemical sensors and other fields. It was proposed that such an architecture could be prepared on gold using linked, helical oligopeptides that contained the components of interest and sulphur functions able to form monolayers on gold by the self-assembly technique. Towards this ultimate aim Self-Assembled Monolayers (SAMs) of monomeric oligopeptides (13-17 residues) were prepared and characterised. Peptides containing three Met residues spaced in the sequence so that their side-chains lay on the same side of the helix were shown by circular dichroism (CD) to be strongly helical in organic solvents. Their self-assembled films on gold were characterised by Reflection-Absorption Infrared Spectroscopy (RAIRS) which showed the peptides adsorbed with the helix axes parallel to the surface, the orientation expected for self-assembly. However the surface coverage measured by cyclic voltammetry (CV) of the peptides' ferrocenyl derivatives on gold electrodes were less than expected for monolayers. Comparison of the films of ferrocenyl derivatives of Met and Cys showed that the thiolate bound more strongly than the thioether. Accordingly an oligopeptide containing two Cys residues at i, i+3, designed to be 3 10 -helical, was prepared. Transformation of the two (Trt)Cys residues of the resin-bound peptide to the intramolecular disulphide by iodine was achieved in acetonitrile but not in DMF. CD suggested that the conformation of this peptide was a mixture of helix and random coil. Films of the peptide-disulphide and the peptide-dithiol adsorbed from protic solvents were characterised as multilayers by ellipsometry. However CV and ellipsometry showed that a monolayer was successfully prepared from acetonitrile. Future targets for

Alpha-Melanocyte Stimulating Hormone Protects against Cytokine-Induced Barrier Damage in Caco-2 Intestinal Epithelial Monolayers.

Directory of Open Access Journals (Sweden)

Judit Váradi

Full Text Available Alpha-melanocyte-stimulating hormone (α-MSH is a potent anti-inflammatory peptide with cytoprotective effect in various tissues. The present investigation demonstrates the ability of α-MSH to interact with intestinal epithelial cell monolayers and mitigate inflammatory processes of the epithelial barrier. The protective effect of α-MSH was studied on Caco-2 human intestinal epithelial monolayers, which were disrupted by exposure to tumor necrosis factor-α and interleukin-1β. The barrier integrity was assessed by measuring transepithelial electric resistance (TEER and permeability for marker molecules. Caco-2 monolayers were evaluated by immunohistochemistry for expression of melanocortin-1 receptor and tight junction proteins ZO-1 and claudin-4. The activation of nuclear factor kappa beta (NF-κB was detected by fluorescence microscopy and inflammatory cytokine expression was assessed by flow cytometric bead array cytokine assay. Exposure of Caco-2 monolayers to proinflammatory cytokines lowered TEER and increased permeability for fluorescein and albumin, which was accompanied by changes in ZO-1 and claudin-4 immunostaining. α-MSH was able to prevent inflammation-associated decrease of TEER in a dose-dependent manner and reduce the increased permeability for paracellular marker fluorescein. Further immunohistochemistry analysis revealed proinflammatory cytokine induced translocation of the NF-κB p65 subunit into Caco-2 cell nuclei, which was inhibited by α-MSH. As a result the IL-6 and IL-8 production of Caco-2 monolayers were also decreased with different patterns by the addition of α-MSH to the culture medium. In conclusion, Caco-2 cells showed a positive immunostaining for melanocortin-1 receptor and α-MSH protected Caco-2 cells against inflammatory barrier dysfunction and inflammatory activation induced by tumor necrosis factor-α and interleukin-1β cytokines.

Boosting the performance of Pt electro-catalysts toward formic acid electro-oxidation by depositing sub-monolayer Au clusters

International Nuclear Information System (INIS)

Bi Xuanxuan; Wang Rongyue; Ding Yi

2011-01-01

Highlights: → Au decoration on Pt nanoparticles simultaneously increases the activity and stability. → Sub-monolayer Au decoration changes the reaction path and results in the activity improvement. → Increasing the Au coverage will increase the specific activity. → Proper Au coverage results in a maximum mass specific activity. - Abstract: CO poisoning is the main obstacle to the application of Pt nanoparticles as anode catalysts in direct formic acid fuel cells (DFAFCs). Significant types of Pt alloys have been investigated, which often demonstrate evidently improved catalytic performance governed by difference mechanisms. By using a well-known electrochemical technique of under potential deposition and in situ redox replacement, sub-monolayer Au clusters are deposited onto Pt nanoparticle surfaces in a highly controlled manner, generating a unique surface alloy structure. Under optimum conditions, the modified Pt nanoparticles can exhibit greatly enhanced specific activity (up to 23-fold increase) at potential of -0.2 V vs. MSE toward formic acid electro-oxidation (FAEO). Interestingly, the mass specific activity can also be improved by a factor of 2.3 at potential of -0.35 V vs. MSE although significant amount of surface Pt atoms are covered by the overlayer Au clusters. The much enhanced catalytic activity can be ascribed to a Pt surface ensemble effect, which induces change of the reaction path. Moreover, the sub-monolayer Au coating on the surface also contributes to the enhanced catalyst durability by inhibiting the Pt oxidation. These results show great potential to rationally design more active and stable nanocatalysts by modifying the Pt surface with otherwise inactive materials.

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

Energy Technology Data Exchange (ETDEWEB)

Raigoza, Annette F.; Fies, Whitney; Lim, Amber; Onyirioha, Kristeen; Webb, Lauren J., E-mail: lwebb@cm.utexas.edu

2017-02-01

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

IR visible sum-frequency vibrational spectroscopy of Biphenyl-3 methylene thiol monolayer on gold and silver: effect of the visible wavelength on the SFG spectrum

Science.gov (United States)

Humbert, C.; Dreesen, L.; Mani, A. A.; Caudano, Y.; Lemaire, J.-J.; Thiry, P. A.; Peremans, A.

2002-04-01

We measured IR-visible sum-frequency generation spectra of CH 3-(C 6H 4) 2-(CH 2) 3-S-H (Biphenyl-3) self-assembled monolayers on a silver and a gold substrate. For the latter substrate, we observed different interference patterns between the resonant signal of the CH vibration and the non-resonant contribution of the substrate as a function of the visible beam wavelength. The non-linear response of the gold substrate is enhanced around 480 nm corresponding to the s-d interband transition. Such effect is not observed for the silver substrate the interband transition of which is located out of the investigated visible spectral range of 450-700 nm.

Photoinduced electron transfer through peptide-based self-assembled monolayers chemisorbed on gold electrodes: directing the flow-in and flow-out of electrons through peptide helices.

Science.gov (United States)

Venanzi, Mariano; Gatto, Emanuela; Caruso, Mario; Porchetta, Alessandro; Formaggio, Fernando; Toniolo, Claudio

2014-08-21

Photoinduced electron transfer (PET) experiments have been carried out on peptide self-assembled monolayers (SAM) chemisorbed on a gold substrate. The oligopeptide building block was exclusively formed by C(α)-tetrasubstituted α-aminoisobutyric residues to attain a helical conformation despite the shortness of the peptide chain. Furthermore, it was functionalized at the C-terminus by a pyrene choromophore to enhance the UV photon capture cross-section of the compound and by a lipoic group at the N-terminus for linking to gold substrates. Electron transfer across the peptide SAM has been studied by photocurrent generation experiments in an electrochemical cell employing a gold substrate modified by chemisorption of a peptide SAM as a working electrode and by steady-state and time-resolved fluorescence experiments in solution and on a gold-coated glass. The results show that the electronic flow through the peptide bridge is strongly asymmetric; i.e., PET from the C-terminus to gold is highly favored with respect to PET in the opposite direction. This effect arises from the polarity of the Au-S linkage (Au(δ+)-S(δ-), junction effect) and from the electrostatic field generated by the peptide helix.

FET immunosensor for hemoglobin A1c using a gold nanofilm grown by a seed-mediated technique and covered with mixed self-assembled monolayers

International Nuclear Information System (INIS)

Xue, Q.; Bian, C.; Tong, J.; Sun, J.; Zhang, H.; Xia, S.

2012-01-01

A micro FET-based immunosensor was developed for the determination of hemoglobin-A1c (HbA1c). The HbA1c/hemoglobin ratio is an important index in diabetes control. The sensor was fabricated by Complementary Metal-Oxide-Semiconductor Transistor (CMOS) and Micro Electronic Mechanical System (MEMS) techniques. The antibodies were immobilized via mixed self-assembled monolayers (SAMs) on a gold nanofilm. The nanofilm was deposited on a gold electrode by seed-mediated growth and gave a uniform and well distributed coverage. Nonspecific sites and interferences by noise were eliminated by covering the AuNPs with mixed SAMs. Compared to the immunosensor fabricated via the mixed SAMs method without gold nanofilm, the immunosensor displays a more than 2-fold sensitivity. The immunosensor is capable of detecting HbA1c and hemoglobin in hemolyzed and diluted whole blood, and results showed good agreement with the established clinical method. (author)

Gold chloride clusters with Au(III) and Au(I) probed by FT-ICR mass spectrometry and MP2 theory.

Science.gov (United States)

Lemke, Kono H

2014-05-07

Microsolvated clusters of gold chloride are probed by electrospray ionization mass spectrometry (ESI-MS) and scalar relativistic electronic structure calculations. Electrospray ionization of aqueous AuCl3 leads to mononuclear clusters of types [AuCl2](+)(H2O)n (n = 0-4), [AuOHCl](+)(H2O)n (n = 0-1) and [AuCl2](+)(HCl)2(H2O)n (n = 0-4). In addition, strong ion signals due to dinuclear [Au2Cl5-xOHx](+)(H2O)n (x = 0-1) are present in ESI mass spectra of aqueous AuCl3, with the abundance of individual dinuclear species controlled by the concentration-dependent variation of the precursor complexes [AuCl2-xOHx](+)(H2O)n and AuCl3. Equilibrium structures, energies and thermodynamic properties of mono- and dinuclear gold clusters have been predicted using MP2 and CCSD(T) theory, and these data have been applied to examine the influence of microsolvation on cluster stability. Specifically, results from CCSD(T) calculations indicate that non-covalently bound ion-neutral complexes Au(+)(Cl2)(H2O)n, with formal Au(I), are the dominant forms of mononuclear gold with n = 0-2, while higher hydrates (n > 2) are covalently bound [AuCl2](+)(H2O)n complexes in which gold exists as Au(III). MP2 calculations show that the lowest energy structure of dinuclear gold is an ion-molecule cluster [Au2Cl(Cl2)2](+) consisting of a single-bridged digold-chloronium ion bound end-on to two dichlorine ligands, with two higher energy isomers, single-bridged [Au2Cl3(Cl2)](+) and double-bridged [Au2Cl5](+) clusters. Finally, AuAu interactions in the singly-bridged clusters [Au2Cl(Cl2)2](+)(H2O)n and [Au2Cl3(Cl2)](+)(H2O)n are examined employing a wide range of computational tools, including natural bond order (NBO) analysis and localized orbital locator (LOL) profiles.

Metal-molecular interface of sulfur-containing amino acid and thiophene on gold surface

International Nuclear Information System (INIS)

Honda, M; Baba, Y; Hirao, N; Sekiguchi, T

2008-01-01

Chemical-bonding states of metal-molecular interface have been investigated for L-cysteine and thiophene on gold by x-ray photoelectron spectroscopy (XPS) and near edge x-ray adsorption fine structure (NEXAFS). A remarkable difference in Au-S bonding states was found between L-cysteine and thiophene. For mono-layered L-cysteine on gold, the binding energy of S 1s in XPS and the resonance energy at the S K-edge in NEXAFS are higher by 8-9 eV than those for multi-layered film (molecular L-cysteine). In contrast, the S K-edge resonance energy for mono-layered thiophene on gold was 2475.0 eV, which is the same as that for molecular L-cysteine. In S 1s XPS for mono-layered thiophene, two peaks were observed. The higher binging-energy and more intense peak at 2473.4 eV are identified as gold sulfide. The binding energy of smaller peak, whose intensity is less than 1/3 of the higher binding energy peak, is 2472.2 eV, which is the same as that for molecular thiophene. These observations indicate that Au-S interface behavior shows characteristic chemical bond only for the Au-S interface of L-cysteine monolayer on gold substrate

A new technique to detect antibody-antigen reaction (biological interactions) on a localized surface plasmon resonance (LSPR) based nano ripple gold chip

Energy Technology Data Exchange (ETDEWEB)

Saleem, Iram, E-mail: iiram.qau@gmail.com [Department of Physics and Texas Center for Superconductivity, University of Houston, Houston, TX 77204 (United States); Widger, William, E-mail: widger@uh.edu [Department of Biology and Biochemistry and Texas Center for Superconductivity, University of Houston, Houston, TX 77204 (United States); Chu, Wei-Kan, E-mail: wkchu@uh.edu [Department of Physics and Texas Center for Superconductivity, University of Houston, Houston, TX 77204 (United States)

2017-07-31

Highlights: • The nano ripple LSPR chip has monolayer molecule-coating sensitivity and specific selectivity. • Gold nano-ripple sensing chip is a low cost, and a label-free method for detecting the antibody-antigen reaction. • The plasmonic resonance shift depends upon the concentration of the biomolecules attached on the surface of the nano ripple pattern. - Abstract: We demonstrate that the gold nano-ripple localized surface plasmon resonance (LSPR) chip is a low cost and a label-free method for detecting the presence of an antigen. A uniform stable layer of an antibody was coated on the surface of a nano-ripple gold pattern chip followed by the addition of different concentrations of the antigen. A red shift was observed in the LSPR spectral peak caused by the change in the local refractive index in the vicinity of the nanostructure. The LSPR chip was fabricated using oblique gas cluster ion beam (GCIB) irradiation. The plasmon-resonance intensity of the scattered light was measured by a simple optical spectroscope. The gold nano ripple chip shows monolayer scale sensitivity and high selectivity. The LSPR substrate was used to detect antibody-antigen reaction of rabbit X-DENTT antibody and DENTT blocking peptide (antigen).

Fabrication of conducting polymer-gold nanoparticles film on electrodes using monolayer protected gold nanoparticles and its electrocatalytic application

Energy Technology Data Exchange (ETDEWEB)

Kannan, Palanisamy [Department of Chemistry, Gandhigram Rural University, Gandhigram 624 302, Dindigul (India); School of Chemical and Biomedical Engineering, N1.3, B4-01, 70 Nanyang Drive, Nanyang Technological University, Singapore 637457 (Singapore); John, S. Abraham, E-mail: abrajohn@yahoo.co.in [Department of Chemistry, Gandhigram Rural University, Gandhigram 624 302, Dindigul (India)

2011-08-01

We wish to report a simple and new strategy for the fabrication of gold nanoparticles-conducting polymer film on glassy carbon (GC) and indium tin oxide (ITO) surfaces using 5-amino-2-mercapto-1,3,4-thiadiazole capped gold nanoparticles (AMT-AuNPs) in 0.01 M H{sub 2}SO{sub 4} by electropolymerization. The presence of amine groups on the surface of the AuNPs was responsible for the deposition of the AMT-AuNPs film on the electrode surface. The atomic force microscopy (AFM) studies reveal that the fabricated p-AMT-AuNPs film showed homogeneously distributed AuNPs with a spherical shape of {approx}8 nm diameter. The XPS spectrum shows the binding energies at 83.8 and 87.5 eV in the Au 4f region corresponding to 4f{sub 7/2} and 4f{sub 5/2}, respectively. The position and difference between these two peaks (3.7 eV) exactly match the value reported for Au{sup 0}. The N1s XPS showed three binding energies at 396.7, 399.6 and 403.3 eV, corresponding to the =NH, -NH- and -N{sup +}H-, respectively, confirming that the electropolymerization proceeded through the oxidation of -NH{sub 2} groups present on the periphery of the AMT-AuNPs. The application of the present p-AMT-AuNPs modified electrode was demonstrated by studying the electro reduction of oxygen at pH 7.2. The p-AMT-AuNPs film enhanced the oxygen reduction current more than three times than that of p-AMT film prepared under identical conditions.

Glucose oxidase-functionalized fluorescent gold nanoclusters as probes for glucose

International Nuclear Information System (INIS)

Xia, Xiaodong; Long, Yunfei; Wang, Jianxiu

2013-01-01

Highlights: ► A glucose oxidase/gold nanocluster conjugates formed by etching chemistry. ► Integration of the bioactivities and fluorescence properties within a single unit. ► These conjugates serve as novel fluorescent probe for glucose. -- Abstract: Creation and application of noble metal nanoclusters have received continuous attention. By integrating enzyme activity and fluorescence for potential applications, enzyme-capped metal clusters are more desirable. This work demonstrated a glucose oxidase (an enzyme for glucose)-functionalized gold cluster as probe for glucose. Under physiological conditions, such bioconjugate was successfully prepared by an etching reaction, where tetrakis (hydroxylmethyl) phosphonium-protected gold nanoparticle and thioctic acid-modified glucose oxidase were used as precursor and etchant, respectively. These bioconjugates showed unique fluorescence spectra (λ em max = 650 nm, λ ex max = 507 nm) with an acceptable quantum yield (ca. 7%). Moreover, the conjugated glucose oxidase remained active and catalyzed reaction of glucose and dissolved O 2 to produce H 2 O 2 , which quenched quantitatively the fluorescence of gold clusters and laid a foundation of glucose detection. A linear range of 2.0 × 10 −6 –140 × 10 −6 M and a detection limit of 0.7 × 10 −6 M (S/N = 3) were obtained. Also, another horseradish peroxidase/gold cluster bioconjugate was produced by such general synthesis method. Such enzyme/metal cluster bioconjugates represented a promising class of biosensors for biologically important targets in organelles or cells

Self-assembled monolayers of semi-fluorinated thiols and disulfides with a potentially antibacterial terminal fragment on gold surfaces

International Nuclear Information System (INIS)

Thebault, P.; Taffin de Givenchy, E.; Guittard, F.; Guimon, C.; Geribaldi, S.

2008-01-01

Attempts to elaborate the best organized cationic self-assembled monolayers (SAMs) with sulfur derivatives containing potentially bactericidal quaternary ammonium salt moieties have been performed on gold with the final aim to obtain contact-active antibacterial surfaces. Four molecules bearing two hydrocarbon spacers with different lengths between the sulfur atom and the quaternized nitrogen atom, and two different terminal semi-fluorinated alkyl chains have been synthesised and used in view to evaluate their capacity for leading to the highest densities and the highest organization of potentially active molecules on the metal surface. The formation and quality of SAMs characterized by X-ray photoelectron spectroscopy, Internal Reflexion Infra Red Imaging, contact angle and blocking factor measurements depend on the lengths of both the hydrocarbon spacer and terminal perfluorinated chain

Total internal reflection sum-frequency generation spectroscopy and dense gold nanoparticles monolayer: a route for probing adsorbed molecules

International Nuclear Information System (INIS)

Tourillon, Gerard; Dreesen, Laurent; Volcke, Cedric; Sartenaer, Yannick; Thiry, Paul A; Peremans, Andre

2007-01-01

We show that sum-frequency generation spectroscopy performed in the total internal reflection configuration (TIR-SFG) combined with a dense gold nanoparticles monolayer allows us to study, with an excellent signal to noise ratio and high signal to background ratio, the conformation of adsorbed molecules. Dodecanethiol (DDT) was used as probe molecules in order to assess the potentialities of the approach. An enhancement of more than one order of magnitude of the SFG signals arising from the adsorbed species is observed with the TIR geometry compared to the external reflection one while the SFG non-resonant contribution remains the same for both configurations. Although further work is required to fully understand the origin of the SFG process on nanoparticles, our work opens new possibilities for studying nanostructures

Sample preconcentration utilizing nanofractures generated by junction gap breakdown assisted by self-assembled monolayer of gold nanoparticles.

Directory of Open Access Journals (Sweden)

Chun-Ping Jen

Full Text Available The preconcentration of proteins with low concentrations can be used to increase the sensitivity and accuracy of detection. A nonlinear electrokinetic flow is induced in a nanofluidic channel due to the overlap of electrical double layers, resulting in the fast accumulation of proteins, referred to as the exclusion-enrichment effect. The proposed chip for protein preconcentration was fabricated using simple standard soft lithography with a polydimethylsiloxane replica. This study extends our previous paper, in which gold nanoparticles were manually deposited onto the surface of a protein preconcentrator. In the present work, nanofractures were formed by utilizing the self-assembly of gold-nanoparticle-assisted electric breakdown. This reliable method for nanofracture formation, involving self-assembled monolayers of nanoparticles at the junction gap between microchannels, also decreases the required electric breakdown voltage. The experimental results reveal that a high concentration factor of 1.5×10(4 for a protein sample with an extremely low concentration of 1 nM was achieved in 30 min by using the proposed chip, which is faster than our previously proposed chip at the same conditions. Moreover, an immunoassay of bovine serum albumin (BSA and anti-BSA was carried out to demonstrate the applicability of the proposed chip.

DNA-mediated self-assembly of carbon nanotubes on gold

International Nuclear Information System (INIS)

Sanchez-Pomales, Germarie; Rivera-Velez, Nelson E; Cabrera, Carlos R

2007-01-01

This report presents the use of disulfide-modified single-stranded DNA (ssDNA) to form DNA self-assembled monolayers (SAMs) and mixed DNA-carbon nanotube (CNT) hybrids SAMs on gold substrates. Mixed DNA-CNT SAMs are composed of DNA, mercaptohexanol (MCH) and DNA-CNT aggregates. Both, DNA-CNT and DNA areas of the mixed SAMs were analyzed and compared to traditional DNA SAMs. The results suggest the formation of a more compact and densely packed monolayer of DNA-CNT in comparison with DNA. The use of DNA-CNT hybrids to form SAMs on gold substrates might represent a new approach to improve the immobilization of DNA strands on gold, and might therefore help with the development of enhanced DNA sensors

Scanning Tunneling Microscopic Observation of Adatom-Mediated Motifs on Gold-Thiol Self-assembled Monolayers at High Coverage

DEFF Research Database (Denmark)

Wang, Yun; Chi, Qijin; Hush, Noel S.

2009-01-01

the structural motifs observed on surfaces at low coverage and on gold nanoparticles to the observed spectroscopic properties of high-coverage SAMs formed by methanethiol. However, the significant role attributed to intermolecular steric packing effects suggests a lack of generality for the adatom-mediated motif......Self-assembled monolayers (SAMs) formed by chemisorption of a branched-chain alkanethiol, 2-methyl-1-propanethiol, on Au(111) surfaces were studied by in situ scanning tunneling microscopy (STM) under electrochemical potential control and analyzed using extensive density functional theory (DFT...... two R−S−Au−S−R adatom-mediated motifs per surface cell, with steric-induced variations in the adsorbate alignment inducing the observed STM image contrasts. Observed pits covering 5.6 ± 0.5% of the SAM surface are consistent with this structure. These results provide the missing link from...

The weak lensing analysis of the CFHTLS and NGVS RedGOLD galaxy clusters

Science.gov (United States)

Parroni, C.; Mei, S.; Erben, T.; Van Waerbeke, L.; Raichoor, A.; Ford, J.; Licitra, R.; Meneghetti, M.; Hildebrandt, H.; Miller, L.; Côté, P.; Covone, G.; Cuillandre, J.-C.; Duc, P.-A.; Ferrarese, L.; Gwyn, S. D. J.; Puzia, T. H.

2017-12-01

An accurate estimation of galaxy cluster masses is essential for their use in cosmological and astrophysical studies. We studied the accuracy of the optical richness obtained by our RedGOLD cluster detection algorithm tep{licitra2016a, licitra2016b} as a mass proxy, using weak lensing and X-ray mass measurements. We measured stacked weak lensing cluster masses for a sample of 1323 galaxy clusters in the Canada-France-Hawaii Telescope Legacy Survey W1 and the Next Generation Virgo Cluster Survey at 0.2z<0.5, in the optical richness range 10-70. We tested different weak lensing mass models that account for miscentering, non-weak shear, the two-halo term, the contribution of the Brightest Cluster Galaxy, and the intrinsic scatter in the mass-richness relation. We calculated the coefficients of the mass-richness relation, and of the scaling relations between the lensing mass and X-ray mass proxies.

Oriented nanocomposites of ultrahigh-molecular-weight polyethylene and gold

NARCIS (Netherlands)

Heffels, W.; Bastiaansen, C.W.M.; Caseri, W.R.; Smith, P.

2000-01-01

Polymer nanocomposites were prepd. by mixing ultrahigh-mol.-wt. polyethylene and gold colloids coated with a self-assembled monolayer of dodecanethiol. Subsequently, these materials were oriented by solid state drawing which induced the formation of uniaxially oriented arrays of gold particles. As a

Glucose oxidase-functionalized fluorescent gold nanoclusters as probes for glucose

Energy Technology Data Exchange (ETDEWEB)

Xia, Xiaodong [College of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China); School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201 (China); Long, Yunfei, E-mail: l_yunfei927@163.com [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201 (China); Wang, Jianxiu, E-mail: jxiuwang@csu.edu.cn [College of Chemistry and Chemical Engineering, Central South University, Changsha 410083 (China)

2013-04-15

Highlights: ► A glucose oxidase/gold nanocluster conjugates formed by etching chemistry. ► Integration of the bioactivities and fluorescence properties within a single unit. ► These conjugates serve as novel fluorescent probe for glucose. -- Abstract: Creation and application of noble metal nanoclusters have received continuous attention. By integrating enzyme activity and fluorescence for potential applications, enzyme-capped metal clusters are more desirable. This work demonstrated a glucose oxidase (an enzyme for glucose)-functionalized gold cluster as probe for glucose. Under physiological conditions, such bioconjugate was successfully prepared by an etching reaction, where tetrakis (hydroxylmethyl) phosphonium-protected gold nanoparticle and thioctic acid-modified glucose oxidase were used as precursor and etchant, respectively. These bioconjugates showed unique fluorescence spectra (λ{sub em} {sub max} = 650 nm, λ{sub ex} {sub max} = 507 nm) with an acceptable quantum yield (ca. 7%). Moreover, the conjugated glucose oxidase remained active and catalyzed reaction of glucose and dissolved O{sub 2} to produce H{sub 2}O{sub 2}, which quenched quantitatively the fluorescence of gold clusters and laid a foundation of glucose detection. A linear range of 2.0 × 10{sup −6}–140 × 10{sup −6} M and a detection limit of 0.7 × 10{sup −6} M (S/N = 3) were obtained. Also, another horseradish peroxidase/gold cluster bioconjugate was produced by such general synthesis method. Such enzyme/metal cluster bioconjugates represented a promising class of biosensors for biologically important targets in organelles or cells.

Triazolobithiophene Light Absorbing Self-Assembled Monolayers: Synthesis and Mass Spectrometry Applications

Directory of Open Access Journals (Sweden)

Denis Séraphin

2011-10-01

Full Text Available The synthesis of five light absorbing triazolobithiophenic thiols, which were utilized for producing self-assembled monolayers (SAMs on gold surfaces, is presented. The monolayer formation was monitored by cyclic voltammetry, indicating excellent surface coverage. The new triazolobithiophenic compounds exhibited an absorption maximum around 340 nm, which is close to the emission wavelength of a standard nitrogen laser. Consequently these compounds could be used to aid ionization in laser desorption mass spectrometry (MS.

Molecular geometries and relative stabilities of titanium oxide and gold-titanium oxide clusters

Energy Technology Data Exchange (ETDEWEB)

Hudson, Rohan J.; Falcinella, Alexander; Metha, Gregory F., E-mail: greg.metha@adelaide.edu.au

2016-09-30

Titanium oxide and gold-titanium oxide clusters of stoichiometry M{sub x}O{sub y} (M{sub x} = Ti{sub 3}, Ti{sub 4} & AuTi{sub 3}; y = 0 − (2x + 2)) have been investigated using density functional theory. Geometries of determined global energy minimum structures are reported and other isomers predicted up to 0.5 eV higher in energy. The Ti{sub 3}O{sub n} geometries build upon a triangular Ti{sub 3} motif, while Ti{sub 4}O{sub n} stoichiometries template upon a pseudo-tetrahedral Ti{sub 4} structure. Addition of a gold atom to the Ti{sub 3}O{sub n} series does not significantly alter the cluster geometry, with the gold atom preferentially binding to titanium atoms over oxygen atoms. Adiabatic ionization energies, electron affinities and HOMO/LUMO energies increase in magnitude with increasing oxygenation. The HOMO-LUMO energy gaps reach the bulk anatase band gap energy at stoichiometry (Au)Ti{sub m}O{sub 2m−1}, and increase above this upon further oxygen addition. The most stable structural moieties are found to be a cage-like, C{sub 3v} symmetric Ti{sub 4}O{sub 6/7} geometry and a Ti{sub 3}O{sub 6} structure with an η{sup 3}-bound oxygen atom.

High photoreactivity in a non-fluorescent photocleavable ligands on gold

Science.gov (United States)

Robinson, Hans D.; Daengngam, Chalongrat; Stoianov, Stefan V.; Thorpe, Steven B.; Guo, Xi; Santos, Webster L.; Morris, John R.

2014-03-01

We report on the photo-patterning of a gold surface functionalized with a self-assembled monolayer of an o-nitrobenzyl-based photocleavable ligand bound to the gold surface with a thiol anchor. We find that the dose of UV light required to induce the photoreaction on gold is very similar to the dose in an alcohol solution, even though many optical phenomena are strongly suppressed on metal surfaces. We attribute this finding to a combination of the large skin depth in gold at UV wavelengths, the high speed of the photoreaction, and the spatially indirect nature of the lowest excited singlet. Any photoreactive compound where the quantum efficiency of fluorescence is sufficiently low, preferably no larger than about 10-5 in the case of gold surfaces, will show a similarly high photoreactivity in metal-surface monolayers. The implications of this result for optically driven self-assembly in plasmonic systems will be discussed. This work was supported by a grant from the National Science Foundation (DMR-106753).

Visualization of red-ox proteins on the gold surface using enzymatic polypyrrole formation

International Nuclear Information System (INIS)

Ramanaviciene, A.; Kausaite-Minkstimiene, A.; Voronovic, J.; Ramanavicius, A.; Oztekin, Y.; Carac, G.; German, N.

2011-01-01

We describe a new method for the visualization of the activity of red-ox proteins on a gold interface. Glucose oxidase was selected as a model system. Surfaces were modified by adhesion of glucose oxidase on (a) electrochemically cleaned gold; (b) gold films modified with gold nanoparticles, (c) a gold surface modified with self-assembled monolayer, and (d) covalent immobilization of protein on the gold surface modified with a self-assembled monolayer. The simple optical method for the visualization of enzyme on the surfaces is based on the enzymatic formation of polypyrrole. The activity of the enzyme was quantified via enzymatic formation of polypyrrole, which was detected and investigated by quartz microbalance and amperometric techniques. The experimental data suggest that the enzymatic formation of the polymer may serve as a method to indicate the adhesion of active redox enzyme on such surfaces. (author)

Controlled electrodeposition of Au monolayer film on ionic liquid

Science.gov (United States)

Ma, Qiang; Pang, Liuqing; Li, Man; Zhang, Yunxia; Ren, Xianpei; Liu, Shengzhong Frank

2016-05-01

Gold (Au) nanoparticles have been attractive for centuries for their vibrant appearance enhanced by their interaction with sunlight. Nowadays, there have been tremendous research efforts to develop them for high-tech applications including therapeutic agents, sensors, organic photovoltaics, medical applications, electronics and catalysis. However, there remains to be a challenge to fabricate a monolayer Au coating with complete coverage in controlled fashion. Here we present a facile method to deposit a uniform Au monolayer (ML) film on the [BMIM][PF6] ionic liquid substrate using an electrochemical deposition process. It demonstrates that it is feasible to prepare a solid phase coating on the liquid-based substrate. Moreover, the thickness of the monolayer coating can be controlled to a layer-by-layer accuracy.

Structural, electronic and magnetic properties of 3d metal trioxide clusters-doped monolayer graphene: A first-principles study

Energy Technology Data Exchange (ETDEWEB)

Rafique, Muhammad [School of Energy Science and Engineering, Harbin Institute of Technology, 92 West Dazhi Street, Harbin 150001 (China); M.U.E.T, S.Z.A.B, Campus Khairpur Mir' s, Sindh (Pakistan); Shuai, Yong, E-mail: shuaiyong1978@gmail.com [School of Energy Science and Engineering, Harbin Institute of Technology, 92 West Dazhi Street, Harbin 150001 (China); Tan, He-Ping; Hassan, Muhammad [School of Energy Science and Engineering, Harbin Institute of Technology, 92 West Dazhi Street, Harbin 150001 (China)

2017-03-31

Highlights: • First-principles calculations are performed for TMO{sub 3} cluster-doped and TM atoms adsorbed at three O atoms-doped graphene. • Significant magnetic coupling behavior is observed between TM atoms and neighboring C and O atoms for both cases. • The direction of charge transfer is always from monolayer graphene to TMO{sub 3} clusters incorporated into graphene. • TiO{sub 3} and VO{sub 3} doped structures display dilute magnetic semiconductor behavior. • Five different orbitals (d{sub xy}, d{sub yz}, d{sub z}{sup 2}, d{sub xz} and d{sub x}{sup 2}{sub -y}{sup 2}) of 3d TM atoms give rise to magnetic moments for both cases. - Abstract: We present first-principles density-functional calculations for the structural, electronic and magnetic properties of monolayer graphene doped with 3d (Ti, V, Cr, Fe, Co, Mn and Ni) metal trioxide TMO{sub 3} halogen clusters. In this paper we used two approaches for 3d metal trioxide clusters (i) TMO{sub 3} halogen cluster was embedded in monolayer graphene substituting four carbon (C) atoms (ii) three C atoms were substituted by three oxygen (O) atoms in one graphene ring and TM atom was adsorbed at the hollow site of O atoms substituted graphene ring. All the impurities were tightly bonded in the graphene ring. In first case of TMO{sub 3} doped graphene layer, the bond length between C−O atom was reduced and bond length between TM-O atom was increased. In case of Cr, Fe, Co and Ni atoms substitution in between the O atoms, leads to Fermi level shifting to conduction band thereby causing the Dirac cone to move into valence band, however a band gap appears at high symmetric K-point. In case of TiO{sub 3} and VO{sub 3} substitution, system exhibits semiconductor properties. Interestingly, TiO{sub 3}-substituted system shows dilute magnetic semiconductor behavior with 2.00 μ{sub B} magnetic moment. On the other hand, the substitution of CoO{sub 3}, CrO{sub 3}, FeO{sub 3} and MnO{sub 3} induced 1.015 μ{sub B}, 2

Cluster dynamics at different cluster size and incident laser wavelengths

International Nuclear Information System (INIS)

Desai, Tara; Bernardinello, Andrea

2002-01-01

X-ray emission spectra from aluminum clusters of diameter -0.4 μm and gold clusters of dia. ∼1.25 μm are experimentally studied by irradiating the cluster foil targets with 1.06 μm laser, 10 ns (FWHM) at an intensity ∼10 12 W/cm 2 . Aluminum clusters show a different spectra compared to bulk material whereas gold cluster evolve towards bulk gold. Experimental data are analyzed on the basis of cluster dimension, laser wavelength and pulse duration. PIC simulations are performed to study the behavior of clusters at higher intensity I≥10 17 W/cm 2 for different size of the clusters irradiated at different laser wavelengths. Results indicate the dependence of cluster dynamics on cluster size and incident laser wavelength

Multiscale Modeling of Plasmon-Exciton Dynamics of Malachite Green Monolayers on Gold Nanoparticles

Science.gov (United States)

Smith, Holden; Karam, Tony; Haber, Louis; Lopata, Kenneth

A multi-scale hybrid quantum/classical approach using classical electrodynamics and a collection of discrete two-level quantum system is used to investigate the coupling dynamics of malachite green monolayers adsorbed to the surface of a spherical gold nanoparticle (NP). This method utilizes finite difference time domain (FDTD) to describe the plasmonic response of the NP and a two-level quantum description for the molecule via the Maxwell/Liouville equation. The molecular parameters are parameterized using CASPT2 for the energies and transition dipole moments, with the dephasing lifetime fit to experiment. This approach is suited to simulating thousands of molecules on the surface of a plasmonic NP. There is good agreement with experimental extinction measurements, predicting the plasmon and molecule depletions. Additionally, this model captures the polariton peaks overlapped with a Fano-type resonance profile observed in the experimental extinction measurements. This technique shows promise for modeling plasmon/molecule interactions in chemical sensing and light harvesting in multi-chromophore systems. This material is based upon work supported by the National Science Foundation under the NSF EPSCoR Cooperative Agreement No. EPS-1003897 and by the Louisiana Board of Regents Research Competitiveness Subprogram under Contract Number LEQSF(2014-17)-RD-A-0.

Efficient surface enhanced Raman scattering on confeito-like gold nanoparticle-adsorbed self-assembled monolayers.

Science.gov (United States)

Chang, Chia-Chi; Imae, Toyoko; Chen, Liang-Yih; Ujihara, Masaki

2015-12-28

Confeito-like gold nanoparticles (AuNPs; average diameter = 80 nm) exhibiting a plasmon absorption band at 590 nm were adsorbed through immersion-adsorption on two self-assembled monolayers (SAMs) of 3-aminopropyltriethoxysilane (APTES-SAM) and polystyrene spheres coated with amine-terminated poly(amido amine) dendrimers (DEN/PS-SAM). The surface enhanced Raman scattering (SERS) effect on the SAM substrates was examined using the molecules of a probe dye, rhodamine 6G (R6G). The Raman scattering was strongly intensified on both substrates, but the enhancement factor (>10,000) of the AuNP/DEN/PS-SAM hierarchy substrate was 5-10 times higher than that of the AuNP/APTES-SAM substrate. This strong enhancement is attributed to the large surface area of the substrate and the presence of hot spots. Furthermore, analyzing the R6G concentration dependence of SERS suggested that the enhancement mechanism effectively excited the R6G molecules in the first layer on the hot spots and invoked the strong SERS effect. These results indicate that the SERS activity of confeito-like AuNPs on SAM substrates has high potential in molecular electronic devices and ultrasensitive analyses.

Targeting Ovarian Cancer with Porphysome Nanotechnology

Science.gov (United States)

2014-10-01

Gross, S. M.; Miles, D. T.; Murray, R. W. Nanometer Gold Clusters Protected by Surface-Bound Monolayers of Thiolated Poly(Ethylene Glycol) Polymer ... Polymeric Micelles in Poorly Permeable Tumours Depends on Size. Nature nanotechnology 2011, 6, 815-823. 13. Pluen, A.; Boucher, Y.; Ramanujan, S...developed for improving their stability, delivery effi ciency, and preferen- tial accumulation at target-tissue, such as polymers loaded with

UV/Vis and NIR Light-Responsive Spiropyran Self-Assembled Monolayers

NARCIS (Netherlands)

Ivashenko, Oleksii; Herpt, Jochem T. van; Feringa, Ben L.; Rudolf, Petra; Browne, Wesley R.

2013-01-01

Self-assembled monolayers of a 6-nitro BIPS spiropyran (SP) modified with a disulfide-terminated aliphatic chain were prepared on polycrystalline gold surfaces and characterized by UV/vis absorption, surface-enhanced Raman scattering (SEAS), and X-ray photoelectron spectroscopies (XPS). The SAMs

Enhanced Emission from Single Isolated Gold Quantum Dots Investigated Using Two-Photon-Excited Fluorescence Near-Field Scanning Optical Microscopy.

Science.gov (United States)

Abeyasinghe, Neranga; Kumar, Santosh; Sun, Kai; Mansfield, John F; Jin, Rongchao; Goodson, Theodore

2016-12-21

New approaches in molecular nanoscopy are greatly desired for interrogation of biological, organic, and inorganic objects with sizes below the diffraction limit. Our current work investigates emergent monolayer-protected gold quantum dots (nanoclusters, NCs) composed of 25 Au atoms by utilizing two-photon-excited fluorescence (TPEF) near-field scanning optical microscopy (NSOM) at single NC concentrations. Here, we demonstrate an approach to synthesize and isolate single NCs on solid glass substrates. Subsequent investigation of the NCs using TPEF NSOM reveals that, even when they are separated by distances of several tens of nanometers, we can excite and interrogate single NCs individually. Interestingly, we observe an enhanced two-photon absorption (TPA) cross section for single Au 25 NCs that can be attributed to few-atom local field effects and to local field-induced microscopic cascading, indicating their potential for use in ultrasensitive sensing, disease diagnostics, cancer cell therapy, and molecular computers. Finally, we report room-temperature aperture-based TPEF NSOM imaging of these NCs for the first time at 30 nm point resolution, which is a ∼5-fold improvement compared to the previous best result for the same technique. This report unveils the unique combination of an unusually large TPA cross section and the high photostability of Au NCs to (non-destructively) investigate stable isolated single NCs using TPEF NSOM. This is the first reported optical study of monolayer-protected single quantum clusters, opening some very promising opportunities in spectroscopy of nanosized objects, bioimaging, ultrasensitive sensing, molecular computers, and high-density data storage.

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

International Nuclear Information System (INIS)

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

2006-01-01

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

Microcontact printing of self-assembled monolayers to pattern the light-emission of polymeric light-emitting diodes

NARCIS (Netherlands)

Brondijk, J. J.; Li, X.; Akkerman, H. B.; Blom, P. W. M.; de Boer, B.

By patterning a self-assembled monolayer (SAM) of thiolated molecules with opposing dipole moments on a gold anode of a polymer light-emitting diode (PLED), the charge injection and, therefore, the light-emission of the device can be controlled with a micrometer-scale resolution. Gold surfaces were

Langmuir isoterms of 4-methylbenzenethiol encapsulated gold nanoparticles and two kinds of poly(ethyleneoxide) derivatives with incorporated Li ions

International Nuclear Information System (INIS)

Capan, I.

2004-01-01

Surface pressure - area isotherms are used to investigate the behavior of monolayers on a water surface by recording surface pressure (□) during reduction of the confinernem area (A). A number of isotherms have been recorded using gold thiol nanoparticles and polymers in different ratios and with LiClO 4 -. salt to provide ions within the monolayer. lt is seen that the area per molecule reduces in size when gold thiol is added to Poly(Ethyleneoxide) derivatives. AIso adding lithium ions modifies the area per molecule for both polymers. A mixed monolayer containing both POlY(Ethyleneoxide)derivatives and gold thiol with Li ions all mixed together shows a plateau region representing a phase transition. All these results will be discussed and isotherms will be used to find out behaviors of the monolayers on the water surface

Deformation of Ag clusters deposited on Au(111) - Experiment and molecular dynamics

Energy Technology Data Exchange (ETDEWEB)

Miroslawski, Natalie; Groenhagen, Niklas; Hoevel, Heinz [TU Dortmund, Experimentelle Physik I (Germany); Issendorff, Bernd von [Universitaet Freiburg, Fakultaet Physik (Germany); Jaervi, Tommi [Fraunhofer Institut fuer Werkstoffmechanik, Freiburg (Germany); Moseler, Michael [Universitaet Freiburg, Fakultaet Physik (Germany); Fraunhofer Institut fuer Werkstoffmechanik, Freiburg (Germany); Freiburger Materialforschungszentrum (Germany)

2011-07-01

Mass selected clusters from Ag{sup +}{sub 55} to Ag{sup +}{sub 147{+-}}{sub 2} were deposited with different deposition energies at 77 K on Au(111) and imaged with STM at 77 K. We observed a deformation of the cluster shape due to the strong metallic interaction between the cluster and the substrate. The clusters became epitaxial and developed a structure composed of several Ag monolayers. The number of these monolayers depends on the number of atoms in the cluster and the deposition energy. The larger the cluster mass the more monolayers the cluster develops on Au(111) and the larger the deposition energy the fewer monolayers occur. These results were verified by molecular dynamic simulations. Additionally the behaviour of Ag{sub N} clusters on Au(111) after different annealing steps was investigated.

Gold nanoparticle-pentacene memory-transistors

OpenAIRE

Novembre , Christophe; Guerin , David; Lmimouni , Kamal; Gamrat , Christian; Vuillaume , Dominique

2008-01-01

We demonstrate an organic memory-transistor device based on a pentacene-gold nanoparticles active layer. Gold (Au) nanoparticles are immobilized on the gate dielectric (silicon dioxide) of a pentacene transistor by an amino-terminated self-assembled monolayer. Under the application of writing and erasing pulses on the gate, large threshold voltage shift (22 V) and on/off drain current ratio of ~3E4 are obtained. The hole field-effect mobility of the transistor is similar in the on and off sta...

The nanocoherer: an electrically and mechanically resettable resistive switching device based on gold clusters assembled on paper

Science.gov (United States)

Minnai, Chloé; Mirigliano, Matteo; Brown, Simon A.; Milani, Paolo

2018-03-01

We report the realization of a resettable resistive switching device based on a nanostructured film fabricated by supersonic cluster beam deposition of gold clusters on plain paper substrates. Through the application of suitable voltage ramps, we obtain, in the same device, either a complex pattern of resistive switchings, or reproducible and stable switchings between low resistance and high resistance states, with an amplitude up to five orders of magnitude. Our device retains a state of internal resistance following the history of the applied voltage similar to that reported for memristors. The two different switching regimes in the same device are both stable, the transition between them is reversible, and it can be controlled by applying voltage ramps or by mechanical deformation of the substrate. The device behavior can be related to the formation, growth and breaking of junctions between the loosely aggregated gold clusters forming the nanostructured films. The fact that our cluster-assembled device is mechanically resettable suggests that it can be considered as the analog of the coherer: a switching device based on metallic powders used for the first radio communication system.

Tuning of metal work functions with self-assembled monolayers

NARCIS (Netherlands)

de Boer, B; Hadipour, A; Mandoc, MM; van Woudenbergh, T; Blom, PWM

2005-01-01

Work functions of gold and silver are varied by over 1.4 and 1.7 eV, respectively, by using self-assembled monolayers. Using these modified electrodes, the hole current in a poly(2-methoxy-5-(2'-ethylhexyloxy)- 1,4-phenylene vinylene) light-emitting diode is tuned by more than six orders of

Kinetics of electron transfer through ferrocene-terminated alkanethiol monolayers on gold

Energy Technology Data Exchange (ETDEWEB)

Smalley, J.F.; Feldberg, S.W.; Newton, M.D.; Liu, Y.P. [Brookhaven National Lab., Upton, NY (United States); Chidsey, C.E.D.; Linford, M.R. [Stanford Univ., CA (United States)

1995-08-31

The kinetics of electron transfer between a substrate gold electrode and a self-assembled monolayer formed from CH{sub 3}(CH{sub 2}){sub n-1}SH and ({eta}{sup 5} C{sub 5}H{sub 5})Fe ({eta}{sup 5}-C{sub 5}H{sub 4})CO{sub 2}(CH{sub 2}){sub n}SH were studied as a function of n, the number of methylenes in the alkyl chain tethering the ferrocene moiety to the electrode, using the indirect laser-induced temperature jump method (ILIT). For 5 {<=} n {<=} 9 the standard electron-transfer rate constants vary according to {kappa}{sub {tau}a,n=0} exp[-{beta}{sub n}n] where {kappa}{sub {tau}a,n=0} is the (extrapolated) rate constant for the electron transfer at n = 0. At {Tau} = 25{degree}C, {kappa}{sub {tau}a,n} 0 {approx_equal} 6 x 10{sup 8} s{sup -1} and {beta}{sub n} = 1.21 x 0.05. The ILIT method allows rates to be measured that are too fast to be measured by conventional chronoamperometry at a macroelectrode, which is limited to rate constants of {<=} 10{sup 4} s{sup -1}. Using a Marcus formalism, the reorganization energy, {lambda}, for the electron-transfer process at a given n was determined from the slope of an Arrhenius plot over the temperature range 15-55{degree}C. Values of {lambda} determined from Arrhenius slopes for n = 8 and 9 using ILIT are in reasonable agreement with the value of {lambda} previously deduced from the potential dependence of the rate constant for n = 16. 39 refs., 13 figs., 3 tabs.

Communication: CO oxidation by silver and gold cluster cations: Identification of different active oxygen species

International Nuclear Information System (INIS)

Popolan, Denisia M.; Bernhardt, Thorsten M.

2011-01-01

The oxidation of carbon monoxide with nitrous oxide on mass-selected Au 3 + and Ag 3 + clusters has been investigated under multicollision conditions in an octopole ion trap experiment. The comparative study reveals that for both gold and silver cations carbon dioxide is formed on the clusters. However, whereas in the case of Au 3 + the cluster itself acts as reactive species that facilitates the formation of CO 2 from N 2 O and CO, for silver the oxidized clusters Ag 3 O x + (n= 1-3) are identified as active in the CO oxidation reaction. Thus, in the case of the silver cluster cations N 2 O is dissociated and one oxygen atom is suggested to directly react with CO, whereas a second kind of oxygen strongly bound to silver is acting as a substrate for the reaction.

Communication: CO oxidation by silver and gold cluster cations: Identification of different active oxygen species

Science.gov (United States)

Popolan, Denisia M.; Bernhardt, Thorsten M.

2011-03-01

The oxidation of carbon monoxide with nitrous oxide on mass-selected Au3+ and Ag3+ clusters has been investigated under multicollision conditions in an octopole ion trap experiment. The comparative study reveals that for both gold and silver cations carbon dioxide is formed on the clusters. However, whereas in the case of Au3+ the cluster itself acts as reactive species that facilitates the formation of CO2 from N2O and CO, for silver the oxidized clusters Ag3Ox+ (n = 1-3) are identified as active in the CO oxidation reaction. Thus, in the case of the silver cluster cations N2O is dissociated and one oxygen atom is suggested to directly react with CO, whereas a second kind of oxygen strongly bound to silver is acting as a substrate for the reaction.

Chiral ligand-protected gold nanoclusters: Considering the optical activity from a viewpoint of ligand dissymmetric field

Directory of Open Access Journals (Sweden)

Hiroshi Yao

2016-10-01

Full Text Available Chirality is a geometric property of a physical, chemical, or biological object, which is not superimposable on its mirror image. Its significant presence has led to a strong demand in the development of chiral drugs, sensors, catalysts, and photofunctional materials. In recent years, chirality of nanoscale organic/inorganic hybrids has received tremendous attention owing to potential applications in chiral nanotechnology. In particular, with the recent progress in the syntheses and characterizations of atomically precise gold nanoclusters protected by achiral thiolates, atomic level origins of their chirality have been unveiled. On the other hand, chirality or optical activity in metal nanoclusters can also be introduced via the surface chiral ligands, which should be universal for the nanosystems. This tutorial review presents some optically-active metal (gold nanoclusters protected by chiral thiolates or phosphines, and their chiroptical (or circular dichroism; CD properties are discussed mostly from a viewpoint of the ligand dissymmetric field scheme. The examples are the gold nanoclusters protected by (R-/(S-2-phenylpropane-1-thiol, (R-/(S-mercaptosuccinic acid, phenylboronate-D/L-fructose complexes, phosphine sulfonate-ephedrinium ion pairs, or glutathione. Some methodologies for versatile asymmetric transformation and chiroptical controls of the nanocluster compounds are also described. In the dissymmetric field model as the origin of optical activity, the chiroptical responses of the gold nanoclusters are strongly associated with coupled oscillator and/or CD stealing mechanisms based on the concept of induced CD (ICD derived from a perturbation theory, so on this basis, some characteristic features of the observed CD responses of chiral ligand-protected gold nanoclusters are presented in detail. We believe that various kinds of origins of chirality found in ligand-protected gold nanoclusters may provide models for understanding those of

Characterization of self-assembled monolayers (SAMs) on silicon substrate comparative with polymer substrate for Escherichia coli O157:H7 detection

International Nuclear Information System (INIS)

Moldovan, Carmen; Mihailescu, Carmen; Stan, Dana; Ruta, Lavinia; Iosub, Rodica; Gavrila, Raluca; Purica, Munizer; Vasilica, Schiopu

2009-01-01

This article presents the characterization of two substrates, silicon and polymer coated with gold, that are functionalized by mixed self-assembled monolayers (SAMs) in order to efficiently immobilize the anti-Escherichia coli O157:H7 polyclonal purified antibody. A biosurface functionalized by SAMs (self-assembled monolayers) technique has been developed. Immobilization of goat anti-E. coli O157:H7 antibody was performed by covalently bonding of thiolate mixed self-assembled monolayers (SAMs) realized on two substrates: polymer coated with gold and silicon coated with gold. The F(ab') 2 fragments of the antibodies have been used for eliminating nonspecific bindings between the Fc portions of antibodies and the Fc receptor on cells. The properties of the monolayers and the biofilm formatted with attached antibody molecules were analyzed at each step using infrared spectroscopy (FTIR-ATR), atomic force microscopy (AFM), scanning electron microscopy (SEM) and cyclic voltammetry (CV). In our study the gold-coated silicon substrates approach yielded the best results. These experimental results revealed the necessity to investigate each stage of the immobilization process taking into account in the same time the factors that influence the chemistry of the surface and the further interactions as well and also provide a solid basis for further studies aiming at elaborating sensitive and specific immunosensor or a microarray for the detection of E. coli O157:H7.

Characterization of self-assembled monolayers (SAMs) on silicon substrate comparative with polymer substrate for Escherichia coli O157:H7 detection

Energy Technology Data Exchange (ETDEWEB)

Moldovan, Carmen, E-mail: carmen.moldovan@imt.ro [National Institute for R and D in Microtechnologies, IMT-Bucharest, 126A Erou Iancu Nicolae, 077190 Bucharest (Romania); Mihailescu, Carmen, E-mail: carmen_mihail28@yahoo.com [University of Bucharest, 90-92 Sos Panduri, Bucharest (Romania); Stan, Dana, E-mail: dana_stan2005@yahoo.com [DDS Diagnostic, 1 Segovia Street, Bucharest (Romania); Ruta, Lavinia, E-mail: laviniacoco@yahoo.com [University of Bucharest, 90-92 Sos Panduri, Bucharest (Romania); Iosub, Rodica, E-mail: rodica.iosub@imt.ro [National Institute for R and D in Microtechnologies, IMT-Bucharest, 126A Erou Iancu Nicolae, 077190 Bucharest (Romania); Gavrila, Raluca, E-mail: raluca.gavrila@imt.ro [National Institute for R and D in Microtechnologies, IMT-Bucharest, 126A Erou Iancu Nicolae, 077190 Bucharest (Romania); Purica, Munizer, E-mail: munizer.purica@imt.ro [National Institute for R and D in Microtechnologies, IMT-Bucharest, 126A Erou Iancu Nicolae, 077190 Bucharest (Romania); Vasilica, Schiopu, E-mail: vasilica.schiopu@imt.ro [National Institute for R and D in Microtechnologies, IMT-Bucharest, 126A Erou Iancu Nicolae, 077190 Bucharest (Romania)

2009-08-30

This article presents the characterization of two substrates, silicon and polymer coated with gold, that are functionalized by mixed self-assembled monolayers (SAMs) in order to efficiently immobilize the anti-Escherichia coli O157:H7 polyclonal purified antibody. A biosurface functionalized by SAMs (self-assembled monolayers) technique has been developed. Immobilization of goat anti-E. coli O157:H7 antibody was performed by covalently bonding of thiolate mixed self-assembled monolayers (SAMs) realized on two substrates: polymer coated with gold and silicon coated with gold. The F(ab'){sub 2} fragments of the antibodies have been used for eliminating nonspecific bindings between the Fc portions of antibodies and the Fc receptor on cells. The properties of the monolayers and the biofilm formatted with attached antibody molecules were analyzed at each step using infrared spectroscopy (FTIR-ATR), atomic force microscopy (AFM), scanning electron microscopy (SEM) and cyclic voltammetry (CV). In our study the gold-coated silicon substrates approach yielded the best results. These experimental results revealed the necessity to investigate each stage of the immobilization process taking into account in the same time the factors that influence the chemistry of the surface and the further interactions as well and also provide a solid basis for further studies aiming at elaborating sensitive and specific immunosensor or a microarray for the detection of E. coli O157:H7.

Optical imaging beyond the diffraction limit by SNEM: effects of AFM tip modifications with thiol monolayers on imaging quality.

Science.gov (United States)

Cumurcu, Aysegul; Diaz, Jordi; Lindsay, Ian D; de Beer, Sissi; Duvigneau, Joost; Schön, Peter; Julius Vancso, G

2015-03-01

Tip-enhanced nanoscale optical imaging techniques such as apertureless scanning near-field optical microscopy (a-SNOM) and scanning near-field ellipsometric microscopy (SNEM) applications can suffer from a steady degradation in performance due to adhesion of atmospheric contaminants to the metal coated tip. Here, we demonstrate that a self-assembled monolayer (SAM) of ethanethiol (EtSH) is an effective means of protecting gold-coated atomic force microscopy (AFM) probe tips from accumulation of surface contaminants during prolonged exposure to ambient air. The period over which they yield consistent and reproducible results for scanning near-field ellipsometric microscopy (SNEM) imaging is thus extended. SNEM optical images of a microphase separated polystyrene-block-poly (methylmethacrylate) (PS-b-PMMA) diblock copolymer film, which were captured with bare and SAM-protected gold-coated AFM probes, both immediately after coating and following five days of storage in ambient air, were compared. During this period the intensity of the optical signals from the untreated gold tip fell by 66%, while those from the SAM protected tip fell by 14%. Additionally, gold coated AFM probe tips were modified with various lengths of alkanethiols to measure the change in intensity variation in the optical images with SAM layer thickness. The experimental results were compared to point dipole model calculations. While a SAM of 1-dodecanethiol (DoSH) was found to strongly suppress field enhancement we find that it can be locally removed from the tip apex by deforming the molecules under load, restoring SNEM image contrast. Copyright © 2014 Elsevier B.V. All rights reserved.

Direct electrochemistry and electrocatalysis of hemoglobin at three-dimensional gold film electrode modified with self-assembled monolayers of 3-mercaptopropylphosphonic acid

International Nuclear Information System (INIS)

Chen Yu; Yang Xiaojing; Guo Lirong; Li Jing; Xia Xinghua; Zheng Limin

2009-01-01

Multilayered hemoglobin (Hb) molecules were successfully immobilized on three-dimensional gold film electrode modified with self-assembled monolayers (SAMs) of 3-mercaptopropylphosphonic acid. Direct electrochemistry of the immobilized multilayered Hb occurs with high thermal stability and electrochemical stability. In the multilayered Hb film, the most inner Hb molecules can directly transfer electron with the electrode, while the Hb protein beyond this layer communicates electron with the electrode via protein-protein electron exchange. In addition, the proposed functional interface can greatly enhance electron transfer rate of the immobilized Hb protein (k s = 15.8 ± 2.0 s -1 ) due to the increase of roughness of the gold substrate. Under optimized experimental conditions, the multilayered Hb film displays good bioelectrocatalytic activity toward the reduction of hydrogen peroxide. This electrochemical sensor shows fast response (less than 1 s), wide linear range (7.8 x 10 -8 to 9.1 x 10 -5 M) and low detection limit (2.5 x 10 -8 M), which can be attributed to good mass transport, large Hb proteins loading per unit area and fast electron transfer rate of Hb protein.

Adsorption characteristics of self-assembled thiol and dithiol layer on gold

International Nuclear Information System (INIS)

Tlili, A.; Abdelghani, A.; Aguir, K.; Gillet, M.; Jaffrezic-Renault, N.

2007-01-01

Monolayers of functional proteins are important in many fields related to pure and applied biochemistry and biophysics. The formation of extended uniform protein monolayers by single- or multiple-step self-chemisorption depends on the quality of the functionalized gold surface. The optical and the electrical properties of the 1-nonanethiol and 1,9-nonanedithiol deposited on gold with the self-assembled technique were investigated. We use cyclic voltammetry and impedance spectroscopy to characterize the insulating properties of the two layers. The analysis of the impedance spectra in terms of equivalent circuit of the gold/electrolyte and gold/SAM/electrolyte interface allows defining the thickness of the two thiols and the percentage of coverage area. Atomic force microscopy, contact angle measurement and Fourier transform infra-red spectroscopy have been used for homogeneity, hydrophobic properties and molecular structure of the formed thiols layer, respectively. The measured thickness with impedance spectroscopy fit well the results found with atomic force microscopy

DNA-Protected Silver Clusters for Nanophotonics

Directory of Open Access Journals (Sweden)

Elisabeth Gwinn

2015-02-01

Full Text Available DNA-protected silver clusters (AgN-DNA possess unique fluorescence properties that depend on the specific DNA template that stabilizes the cluster. They exhibit peak emission wavelengths that range across the visible and near-IR spectrum. This wide color palette, combined with low toxicity, high fluorescence quantum yields of some clusters, low synthesis costs, small cluster sizes and compatibility with DNA are enabling many applications that employ AgN-DNA. Here we review what is known about the underlying composition and structure of AgN-DNA, and how these relate to the optical properties of these fascinating, hybrid biomolecule-metal cluster nanomaterials. We place AgN-DNA in the general context of ligand-stabilized metal clusters and compare their properties to those of other noble metal clusters stabilized by small molecule ligands. The methods used to isolate pure AgN-DNA for analysis of composition and for studies of solution and single-emitter optical properties are discussed. We give a brief overview of structurally sensitive chiroptical studies, both theoretical and experimental, and review experiments on bringing silver clusters of distinct size and color into nanoscale DNA assemblies. Progress towards using DNA scaffolds to assemble multi-cluster arrays is also reviewed.

Determination of the structures of small gold clusters on stepped magnesia by density functional calculations.

Science.gov (United States)

Damianos, Konstantina; Ferrando, Riccardo

2012-02-21

The structural modifications of small supported gold clusters caused by realistic surface defects (steps) in the MgO(001) support are investigated by computational methods. The most stable gold cluster structures on a stepped MgO(001) surface are searched for in the size range up to 24 Au atoms, and locally optimized by density-functional calculations. Several structural motifs are found within energy differences of 1 eV: inclined leaflets, arched leaflets, pyramidal hollow cages and compact structures. We show that the interaction with the step clearly modifies the structures with respect to adsorption on the flat defect-free surface. We find that leaflet structures clearly dominate for smaller sizes. These leaflets are either inclined and quasi-horizontal, or arched, at variance with the case of the flat surface in which vertical leaflets prevail. With increasing cluster size pyramidal hollow cages begin to compete against leaflet structures. Cage structures become more and more favourable as size increases. The only exception is size 20, at which the tetrahedron is found as the most stable isomer. This tetrahedron is however quite distorted. The comparison of two different exchange-correlation functionals (Perdew-Burke-Ernzerhof and local density approximation) show the same qualitative trends. This journal is © The Royal Society of Chemistry 2012

Molecular printboards: monolayers of beta-cyclodextrins on silicon oxide surfaces.

Science.gov (United States)

Onclin, Steffen; Mulder, Alart; Huskens, Jurriaan; Ravoo, Bart Jan; Reinhoudt, David N

2004-06-22

Monolayers of beta-cyclodextrin host molecules have been prepared on SiO2 surfaces. An ordered and stable cyano-terminated monolayer was modified in three consecutive surface reactions. First, the cyanide groups were reduced to their corresponding free amines using Red Al as a reducing agent. Second, 1,4-phenylene diisothiocyanate was used to react with the amine monolayer where it acts as a linking molecule, exposing isothiocyanates that can be derivatized further. Finally, per-6-amino beta-cyclodextrin was reacted with these isothiocyanate functions to yield a monolayer exposing beta-cyclodextrin. All monolayers were characterized by contact angle measurements, ellipsometric thickness measurements, Brewster angle Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry, which indicate the formation of a densely packed cyclodextrin surface. It was demonstrated that the beta-cyclodextrin monolayer could bind suitable guest molecules in a reversible manner. A fluorescent molecule (1), equipped with two adamantyl groups for complexation, was adsorbed onto the host monolayer from solution to form a monolayer of guest molecules. Subsequently, the guest molecules were desorbed from the surface by competition with increasing beta-cyclodextrin concentration in solution. The data were fitted using a model. An intrinsic binding constant of 3.3 +/- 1 x 10(5) M(-1) was obtained, which corresponds well to previously obtained results with a divalent guest molecule on beta-cyclodextrin monolayers on gold. In addition, the number of guest molecules bound to the host surface was determined, and a surface coverage of ca. 30% was found.

Multinational Subsidiary Knowledge Protection - Do Mandates and Clusters Matter?

DEFF Research Database (Denmark)

Sofka, Wolfgang; Shehu, Edlira; de Faria, Pedro

2014-01-01

knowledge protection intensity. In addition, technological cluster regions in the host country can be expected to provide opportunities for knowledge sourcing and MNC subsidiaries may be willing to protect knowledge less intensively to participate in cluster networks. We test our hypotheses using a dataset...... of knowledge protection intensity of MNC subsidiaries. We argue that knowledge protection intensity is determined by MNC subsidiary mandates and by opportunities and risks originating from the host region. We hypothesize that not just competence-creating but also competence-exploiting mandates increase...... of 694 observations of 631 MNC subsidiaries in Germany and develop recommendations for research, managers and policy makers....

Stabilizing ultrasmall Au clusters for enhanced photoredox catalysis.

Science.gov (United States)

Weng, Bo; Lu, Kang-Qiang; Tang, Zichao; Chen, Hao Ming; Xu, Yi-Jun

2018-04-18

Recently, loading ligand-protected gold (Au) clusters as visible light photosensitizers onto various supports for photoredox catalysis has attracted considerable attention. However, the efficient control of long-term photostability of Au clusters on the metal-support interface remains challenging. Herein, we report a simple and efficient method for enhancing the photostability of glutathione-protected Au clusters (Au GSH clusters) loaded on the surface of SiO 2 sphere by utilizing multifunctional branched poly-ethylenimine (BPEI) as a surface charge modifying, reducing and stabilizing agent. The sequential coating of thickness controlled TiO 2 shells can further significantly improve the photocatalytic efficiency, while such structurally designed core-shell SiO 2 -Au GSH clusters-BPEI@TiO 2 composites maintain high photostability during longtime light illumination conditions. This joint strategy via interfacial modification and composition engineering provides a facile guideline for stabilizing ultrasmall Au clusters and rational design of Au clusters-based composites with improved activity toward targeting applications in photoredox catalysis.

Dual effects of water vapor on ceria-supported gold clusters.

Science.gov (United States)

Li, Zhimin; Li, Weili; Abroshan, Hadi; Ge, Qingjie; Li, Gao; Jin, Rongchao

2018-04-05

Atomically precise nanocatalysts are currently being intensely pursued in catalysis research. Such nanocatalysts can serve as model catalysts for gaining fundamental insights into catalytic processes. In this work we report a discovery that water vapor provokes the mild removal of surface long-chain ligands on 25-atom Au25(SC12H25)18 nanoclusters in a controlled manner. Using the resultant Au25(SC12H25)18-x/CeO2 catalyst and CO oxidation as a probe reaction, we found that the catalytic activity of cluster/CeO2 is enhanced from nearly zero conversion of CO (in the absence of water) to 96.2% (in the presence of 2.3 vol% H2O) at the same temperature (100 °C). The cluster catalysts exhibit high stability during the CO oxidation process under moisture conditions (up to 20 vol% water vapor). Water vapor plays a dual role in gold cluster-catalyzed CO oxidation. FT-IR and XPS analyses in combination with density functional theory (DFT) simulations suggest that the "-SC12H25" ligands are easier to be removed under a water vapor atmosphere, thus generating highly active sites. Moreover, the O22- peroxide species constitutes the active oxygen species in CO oxidation, evidenced by Raman spectroscopy analysis and isotope experiments on the CeO2 and cluster/CeO2. The results also indicate the perimeter sites of the interface of Au25(SC12H25)18-x/CeO2 to be active sites for catalytic CO oxidation. The controlled exposure of active sites under mild conditions is of critical importance for the utilization of clusters in catalysis.

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

Science.gov (United States)

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.

Structure and bonding in gold compounds

International Nuclear Information System (INIS)

Parish, R.V.

1988-01-01

Recent developments in chemical applications of 197 Au Moessbauer spectroscopy are reviewed. For gold(I) and gold(III), systematic variations in isomer shift and quadrupole splitting are seen as the ligands are changed; the effects of change in coordination number of the gold atoms are also systematic. Data for gold(II) systems involving gold-gold bonds lie between those for corresponding gold(I) and gold(III) materials, showing a small increase in isomer shift and a larger increase in quadrupole splitting as the oxidation state decreases; these trends are explained in terms of the structures. Data for mixed-metal cluster compounds are much more sensitive to structural effects than in homonuclear clusters. Both sets of data show systematic changes with increase in the number of metal atoms to which the gold atom is bound. The connectivity also influences the recoil-free fraction. (orig.)

Spectroscopic Identification of the Au-C Bond Formation upon Electroreduction of an Aryl Diazonium Salt on Gold.

Science.gov (United States)

Guo, Limin; Ma, Lipo; Zhang, Yelong; Cheng, Xun; Xu, Ye; Wang, Jin; Wang, Erkang; Peng, Zhangquan

2016-11-08

Electroreduction of aryl diazonium salts on gold can produce organic films that are more robust than their analogous self-assembled monolayers formed from chemical adsorption of organic thiols on gold. However, whether the enhanced stability is due to the Au-C bond formation remains debated. In this work, we report the electroreduction of an aryl diazonium salt of 4,4'-disulfanediyldibenzenediazonium on gold forming a multilayer of Au-(Ar-S-S-Ar) n , which can be further degraded to a monolayer of Au-Ar-S - by electrochemical cleavage of the S-S moieties within the multilayer. By conducting an in situ surface-enhanced Raman spectroscopic study of both the multilayer formation/degradation and the monolayer reduction/oxidation processes, coupled to density functional theory calculations, we provide compelling evidence that an Au-C bond does form upon electroreduction of aryl diazonium salts on gold and that the enhanced stability of the electrografted organic films is due to the Au-C bond being intrinsically stronger than the Au-S bond for a given phenylthiolate compound by ca. 0.4 eV.

Evaluation on corrosively dissolved gold induced by alkanethiol monolayer with atomic absorption spectroscopy

International Nuclear Information System (INIS)

Cao Zhong; Zhang Ling; Guo Chaoyan; Gong Fuchun; Long Shu; Tan Shuzhen; Xia Changbin; Xu Fen; Sun Lixian

2009-01-01

We have monitored a gold corrosive dissolution behavior accompanied in n-alkanethiol like n-dodecanethiol assembled process with in situ quartz crystal microbalance (QCM), and then observed it with atomic force microscopy (AFM) which showed an evident image of corrosive defects or holes produced on gold substrate, corresponding to gold dissolution induced by the alkanethiol molecules in the presence of oxygen. For detection of the dissolved gold defects during alkanethiol assembled process, an atomic absorption spectroscopy (AAS) has been carried out in this paper, and the detection limit for the dissolved gold could be evaluated to be 15.4 ng/mL. The amount of dissolved gold from the substrates of gold plates as functions of immersion time, acid media, solvents and thiol concentration has been examined in the oxygen saturated solutions. In comparison with in situ QCM method, the kinetics behavior of the long-term gold corrosion on the gold plates in 1.0 mmol/L of n-dodecanethiol solution determined with AAS method was a slow process, and its corrosion rate on gold dissolution could be evaluated to be about 4.4 x 10 -5 ng.cm -2 .s -1 , corresponding to 1.3 x 10 8 Au atoms.cm -2 .s -1 , that was much smaller than that of initial rate monitored with in situ QCM. Both kinetics equations obtained with QCM and AAS showed a consistent corrosion behavior on gold surfaces.

Resistivity of thiol-modified gold thin films

International Nuclear Information System (INIS)

Correa-Puerta, Jonathan; Del Campo, Valeria; Henríquez, Ricardo; Häberle, Patricio

2014-01-01

In this work, we study the effect of thiol self assembled monolayers on the electrical resistivity of metallic thin films. The analysis is based on the Fuchs–Sondheimer–Lucas theory and on electrical transport measurements. We determined resistivity change due to dodecanethiol adsorption on gold thin films. For this purpose, we controlled the deposition and annealing temperatures of the films to change the surface topography and to diminish the effect of electron grain boundary scattering. Results show that the electrical response to the absorption of thiols strongly depends on the initial topography of the surface. - Highlights: • We study the effect of self assembled monolayers on the resistivity of thin films. • Fuchs–Sondheimer theory reproduces the resistivity increase due to thiol deposition. • We determined resistivity change due to dodecanethiol deposition on gold thin films. • The electrical response strongly depends on the substrate surface topography

Resistivity of thiol-modified gold thin films

Energy Technology Data Exchange (ETDEWEB)

Correa-Puerta, Jonathan [Instituto de Física, Pontificia Universidad Católica de Valparaíso, Av. Universidad 330, Curauma, Valparaíso (Chile); Del Campo, Valeria [Departamento de Física, Universidad Técnica Federico Santa María, Av. España 1680, Valparaiso 2390123 (Chile); Henríquez, Ricardo, E-mail: ricardo.henriquez@usm.cl [Departamento de Física, Universidad Técnica Federico Santa María, Av. España 1680, Valparaiso 2390123 (Chile); Häberle, Patricio [Departamento de Física, Universidad Técnica Federico Santa María, Av. España 1680, Valparaiso 2390123 (Chile)

2014-11-03

In this work, we study the effect of thiol self assembled monolayers on the electrical resistivity of metallic thin films. The analysis is based on the Fuchs–Sondheimer–Lucas theory and on electrical transport measurements. We determined resistivity change due to dodecanethiol adsorption on gold thin films. For this purpose, we controlled the deposition and annealing temperatures of the films to change the surface topography and to diminish the effect of electron grain boundary scattering. Results show that the electrical response to the absorption of thiols strongly depends on the initial topography of the surface. - Highlights: • We study the effect of self assembled monolayers on the resistivity of thin films. • Fuchs–Sondheimer theory reproduces the resistivity increase due to thiol deposition. • We determined resistivity change due to dodecanethiol deposition on gold thin films. • The electrical response strongly depends on the substrate surface topography.

Detection of submonolayer oxygen-18 on a gold surface by nuclear reaction analysis

Energy Technology Data Exchange (ETDEWEB)

Wielunski, L.S.; Kenny, M.J.; Wieczorek, L. [Commonwealth Scientific and Industrial Research Organisation (CSIRO), Lindfield, NSW (Australia). Div. of Applied Physics

1993-12-31

A gold substrate is the preferred solid surface for formation of an organic self-assembled monolayer ( SAM ). Device fabrication process may require the gold film to be exposed to photolithographic processing and plasma treatment prior to molecular assembly. It has been observed that oxygen plasma treatment prevents the formation of SAMs; however, subsequent treatment with an argon plasma allows assembly of the organic monolayers. To understand the mechanisms involved, a plasma containing 98% {sup 18}O was used and the film surface was analysed using the {sup 18}O (p,{alpha}){sup 15}N nuclear reaction. 5 refs., 1 tab., 3 figs.

Detection of submonolayer oxygen-18 on a gold surface by nuclear reaction analysis

Energy Technology Data Exchange (ETDEWEB)

Wielunski, L S; Kenny, M J; Wieczorek, L [Commonwealth Scientific and Industrial Research Organisation (CSIRO), Lindfield, NSW (Australia). Div. of Applied Physics

1994-12-31

A gold substrate is the preferred solid surface for formation of an organic self-assembled monolayer ( SAM ). Device fabrication process may require the gold film to be exposed to photolithographic processing and plasma treatment prior to molecular assembly. It has been observed that oxygen plasma treatment prevents the formation of SAMs; however, subsequent treatment with an argon plasma allows assembly of the organic monolayers. To understand the mechanisms involved, a plasma containing 98% {sup 18}O was used and the film surface was analysed using the {sup 18}O (p,{alpha}){sup 15}N nuclear reaction. 5 refs., 1 tab., 3 figs.

Optical imaging beyond the diffraction limit by SNEM: Effects of AFM tip modifications with thiol monolayers on imaging quality

Energy Technology Data Exchange (ETDEWEB)

Cumurcu, Aysegul [Materials Science and Technology of Polymers, MESA+ Institute for Nanotechnology, University of Twente, Enschede NL-7500 (Netherlands); Dutch Polymer Institute (DPI), P.O. Box 902, 5600 AX, Eindhoven (Netherlands); Diaz, Jordi [Scientific and Technological Centers of the University of Barcelona, C/ Lluís Solé i Sabaris, 1-3, 08028 Barcelona (Spain); Lindsay, Ian D. [Nanophysics and Soft Matter Group, H.H. Wills Physics Laboratory, University of Bristol, Tyndall Avenue, Bristol BS8 1TL (United Kingdom); Beer, Sissi de; Duvigneau, Joost [Materials Science and Technology of Polymers, MESA+ Institute for Nanotechnology, University of Twente, Enschede NL-7500 (Netherlands); Schön, Peter [Materials Science and Technology of Polymers, MESA+ Institute for Nanotechnology, University of Twente, Enschede NL-7500 (Netherlands); NanoBioInterface, Research Center Design and Technology, Saxion University of Applied Sciences, 7500 KB Enschede (Netherlands); Julius Vancso, G., E-mail: g.j.vancso@utwente.nl [Materials Science and Technology of Polymers, MESA+ Institute for Nanotechnology, University of Twente, Enschede NL-7500 (Netherlands)

2015-03-15

Tip-enhanced nanoscale optical imaging techniques such as apertureless scanning near-field optical microscopy (a-SNOM) and scanning near-field ellipsometric microscopy (SNEM) applications can suffer from a steady degradation in performance due to adhesion of atmospheric contaminants to the metal coated tip. Here, we demonstrate that a self-assembled monolayer (SAM) of ethanethiol (EtSH) is an effective means of protecting gold-coated atomic force microscopy (AFM) probe tips from accumulation of surface contaminants during prolonged exposure to ambient air. The period over which they yield consistent and reproducible results for scanning near-field ellipsometric microscopy (SNEM) imaging is thus extended. SNEM optical images of a microphase separated polystyrene-block-poly (methylmethacrylate) (PS-b-PMMA) diblock copolymer film, which were captured with bare and SAM-protected gold-coated AFM probes, both immediately after coating and following five days of storage in ambient air, were compared. During this period the intensity of the optical signals from the untreated gold tip fell by 66%, while those from the SAM protected tip fell by 14%. Additionally, gold coated AFM probe tips were modified with various lengths of alkanethiols to measure the change in intensity variation in the optical images with SAM layer thickness. The experimental results were compared to point dipole model calculations. While a SAM of 1-dodecanethiol (DoSH) was found to strongly suppress field enhancement we find that it can be locally removed from the tip apex by deforming the molecules under load, restoring SNEM image contrast. - Highlights: • SAM of ethanethiol is used to prevent contamination of gold coated tips. • Functionalizing gold coated tips with a SAM lead to reproducible SNEM imaging. • Point dipole model agreed with the experimental results of the SNEM images. • SAM of 1-dodecanethiol was found to strongly suppress field enhancement in SNEM. • SAM of 1-dodecanethiol

Electron energy loss spectroscopy of gold nanoparticles on graphene

International Nuclear Information System (INIS)

DeJarnette, Drew; Roper, D. Keith

2014-01-01

Plasmon excitation decay by absorption, scattering, and hot electron transfer has been distinguished from effects induced by incident photons for gold nanoparticles on graphene monolayer using electron energy loss spectroscopy (EELS). Gold nano-ellipses were evaporated onto lithographed graphene, which was transferred onto a silicon nitride transmission electron microscopy grid. Plasmon decay from lithographed nanoparticles measured with EELS was compared in the absence and presence of the graphene monolayer. Measured decay values compared favorably with estimated radiative and non-radiative contributions to decay in the absence of graphene. Graphene significantly enhanced low-energy plasmon decay, increasing mode width 38%, but did not affect higher energy plasmon or dark mode decay. This decay beyond expected radiative and non-radiative mechanisms was attributed to hot electron transfer, and had quantum efficiency of 20%, consistent with previous reports

Documentation to the workshop 'Cluster in the environmental protection economy'; Dokumentation zum Workshop ''Cluster in der Umweltschutzwirtschaft''

Energy Technology Data Exchange (ETDEWEB)

NONE

2009-12-11

Within the workshop 'Cluster in the environmental protection economy' at the Umweltbundesamt (Dessau-Rosslau, Federal Republic of Germany) at 27th November, 2008, the following lectures were held: (a) Which contribution can cluster and cluster politics contribute to the promotion of the environmental protection economy? (Harald Legler); (b) Cluster in the environmental protection economy: Targets and expectations (Dieter Rehfeld); (c) Demands at the management of clusters (Karin Hoerhan); (d) Demands at the cluster politics in the environmental protection economy (Bernhard Hausberg); (e) Photovoltaics in Eastern Germany (Johann Wackenbauer); (f) Automotive industry in Bergisches Land (Thomas Lemken); (g) Competence centre environment Augsburg-Schwaben (Egon Beckord).

Cyclic voltammetry and scanning electrochemical microscopy studies of methylene blue immobilized on the self-assembled monolayer of n-dodecanethiol

International Nuclear Information System (INIS)

Salamifar, Seyed Ehsan; Mehrgardi, Masoud Ayatollahi; Kazemi, Sayed Habib; Mousavi, Mir Fazllollah

2010-01-01

Electron transfer (ET) kinetics through n-dodecanethiol (C 12 SH) self-assembled monolayer on gold electrode was studied using cyclic voltammetry (CV), scanning electrochemical microscopy (SECM) and electrochemical impedance spectroscopy (EIS). An SECM model for compensating pinhole contribution, was used to measure the ET kinetics of solution-phase probes of ferrocyanide/ferricyanide (Fe(CN) 6 4-/3- ) and ferrocenemethanol/ferrociniummethanol (FMC 0/+ ) through the C 12 SH monolayer yielding standard tunneling rate constant (k ET 0 ) of (4 ± 1) x 10 -11 and (3 ± 1) x 10 -10 cm s -1 for Fe(CN) 6 4-/3- and FMC 0/+ respectively. Decay tunneling constants (β) of 0.97 and 0.96 A -1 for saturated alkane thiol chains were obtained using Fe(CN) 6 4- and FMC respectively. Also, it was found that methylene blue (MB) molecules are effectively immobilized on the C 12 SH monolayer and can mediate the ET between the solution-phase probes and underlying gold substrate. SECM-mediated model was used to simultaneously measure the bimolecular ET between the solution-phase probes and the monolayer-immobilized MB molecules, as well as tunneling ET between the monolayer-immobilized MB molecules and the underlying gold electrode, allowing the measurement of k BI = (5 ± 1) x 10 6 and (4 ± 2) x 10 7 cm 3 mol -1 s -1 for the bimolecular ET and k ET/MB 0 =(1±0.3)x10 -3 and (7 ± 3) x 10 -2 s -1 for the standard tunneling rate constant of ET using Fe(CN) 6 4-/3- and FMC 0/+ probes respectively.

Sensitive detection of plastic explosives with self-assembled monolayer-coated microcantilevers

Science.gov (United States)

Pinnaduwage, L. A.; Boiadjiev, V.; Hawk, J. E.; Thundat, T.

2003-08-01

We report the detection of 10-30 parts-per-trillion levels of pentaerythritol tetranitrate and hexahydro-1,3,5-triazine within 20 s of exposure to a silicon microcantilever with its gold surface modified with a self-assembled monolayer of 4-mercaptobenzoic acid. These measurements correspond to a limit of detection of a few fg.

Geometric, stability, and electronic properties of gold-doped Pd clusters (Pd{sub n}Au, n = 3~20)

Energy Technology Data Exchange (ETDEWEB)

Huan, Hao; Chen, Yan; Wang, Tao; Ye, Xiang, E-mail: yexiang@shnu.edu.cn [Shanghai Normal University, Department of Physics (China); Gu, Xiao, E-mail: gx@cqu.edu.cn [Chongqing University, Department of Applied Physics (China)

2016-11-15

The structure, stability, and electronic properties of Pd{sub n}Au (n = 3~20) clusters are studied by density functional theory. The results show that the clusters studied here prefer three-dimensional structures even with very small atom number. It is found that the binding energies of Pd{sub n}Au clusters are higher than the corresponding pure Pd{sub n} clusters with the same atom number. Most Pd{sub n}Au clusters studied here are magnetic with magnetic moments ranging from 1.0 to 7.0 μ{sub B.} The dissociation energies of Pd atoms are lower than the doped gold atom, that is the doped Au atom will increase the mother clusters stability and activity.

Formation of n-Alkyl Monolayers by Organomercury Deposition on Gold

Czech Academy of Sciences Publication Activity Database

Scholz, F.; Kaletová, Eva; Stensrud, Elizabeth; Ford, W. E.; Kohutová, Anna; Mucha, Malgorzata; Stibor, Ivan; Michl, Josef; Wrochem von, F.

2013-01-01

Roč. 4, č. 16 (2013), s. 2624-2629 ISSN 1948-7185 R&D Projects: GA ČR GA203/07/1619; GA ČR GA203/09/0705 EU Projects: European Commission(XE) 213382 - FUNMOL; European Commission(XE) 227756 - DIPOLAR ROTOR ARRAY Institutional support: RVO:61388963 Keywords : self-assembled monolayers * ray photoelectron-spectroscopy * altitudinal molecular rotors Subject RIV: CC - Organic Chemistry Impact factor: 6.687, year: 2013

Faradaic impedance titration and control of electron transfer of 1-(12-mercaptododecyl)imidazole monolayer on a gold electrode

International Nuclear Information System (INIS)

Hwang, Seongpil; Lee, Bang Sook; Chi, Young Shik; Kwak, Juhyoun; Choi, Insung S.; Lee, Sang-gi

2008-01-01

In this work, we studied interfacial proton transfer of the self-assembled monolayer (SAM) of 1-(12-mercaptododecyl)imidazole on a gold electrode by faradaic impedance titration method with Fe(CN) 6 3- as an anionic redox probe molecule. The surface pK 1/2 was found to be 7.3, which was nearly the same as that of 1-alkylimidazole in solution. We also investigated the electrochemical properties of the SAM-modified electrode by cyclic voltammetry. Cyclic voltammetry was performed (1) in the solution containing Fe(CN) 6 3- with repeated alternation of pH values to investigate the electrostatic interaction of the protonated or deprotonated imidazole with Fe(CN) 6 3- and (2) in the acidic or basic electrolyte containing Ru(NH 3 ) 6 3+ as a cationic redox probe to verify the effect of the polarity of a redox probe. We observed the reversible adsorption/desorption of Fe(CN) 6 3- and concluded that the adsorbed Fe(CN) 6 3- catalyzed the electron transfer of both Fe(CN) 6 3- itself and cationic Ru(NH 3 ) 6 3+

Probing the conformational energetics of alkyl thiols on gold surfaces by means of a morphing/steering non-equilibrium tool.

Science.gov (United States)

Piserchia, Andrea; Zerbetto, Mirco; Frezzato, Diego

2015-03-28

In this work we show that a non-equilibrium statistical tool based on Jarzynski's equality (JE) can be applied to achieve a sufficiently accurate mapping of the torsion free energy, bond-by-bond, for an alkyl thiol ligand tethered to a gold surface and sensing the presence of the surrounding cluster of similar chains. The strength of our approach is the employment of a strategy to let grow the internal energetics of the whole system (namely, the "energy morphing" stage recently presented by us in J. Comput. Chem., 2014, 35, 1865-1881) before initiating the rotational steering, which yields accurate results in terms of statistical uncertainties and bias on the free energy profiles. The work is mainly methodological and illustrates the feasibility of this kind of inspection on nanoscale molecular clusters with conformational flexibility. The outcomes for the archetype of self-assembled-monolayers considered here, a regular pattern of 10-carbon alkyl thiols on an ideal gold surface, give information on the conformational mobility of the ligands. Notably, such information is unlikely to be obtained by means of standard equilibrium techniques or by conventional molecular dynamics simulations.

Time-of-flight secondary-ion mass spectrometry on thiole self-assembly monolayers on gold; Flugzeit-Sekundaerionenmassenspektrometrie an Thiol self assembly Monolagen auf Gold

Energy Technology Data Exchange (ETDEWEB)

Schroeder, M.

2006-07-01

Aim of this thesis was to get a deeper understanding for the influence of different matrix effects on the emission of molecular secondary ions. For the estimation of the influence of the primary-ion surface interaction a series of different primary-ion species was applied, which differ by mass, kinetic energy, and composition (monoatomic or polyatomic). In the framework of the presented results different matrix effects were studied. For this systematically the influence of the substrate-thiolate, the thiolate-thiolate, and the primary-ion substrate interaction on the formation of characteristic secondary ions was quantified. For the corresponding considerations beside the thiolate secondary ions M{sup -} the gold-thiolate clusters of the type Au{sub x+1}M{sub x}{sup -} were referred to.

Adsorption behavior of Fe atoms on a naphthalocyanine monolayer on Ag(111) surface

Energy Technology Data Exchange (ETDEWEB)

Yan, Linghao; Wu, Rongting; Bao, Deliang; Ren, Junhai; Zhang, Yanfang; Zhang, Haigang; Huang, Li; Wang, Yeliang; Du, Shixuan; Huan, Qing; Gao, Hong-Jun

2015-05-29

Adsorption behavior of Fe atoms on a metal-free naphthalocyanine (H₂Nc) monolayer on Ag(111) surface at room temperature has been investigated using scanning tunneling microscopy combined with density functional theory (DFT) based calculations. We found that the Fe atoms adsorbed at the centers of H₂Nc molecules and formed Fe-H₂Nc complexes at low coverage. DFT calculations show that the configuration of Fe at the center of a molecule is the most stable site, in good agreement with the experimental observations. After an Fe-H₂Nc complex monolayer was formed, the extra Fe atoms self-assembled to Fe clusters of uniform size and adsorbed dispersively at the interstitial positions of Fe-H₂Nc complex monolayer. Furthermore, the H₂Nc monolayer grown on Ag(111) could be a good template to grow dispersed magnetic metal atoms and clusters at room temperature for further investigation of their magnetism-related properties.

Controlling the reproducibility of Coulomb blockade phenomena for gold nanoparticles on an organic monolayer/silicon system.

Science.gov (United States)

Caillard, L; Sattayaporn, S; Lamic-Humblot, A-F; Casale, S; Campbell, P; Chabal, Y J; Pluchery, O

2015-02-13

Two types of highly ordered organic layers were prepared on silicon modified with an amine termination for binding gold nanoparticles (AuNPs). These two grafted organic monolayers (GOMs), consisting of alkyl chains with seven or 11 carbon atoms, were grafted on oxide-free Si(111) surfaces as tunnel barriers between the silicon electrode and the AuNPs. Three kinds of colloidal AuNPs were prepared by reducing HAuCl4 with three different reactants: citrate (Turkevich synthesis, diameter ∼16 nm), ascorbic acid (diameter ∼9 nm), or NaBH4 (Natan synthesis, diameter ∼7 nm). Scanning tunnel spectroscopy (STS) was performed in a UHV STM at 40 K, and Coulomb blockade behaviour was observed. The reproducibility of the Coulomb behavior was analysed as a function of several chemical and physical parameters: size, crystallinity of the AuNPs, influence of surrounding surfactant molecules, and quality of the GOM/Si interface (degree of oxidation after the full processing). Samples were characterized with scanning tunneling microscope, STS, atomic force microscope, Fourier transform infrared spectroscopy, x-ray photoelectron spectroscopy (XPS), and high resolution transmission electronic microscope. We show that the reproducibility in observing Coulomb behavior can be as high as ∼80% with the Natan synthesis of AuNPs and GOMs with short alkyl chains.

Molecular monolayers and interfacial electron transfer of pseudomonas aeruginosa azurin on Au(111)

DEFF Research Database (Denmark)

Chi, Qijin; Zhang, Jingdong; Nielsen, Jens Ulrik

2000-01-01

disulfide group to form a monolayer. The adsorption of this protein on Au(111) via a gold-sulfur binding mode is further supported by XPS measurements. In situ STM images with molecular resolution have been recorded and show a dense monolayer organization of adsorbed azurin molecules. Direct electron......We provide a comprehensive approach to the formation and characterization of molecular monolayers of the blue copper protein Pseudomonas aeruginosa azurin on Au(111) in aqueous ammonium acetate solution. Main issues are adsorption patterns, reductive desorption, properties of the double layer......, and long-range electrochemical electron transfer between the electrode and the copper center. Voltammetry, electrochemical impedance spectroscopy (EIS), in situ scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS) have been employed to disclose features of these issues. Zn...

Atomically Precise Nanocluster Assemblies Encapsulating Plasmonic Gold Nanorods.

Science.gov (United States)

Chakraborty, Amrita; Fernandez, Ann Candice; Som, Anirban; Mondal, Biswajit; Natarajan, Ganapati; Paramasivam, Ganesan; Lahtinen, Tanja; Häkkinen, Hannu; Nonappa, Nonappa; Pradeep, Thalappil

2018-04-01

We present the self-assembled structures of atomically precise, ligand-protected noble metal nanoclusters leading to encapsulation of plasmonic gold nanorods (GNRs). Unlike highly sophisticated DNA nanotechnology, our approach demonstrates a strategically simple hydrogen bonding-directed self-assembly of nanoclusters leading to octahedral nanocrystals encapsulating GNRs. Specifically, we use the p-mercaptobenzoic acid (pMBA) protected atomically precise nanocluster, Na4[Ag44(pMBA)30] and pMBA functionalized GNRs. High resolution transmission and scanning transmission electron tomographic reconstructions suggest that the geometry of the GNR surface is responsible for directing the assembly of silver nanoclusters via H-bonding leading to octahedral symmetry. Further, use of water dispersible gold nanoclusters, Au~250(pMBA)n and Au102(pMBA)44 also formed layered shells encapsulating GNRs. Such cluster assemblies on colloidal particles present a new category of precision hybrids with diverse possibilities. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cyclic voltammetry and scanning electrochemical microscopy studies of methylene blue immobilized on the self-assembled monolayer of n-dodecanethiol

Energy Technology Data Exchange (ETDEWEB)

Salamifar, Seyed Ehsan [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of); Mehrgardi, Masoud Ayatollahi [Department of Chemistry, University of Isfahan, Isfahan (Iran, Islamic Republic of); Kazemi, Sayed Habib [Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan (Iran, Islamic Republic of); Mousavi, Mir Fazllollah, E-mail: mousavim@modares.ac.i [Department of Chemistry, Tarbiat Modares University, P.O. Box 14115-175, Tehran (Iran, Islamic Republic of)

2010-12-30

Electron transfer (ET) kinetics through n-dodecanethiol (C{sub 12}SH) self-assembled monolayer on gold electrode was studied using cyclic voltammetry (CV), scanning electrochemical microscopy (SECM) and electrochemical impedance spectroscopy (EIS). An SECM model for compensating pinhole contribution, was used to measure the ET kinetics of solution-phase probes of ferrocyanide/ferricyanide (Fe(CN){sub 6}{sup 4-/3-}) and ferrocenemethanol/ferrociniummethanol (FMC{sup 0/+}) through the C{sub 12}SH monolayer yielding standard tunneling rate constant (k{sub ET}{sup 0}) of (4 {+-} 1) x 10{sup -11} and (3 {+-} 1) x 10{sup -10} cm s{sup -1} for Fe(CN){sub 6}{sup 4-/3-} and FMC{sup 0/+} respectively. Decay tunneling constants ({beta}) of 0.97 and 0.96 A{sup -1} for saturated alkane thiol chains were obtained using Fe(CN){sub 6}{sup 4-} and FMC respectively. Also, it was found that methylene blue (MB) molecules are effectively immobilized on the C{sub 12}SH monolayer and can mediate the ET between the solution-phase probes and underlying gold substrate. SECM-mediated model was used to simultaneously measure the bimolecular ET between the solution-phase probes and the monolayer-immobilized MB molecules, as well as tunneling ET between the monolayer-immobilized MB molecules and the underlying gold electrode, allowing the measurement of k{sub BI} = (5 {+-} 1) x 10{sup 6} and (4 {+-} 2) x 10{sup 7} cm{sup 3} mol{sup -1} s{sup -1} for the bimolecular ET and k{sub ET/MB}{sup 0}=(1{+-}0.3)x10{sup -3} and (7 {+-} 3) x 10{sup -2} s{sup -1} for the standard tunneling rate constant of ET using Fe(CN){sub 6}{sup 4-/3-} and FMC{sup 0/+} probes respectively.

Cluster-to-cluster transformation among Au6, Au8 and Au11 nanoclusters.

Science.gov (United States)

Ren, Xiuqing; Fu, Junhong; Lin, Xinzhang; Fu, Xuemei; Yan, Jinghui; Wu, Ren'an; Liu, Chao; Huang, Jiahui

2018-05-22

We present the cluster-to-cluster transformations among three gold nanoclusters, [Au6(dppp)4]2+ (Au6), [Au8(dppp)4Cl2]2+ (Au8) and [Au11(dppp)5]3+ (Au11). The conversion process follows a rule that states that the transformation of a small cluster to a large cluster is achieved through an oxidation process with an oxidizing agent (H2O2) or with heating, while the conversion of a large cluster to a small one occurs through a reduction process with a reducing agent (NaBH4). All the reactions were monitored using UV-Vis spectroscopy and ESI-MS. This work may provide an alternative approach to the synthesis of novel gold nanoclusters and a further understanding of the structural transformation relationship of gold nanoclusters.

Study of gold-platinum and platinum-gold surface modification and its influence on hydrogen evolution and oxygen reduction

Directory of Open Access Journals (Sweden)

BRANIMIR N. GRGUR

2005-02-01

Full Text Available Surface modification of the electrodes was conducted from sulfuric acid solutions containing the corresponding metal–chloride complexes using cyclic voltammetry. Comparing the charges of the hydrogen underpotential deposition region, and the corresponding oxide reduction regions, it is concluded that a platinum overlayer on gold forms 3D islands, while gold on platinum forms 2D islands. Foreign metals present in an amount of up to one monolayer exert an influence on the change in reaction rate with respect to both hydrogen evolution (HER and oxygen reduction (ORR reactions. Aplatinum overlayer on a gold substrate increases the activity forHER and for ORR, compared with pure gold. These results can be understood in terms of a simple model, in which the change in the H and OH binding energies are directly proportional to the shift of the d-bond center of the overlayer. On the contrary, a gold layer on platinum slightly decreases the activity for both reactions compared with pure platinum.

Plasmon resonances in large noble-metal clusters

International Nuclear Information System (INIS)

Soennichsen, C; Franzl, T; Wilk, T; Plessen, G von; Feldmann, J

2002-01-01

We investigate the optical properties of spherical gold and silver clusters with diameters of 20 nm and larger. The light scattering spectra of individual clusters are measured using dark-field microscopy, thus avoiding inhomogeneous broadening effects. The dipolar plasmon resonances of the clusters are found to have nearly Lorentzian line shapes. With increasing size we observe polaritonic red-shifts of the plasmon line and increased radiation damping for both gold and silver clusters. Apart from some cluster-to-cluster variations of the plasmon lines, agreement with Mie theory is reasonably good for the gold clusters. However, it is less satisfactory for the silver clusters, possibly due to cluster faceting or chemical effects

Mercaptobenzothiazole on gold biosensor systems for organophosphate and carbamate pesticide compounds

CSIR Research Space (South Africa)

Somerset, VS

2010-05-01

Full Text Available .............................................. 179 2.5.2.1.3 Poly(2,5-dimethoxy aniline), PDMA........................................ 182 2.5.3 Conducting mechanism of PANI .......................................................... 184 2.5.4 Synthesis of polyaniline, PANI... of mercaptobenzothiazole self-assembled monolayer on gold electrode 242 3.4.2 Characterisation of Au/MBT SAM-modified electrode ....................... 242 3.5 Synthesis of polyaniline films onto gold disk (Au), MBT SAM modified electrode...

Stabilization of gold nanoparticles by 6-mercaptopurine monolayers. Effects of the solvent properties.

Science.gov (United States)

Viudez, Alfonso J; Madueño, Rafael; Pineda, Teresa; Blázquez, Manuel

2006-09-14

6-Mercaptopurine-coated gold nanoparticles (6MP-AuNPs) have been prepared by modification of the nanoparticle surface with 6MP upon displacement of the protective layer of citrate anions. The modification has been studied by UV-vis and FTIR spectroscopies. A study of the stability of these 6MP-AuNPs in aqueous solutions as a function of ionic strength and pH has shown the importance of the charges on the stabilization. The protonation of N9 of the 6MP molecules brings about a sudden flocculation phenomenon. However, the flocculation is reversible upon changing the pH to values where the molecules become newly charged. Evidence of the competence between the interaction of capping solvent molecules and the attractive forces between particles is also shown in this paper.

Gold/silver/gold trilayer films on nanostructured polycarbonate substrates for direct and label-free nanoplasmonic biosensing.

Science.gov (United States)

López-Muñoz, Gerardo A; Estévez, M-Carmen; Vázquez-García, Marc; Berenguel-Alonso, Miguel; Alonso-Chamarro, Julián; Homs-Corbera, Antoni; Lechuga, Laura M

2018-05-01

Ultrasmooth gold/silver/gold trilayer nanostructured plasmonic sensors were obtained using commercial Blu-ray optical discs as nanoslits-based flexible polymer substrates. A thin gold film was used as an adhesion and nucleation layer to improve the chemical stability and reduce the surface roughness of the overlying silver film, without increasing ohmic plasmon losses. The structures were physically and optically characterized and compared with nanostructures of single gold layer. Ultrasmooth and chemically stable trilayer nanostructures with a surface roughness <0.5 nm were obtained following a simple and reproducible fabrication process. They showed a figure of merit (FOM) value up to 69.2 RIU -1 which is significantly higher (more than 95%) than the gold monolayer counterpart. Their potential for biosensing was demonstrated by employing the trilayer sensor for the direct and refractometric (label-free) detection of C-reactive protein (CRP) biomarker in undiluted urine achieving a Limit of Detection (LOD) in the pM order. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Is the largest aqueous gold cluster a superatom complex? Electronic structure & optical response of the structurally determined Au146(p-MBA)57.

Science.gov (United States)

López-Lozano, Xóchitl; Plascencia-Villa, G; Calero, G; Whetten, R L; Weissker, Hans-Christian

2017-12-07

The new water-soluble gold cluster Au 146 (p-MBA) 57 , the structure of which has been recently determined at sub-atomic resolution by Vergara et al., is the largest aqueous gold cluster ever structurally determined and likewise the smallest cluster with a stacking fault. The core presents a twinned truncated octahedron, while additional peripheral gold atoms follow a C 2 rotational symmetry. According to the usual counting rules of the superatom complex (SAC) model, the compound attains a number of 92 SAC electrons if the overall net charge is 3- (three additional electrons). As this is the number of electrons required for a major shell closing, the question arises of whether Au 146 (p-MBA) 57 should be regarded as a superatom complex. Starting from the experimental coordinates we have analyzed the structure using density-functional theory. The optimized (relaxed) structure retains all the connectivity of the experimental coordinates, while removing much of its irregularities in interatomic distances, thereby enhancing the C 2 -symmetry feature. On analyzing the angular-momentum-projected states, we show that, despite a small gap, the electronic structure does not exhibit SAC model character. In addition, optical absorption spectra are found to be relatively smooth compared to the example of the Au 144 (SR) 60 cluster. The Au 146 (SR) 57 does not derive its stability from SAC character; it cannot be considered as a superatom complex.

Lipophilic phosphorescent gold(I) clusters as selective probes for visualization of lipid droplets by two-photon microscopy

Czech Academy of Sciences Publication Activity Database

Koshel, E. I.; Cheluskin, P. S.; Melnikov, A. S.; Serdobintsev, P. Y.; Stolbovaia, A. Y.; Saifitdinova, A. F.; Scheslavskiy, V. I.; Chernyavskiy, Oleksandr; Gaginskaya, E. R.; Koshevoy, I. O.; Tunik, S. P.

2017-01-01

Roč. 332, Jan 1 (2017), s. 122-130 ISSN 1010-6030 R&D Projects: GA MŠk(CZ) LM2015062 Institutional support: RVO:67985823 Keywords : polynuclear gold-alkynyl cluster * lipophilic probe * phosphorescence * adipocyte * two-photon microscopy * PLIM Subject RIV: EB - Genetics ; Molecular Biology OBOR OECD: Medical laboratory technology (including laboratory samples analysis Impact factor: 2.625, year: 2016

Cosensitization Properties of Glutathione-Protected Au25 Cluster on Ruthenium Dye-Sensitized TiO2 Photoelectrode

Directory of Open Access Journals (Sweden)

Kazuya Nakata

2013-01-01

Full Text Available Cosensitization by glutathione-protected Au25 clusters on Ru complex, N719-sensitized TiO2 photoelectrodes is demonstrated. Glutathione-protected Au25 clusters showed no significant changes in properties after adsorption onto TiO2 particles, as confirmed by optical absorption spectroscopy, transmission electron microscopy, and laser desorption/ionization mass spectrometry. Adsorption property of the glutathione-protected Au25 clusters depends on the pH, which affects the incident photon-to-current conversion efficiency (IPCE of the TiO2 photoelectrode containing Au25 clusters. When pH 7. The IPCE of a TiO2 photoelectrode sensitized by both glutathione-protected Au25 clusters and N719 was increased compared with photoelectrodes containing either glutathione-protected Au25 clusters or N719, which suggests that glutathione-protected Au25 clusters act as a coadsorbent for N719 on TiO2 photoelectrodes. This is also supported by the results that the IPCE of N719-sensitized TiO2 photoelectrodes increased upon addition of glutathione. Furthermore, cosensitization by glutathione-protected Au25 clusters on N719-sensitized TiO2 photoelectrodes allows that wavelength of photoelectric conversion was extended to the near infrared (NIR region. These results suggest that glutathione-protected Au25 clusters act not only as a coadsorbent to increase IPCE but also as an NIR-active sensitizer.

Manipulation of charge carrier injection into organic field-effect transistors by self-assembled monolayers of alkanethiols

NARCIS (Netherlands)

Asadi, Kamal; Gholamrezaie, Fatemeh; Smits, Edsger C. P.; Blom, Paul W. M.; de Boer, Bert

2007-01-01

Charge carrier injection into two semiconducting polymers is investigated in field-effect transistors using gold source and drain electrodes that are modified by self-assembled monolayers of alkanethiols and perfluorinated alkanethiols. The presence of an interfacial dipole associated with the

Controlled AFM detachments and movement of nanoparticles: gold clusters on HOPG at different temperatures.

Science.gov (United States)

Tripathi, Manoj; Paolicelli, Guido; D'Addato, Sergio; Valeri, Sergio

2012-06-22

The effect of temperature on the onset of movement of gold nanoclusters (diameter 27 nm) deposited on highly oriented pyrolytic graphite (HOPG) has been studied by atomic force microscopy (AFM) techniques. Using the AFM with amplitude modulation (tapping mode AFM) we have stimulated and controlled the movement of individual clusters. We show how, at room temperature, controlled detachments and smooth movements can be obtained for clusters having dimensions comparable to or smaller than the tip radius. Displacement is practically visible in real time and it can be started and stopped easily by adjusting only one parameter, the tip amplitude oscillation. Analysing the energy dissipation signal at the onset of nanocluster sliding we evaluated a detachment threshold energy as a function of temperature in the range 300-413 K. We also analysed single cluster thermal induced displacement and combining this delicate procedure with AFM forced movement behaviour we conclude that detachment threshold energy is directly related to the activation energy of nanocluster diffusion and it scales linearly with temperature as expected for a single-particle thermally activated process.

Ultrasensitive electrochemical biosensor based on the oligonucleotide self-assembled monolayer-mediated immunosensing interface

Energy Technology Data Exchange (ETDEWEB)

Liu, Dengyou; Luo, Qimei [Science College of Hunan Agricultural University, Changsha 410128 (China); Deng, Fawen [The Fourth Hospital of Chansha, Changsha 410006 (China); Li, Zhen [Science College of Hunan Agricultural University, Changsha 410128 (China); Li, Benxiang, E-mail: 172170960@qq.com [Science College of Hunan Agricultural University, Changsha 410128 (China); Shen, Zhifa, E-mail: shenzhifa@wmu.edu.cn [Key Laboratory of Laboratory Medicine, Ministry of Education, Zhejiang Provincial Key Laboratory of Medical Genetics, College of Laboratory Medicine and Life Sciences, Wenzhou Medical University, Wenzhou 325035 (China)

2017-06-08

Highly sensitive and selective quantitation of a variety of proteins over a wide concentration range is highly desirable for increased accuracy of biomarker detection or for multidisease diagnostics. In the present contribution, using human immunoglobulin G (HIgG) as the model target protein, an electrochemical ultrasensitive immunosensing platform was developed based on the oligonucleotide self-assembled monolayer-mediated (OSAM) sensing interface. For this immunosensor, the “signal-on” signaling mechanism and enzymatic signal amplification effect were integrated into one sensing architecture. Moreover, the thiolated flexible single-stranded DNAs immobilized onto gold electrode surface not only performs the wobbling motion to facilitate the electron transfer between the electrode surface and biosensing layer but also fundamentally prohibiting the direct interaction of proteins with gold substrate. Thus, the electrochemical signal could be efficiently enhanced and the unspecific adsorption or cross-reaction might be eliminated. As a result, utilizing the newly-proposed immunosensor, the HIgG can be detected down to 0.5 ng/mL, and the high detection specificity is offered. The successful design of OSAM and the highly desirable detection capability of new immunosensor are expected to provide a perspective for fabricating new robust immunosensing platform and for promising potential of oligonucleotide probe in biological research and biomedical diagnosis. - Highlights: • An electrochemical ultrasensitive immunosensing platform was developed based on the oligonucleotide self-assembled monolayer (OASM). • OASM severs as a flexible monolayer to promote electron transfer and prohibits the direct interaction of proteins with gold substrate. • The electrochemical signal is efficiently enhanced and the unspecific adsorption or cross-reaction is eliminated. • Target protein can be detected down to 0.5 ng/mL, and the high detection specificity can be obtained. �

Vacancy clusters at nanoparticle surfaces

Energy Technology Data Exchange (ETDEWEB)

Xu, J.; Moxom, J.; Somieski, B.; White, C.W. [Oak Ridge National Lab., TN (United States); Mills, A.P. Jr. [Bell Labs., Lucent Technologies, Murray Hill, NJ (United States); Suzuki, R.; Ishibashi, S. [Electrotechnical Lab., Tsukuba, Ibaraki (Japan); Ueda, A.; Henderson, D. [Physics Dept., Fisk Univ., Nashville, TN (United States)

2001-07-01

We detect vacancy clusters at Au nanoparticle surfaces using a combination of positron lifetime spectroscopy, 1- detector, and 2-detector measurements of Doppler broadening of annihilation radiation. Gold nanoparticles are formed by MeV implantation of gold ions into MgO (100) followed by annealing. Clusters of two Mg and two O vacancies (v{sub 4}) are attached to the gold nanoparticle surfaces within the projected range (R{sub p}). (orig.)

Vacancy clusters at nanoparticle surfaces

International Nuclear Information System (INIS)

Xu, J.; Moxom, J.; Somieski, B.; White, C.W.; Mills, A.P. Jr.; Suzuki, R.; Ishibashi, S.; Ueda, A.; Henderson, D.

2001-01-01

We detect vacancy clusters at Au nanoparticle surfaces using a combination of positron lifetime spectroscopy, 1- detector, and 2-detector measurements of Doppler broadening of annihilation radiation. Gold nanoparticles are formed by MeV implantation of gold ions into MgO (100) followed by annealing. Clusters of two Mg and two O vacancies (v 4 ) are attached to the gold nanoparticle surfaces within the projected range (R p ). (orig.)

A comparison of three clustering methods for finding subgroups in MRI, SMS or clinical data: SPSS TwoStep Cluster analysis, Latent Gold and SNOB.

Science.gov (United States)

Kent, Peter; Jensen, Rikke K; Kongsted, Alice

2014-10-02

There are various methodological approaches to identifying clinically important subgroups and one method is to identify clusters of characteristics that differentiate people in cross-sectional and/or longitudinal data using Cluster Analysis (CA) or Latent Class Analysis (LCA). There is a scarcity of head-to-head comparisons that can inform the choice of which clustering method might be suitable for particular clinical datasets and research questions. Therefore, the aim of this study was to perform a head-to-head comparison of three commonly available methods (SPSS TwoStep CA, Latent Gold LCA and SNOB LCA). The performance of these three methods was compared: (i) quantitatively using the number of subgroups detected, the classification probability of individuals into subgroups, the reproducibility of results, and (ii) qualitatively using subjective judgments about each program's ease of use and interpretability of the presentation of results.We analysed five real datasets of varying complexity in a secondary analysis of data from other research projects. Three datasets contained only MRI findings (n = 2,060 to 20,810 vertebral disc levels), one dataset contained only pain intensity data collected for 52 weeks by text (SMS) messaging (n = 1,121 people), and the last dataset contained a range of clinical variables measured in low back pain patients (n = 543 people). Four artificial datasets (n = 1,000 each) containing subgroups of varying complexity were also analysed testing the ability of these clustering methods to detect subgroups and correctly classify individuals when subgroup membership was known. The results from the real clinical datasets indicated that the number of subgroups detected varied, the certainty of classifying individuals into those subgroups varied, the findings had perfect reproducibility, some programs were easier to use and the interpretability of the presentation of their findings also varied. The results from the artificial datasets

Method of making gold thiolate and photochemically functionalized microcantilevers

Science.gov (United States)

Boiadjiev, Vassil I [Knoxville, TN; Brown, Gilbert M [Knoxville, TN; Pinnaduwage, Lal A [Knoxville, TN; Thundat, Thomas G [Knoxville, TN; Bonnesen, Peter V [Knoxville, TN; Goretzki, Gudrun [Nottingham, GB

2009-08-25

Highly sensitive sensor platforms for the detection of specific reagents, such as chromate, gasoline and biological species, using microcantilevers and other microelectromechanical systems (MEMS) whose surfaces have been modified with photochemically attached organic monolayers, such as self-assembled monolayers (SAM), or gold-thiol surface linkage are taught. The microcantilever sensors use photochemical hydrosilylation to modify silicon surfaces and gold-thiol chemistry to modify metallic surfaces thereby enabling individual microcantilevers in multicantilever array chips to be modified separately. Terminal vinyl substituted hydrocarbons with a variety of molecular recognition sites can be attached to the surface of silicon via the photochemical hydrosilylation process. By focusing the activating UV light sequentially on selected silicon or silicon nitride hydrogen terminated surfaces and soaking or spotting selected metallic surfaces with organic thiols, sulfides, or disulfides, the microcantilevers are functionalized. The device and photochemical method are intended to be integrated into systems for detecting specific agents including chromate groundwater contamination, gasoline, and biological species.

Nanoscale Trapping and Squeeze-Out of Confined Alkane Monolayers.

Science.gov (United States)

Gosvami, N N; O'Shea, S J

2015-12-01

We present combined force curve and conduction atomic force microscopy (AFM) data for the linear alkanes CnH2n+2 (n = 10, 12, 14, 16) confined between a gold-coated AFM tip and a graphite surface. Solvation layering is observed in the force curves for all liquids, and conduction AFM is used to study in detail the removal of the confined (mono)layer closest to the graphite surface. The squeeze-out behavior of the monolayer can be very different depending upon the temperature. Below the monolayer melting transition temperatures the molecules are in an ordered state on the graphite surface, and fast and complete removal of the confined molecules is observed. However, above the melting transition temperature the molecules are in a disordered state, and even at large applied pressure a few liquid molecules are trapped within the tip-sample contact zone. These findings are similar to a previous study for branched alkanes [ Gosvami Phys. Rev. Lett. 2008, 100, 076101 ], but the observation for the linear alkane homologue series demonstrates clearly the dependence of the squeeze-out and trapping on the state of the confined material.

Switching on/off the chemisorption of thioctic-based self-assembled monolayers on gold by applying a moderate cathodic/anodic potential.

Science.gov (United States)

Sahli, Rihab; Fave, Claire; Raouafi, Noureddine; Boujlel, Khaled; Schöllhorn, Bernd; Limoges, Benoît

2013-04-30

An in situ and real-time electrochemical method has been devised for quantitatively monitoring the self-assembly of a ferrocene-labeled cyclic disulfide derivative (i.e., a thioctic acid derivative) on a polycrystalline gold electrode under electrode polarization. Taking advantage of the high sensitivity, specificity, accuracy, and temporal resolution of this method, we were able to demonstrate an unexpectedly facilitated formation of the redox-active SAM when the electrode was held at a moderate cathodic potential (-0.4 V vs SCE in CH3CN), affording a saturated monolayer from only micromolar solutions in less than 10 min, and a totally impeded SAM growth when the electrode was polarized at a slightly anodic potential (+0.5 V vs SCE in CH3CN). This method literally allows for switching on/off the formation of SAMs under "soft" conditions. Moreover the cyclic disulfide-based SAM was completely desorbed at this potential contrary to the facilitated deposition of a ferrocene-labeled alkanethiol. Such a strikingly contrasting behavior could be explained by an energetically favored release of the thioctic-based SAM through homolytic cleavage of the Au-S bond followed by intramolecular cyclization of the generated thiyl diradicals. Moreover, the absence of a discernible transient faradaic current response during the potential-assisted adsorption/desorption of the redox-labeled cyclic disulfide led us to conclude in a potential-dependent reversible surface reaction where no electron is released or consumed. These results provide new insights into the formation of disulfide-based SAMs on gold but also raise some fundamental questions about the intimate mechanism involved in the facilitated adsorption/desorption of SAMs under electrode polarization. Finally, the possibility to easily and selectively address the formation/removal of thioctic-based SAMs on gold by applying a moderate cathodic/anodic potential offers another degree of freedom in tailoring their properties and

Photo-Thermal Effects in 1D Gratings of Gold Nanoparticles

Directory of Open Access Journals (Sweden)

Giovanna Palermo

2017-01-01

Full Text Available This work investigates the heat delivered by a mono-layer 1D grating of gold nanoparticles (GNPs created by photo-reduction through two-photon direct laser writing (2P-DLW in a poly-vinyl alcohol (PVA matrix doped with HAuCl4, under resonant laser radiation. We drop cast a film of a PVA + HAuCl4 mixture onto a glass substrate, in which we create gratings of 1 mm2 made by stripes of GNPs characterized by high polydispersivity. We demonstrate that, by controlling the pitch of the GNP stripes, we obtain different values of the photo-induced temperature variations. In the framework of thermo-plasmonics, the experimental investigation of the heat generation from a monolayer of gold nanoparticles represents a key element as a starting point to design thermo-smart platforms for sensing, solar energy harvesting and thermo-catalysis.

Optical constants and self-assembly of phenylene ethynylene oligomer monolayers

DEFF Research Database (Denmark)

Marx, E.; Walzer, Karsten; Less, R.J.

2004-01-01

This paper studies the self-assembly on gold surfaces of 1,4-ethynylphenyl-4'-ethynylphenyl-2'-nitro-1-benzenedithiolate (EP2NO(2)), a substituted phenylene ethynylene trimer with applications in molecular electronics. We develop an ellipsometric technique to measure the optical constants...... of these self-assembled monolayers, and we also use attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and scanning tunneling microscopy (STM) to confirm the structure of the films....

Uniformly sized gold nanoparticles derived from PS-b-P2VP block copolymer templates for the controllable synthesis of Si nanowires.

Science.gov (United States)

Lu, Jennifer Q; Yi, Sung Soo

2006-04-25

A monolayer of gold-containing surface micelles has been produced by spin-coating solution micelles formed by the self-assembly of the gold-modified polystyrene-b-poly(2-vinylpyridine) block copolymer in toluene. After oxygen plasma removed the block copolymer template, highly ordered and uniformly sized nanoparticles have been generated. Unlike other published methods that require reduction treatments to form gold nanoparticles in the zero-valent state, these as-synthesized nanoparticles are in form of metallic gold. These gold nanoparticles have been demonstrated to be an excellent catalyst system for growing small-diameter silicon nanowires. The uniformly sized gold nanoparticles have promoted the controllable synthesis of silicon nanowires with a narrow diameter distribution. Because of the ability to form a monolayer of surface micelles with a high degree of order, evenly distributed gold nanoparticles have been produced on a surface. As a result, uniformly distributed, high-density silicon nanowires have been generated. The process described herein is fully compatible with existing semiconductor processing techniques and can be readily integrated into device fabrication.

Effects of interface roughness on cohesive strength of self-assembled monolayers

Energy Technology Data Exchange (ETDEWEB)

Zhang, Chen [Department of Aerospace Engineering, University of Illinois at Urbana-Champaign, IL 61801 (United States); Awasthi, Amnaya P. [Department of Mechanical and Aerospace Engineering, University of Florida, Gainesville, 32611 (United States); Geubelle, Philippe H., E-mail: geubelle@illinois.edu [Department of Aerospace Engineering, University of Illinois at Urbana-Champaign, IL 61801 (United States); Grady, Martha E.; Sottos, Nancy R. [Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign, IL 61801 (United States)

2017-03-01

Highlights: • Self-assembled monolayer/transfer-printed gold interface modeled using continuum-level simulation. • Initial deformed film profile analyzed and instability assessed. • Effective cohesive response of SAM-enhanced interface extracted from spallation model. • Reduction of up to 70% cohesive strength of the interface from incorporation of roughness demonstrated. - Abstract: Self-assembled monolayers (SAMs) are aggregates of small molecular chains that have the property to form highly ordered assemblies. The choice of terminal groups on the chains makes them excellent contenders of molecular-level tailoring. Molecular dynamics (MD) simulations and experimental observations of spallation of two SAM-enhanced gold-film/silicon-substrate interfaces have shown that the cohesive strength of SAM-enriched transfer-printed interfaces is strongly dependent on the choice of terminal groups. Though the MD results of perfectly ordered atomistic surfaces show the same qualitative trend as the experiments, they over-predict the interfacial cohesive strengths by a factor of about 50. Results from AFM studies have revealed that the roughness of these interfaces is of the same order (∼1 nm) as the range of atomistic interactions. Hence, surface roughness is a key contributor in significantly reducing interfacial cohesive strength in these systems. In this manuscript, a continuum-level study is performed to investigate the influence of surface roughness on the cohesive strength of the interface between a Si/SAM substrate and a transfer-printed gold film. We approximate the film as a deformable continuum interacting with a rough substrate of SAMs represented by a harmonic function. Using a cohesive law derived from MD, spallation is simulated to evaluate the effective traction-separation characteristics for the rough SAM–gold interface. Our analysis shows that incorporating roughness may reduce the interfacial cohesive strength by an order of magnitude depending

Structure and Stability of GeAun, n = 1-10 clusters: A Density Functional Study

International Nuclear Information System (INIS)

Priyanka,; Dharamvir, Keya; Sharma, Hitesh

2011-01-01

The structures of Germanium doped gold clusters GeAu n (n = 1-10) have been investigated using ab initio calculations based on density functional theory (DFT). We have obtained ground state geometries of GeAu n clusters and have it compared with Silicon doped gold clusters and pure gold clusters. The ground state geometries of the GeAu n clusters show patterns similar to silicon doped gold clusters except for n = 5, 6 and 9. The introduction of germanium atom increases the binding energy of gold clusters. The binding energy per atom of germanium doped cluster is smaller than the corresponding silicon doped gold cluster. The HUMO-LOMO gap for Au n Ge clusters have been found to vary between 0.46 eV-2.09 eV. The mullikan charge analysis indicates that charge of order of 0.1e always transfers from germanium atom to gold atom.

Extracellular biosynthesis of monodispersed gold nanoparticles by a SAM capping route

Science.gov (United States)

Wen, Li; Lin, Zhonghua; Gu, Pingying; Zhou, Jianzhang; Yao, Bingxing; Chen, Guoliang; Fu, Jinkun

2009-02-01

Monodispersed gold nanoparticles capped with a self-assembled monolayer of dodecanethiol were biosynthesized extracellularly by an efficient, simple, and environmental friendly procedure, which involved the use of Bacillus megatherium D01 as the reducing agent and the use of dodecanethiol as the capping ligand at 26 °C. The kinetics of gold nanoparticle formation was followed by transmission electron microscope (TEM) and UV-vis spectroscopy. It was shown that reaction time was an important parameter in controlling the morphology of gold nanoparticles. The effect of thiol on the shape, size, and dispersity of gold nanoparticles was also studied. The results showed that the presence of thiol during the biosynthesis could induce the formation of small size gold nanoparticles (gold nanoparticles capped with thiol of 1.9 ± 0.8 nm size were formed by using Bacillus megatherium D01.

Charge-Transfer Effects in Ligand Exchange Reactions of Au25 Monolayer-Protected Clusters.

Science.gov (United States)

Carducci, Tessa M; Blackwell, Raymond E; Murray, Royce W

2015-04-16

Reported here are second-order rate constants of associative ligand exchanges of Au25L18 nanoparticles (L = phenylethanethiolate) of various charge states, measured by proton nuclear magnetic resonance at room temperature and below. Differences in second-order rate constants (M(-1) s(-1)) of ligand exchange (positive clusters ∼1.9 × 10(-5) versus negative ones ∼1.2 × 10(-4)) show that electron depletion retards ligand exchange. The ordering of rate constants between the ligands benzeneselenol > 4-bromobenzene thiol > benzenethiol reveals that exchange is accelerated by higher acidity and/or electron donation capability of the incoming ligand. Together, these observations indicate that partial charge transfer occurs between the nanoparticle and ligand during the exchange and that this is a rate-determining effect in the process.

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

The effect of phase transfer agent in the dynamics of monolayer protected gold nanoparticles has been investigated by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopies. The experiments were performed with octadecane thiol and dodecane thiol protected gold nanoparticles. The materials prepared were ...

Patterned Array of Poly(ethylene glycol Silane Monolayer for Label-Free Detection of Dengue

Directory of Open Access Journals (Sweden)

Nor Zida Rosly

2016-08-01

Full Text Available In the present study, the construction of arrays on silicon for naked-eye detection of DNA dengue was demonstrated. The array was created by exposing a polyethylene glycol (PEG silane monolayer to 254 nm ultraviolet (UV light through a photomask. Formation of the PEG silane monolayer and photomodifed surface properties was thoroughly characterized by using atomic force microscopy (AFM, X-ray photoelectron spectroscopy (XPS, and contact angle measurements. The results of XPS confirmed that irradiation of ultraviolet (UV light generates an aldehyde functional group that offers conjugation sites of amino DNA probe for detection of a specific dengue virus target DNA. Employing a gold enhancement process after inducing the electrostatic interaction between positively charged gold nanoparticles and the negatively charged target DNA hybridized to the DNA capture probe allowed to visualize the array with naked eye. The developed arrays demonstrated excellent performance in diagnosis of dengue with a detection limit as low as 10 pM. The selectivity of DNA arrays was also examined using a single base mismatch and noncomplementary target DNA.

Characterization of Functionalized Self-Assembled Monolayers and Surface-Attached Interlocking Molecules Using Near-Edge X-ray Absorption Fine Structure Spectroscopy

International Nuclear Information System (INIS)

Willey, T; Willey, T

2004-01-01

Quantitative knowledge of the fundamental structure and substrate binding, as well as the direct measurement of conformational changes, are essential to the development of self-assembled monolayers (SAMs) and surface-attached interlocking molecules, catenanes and rotaxanes. These monolayers are vital to development of nano-mechanical, molecular electronic, and biological/chemical sensor applications. This dissertation investigates properties of functionalized SAMs in sulfur-gold based adsorbed molecular monolayers using quantitative spectroscopic techniques including near-edge x-ray absorption fine structure spectroscopy (NEXAFS) and x-ray photoelectron spectroscopy (XPS). The stability of the gold-thiolate interface is addressed. A simple model SAM consisting of dodecanethiol adsorbed on Au(111) degrades significantly in less than 24 hours under ambient laboratory air. S 2p and O 1s XPS show the gold-bound thiolates oxidize to sulfinates and sulfonates. A reduction of organic material on the surface and a decrease in order are observed as the layer degrades. The effect of the carboxyl vs. carboxylate functionalization on SAM structure is investigated. Carboxyl-terminated layers consisting of long alkyl-chain thiols vs. thioctic acid with short, sterically separated, alkyl groups are compared and contrasted. NEXAFS shows a conformational change, or chemical switchability, with carboxyl groups tilted over and carboxylate endgroups more upright. Surface-attached loops and simple surface-attached rotaxanes are quantitatively characterized, and preparation conditions that lead to desired films are outlined. A dithiol is often insufficient to form a molecular species bound at each end to the substrate, while a structurally related disulfide-containing polymer yields surface-attached loops. Similarly, spectroscopic techniques show the successful production of a simple, surface-attached rotaxane that requires a ''molecular riveting'' step to hold the mechanically attached

Ionic interactions in electroactive self-assembled monolayers of ferrocene species

Science.gov (United States)

Delong, Hugh C.; Donohue, John J.; Buttry, Daniel A.

1991-04-01

The electrochemical and interfacial behavior of two types of electroactive self-assembled monolayer systems is investigated at gold electrodes. The first type is a ferrocene-based surfactant (a redox surfactant) derived from (dimethylamino)methylferrocene via quaternization of the amino group with various n-alkylbromides. These have a long alkyl chain with 16 or 18 carbons in the chain pendent from the cationic ammonium group. These are referred to as C16 and C18. The second type is a ferrocene-based dimeric species with a disulfide functional group capable of providing a permanent anchor to the Au electrode, thus endowing monolayers of this species with exceptional stability towards desorption. The electrochemical quartz crystal microbalance (EQM) is used to monitor the mass changes which occur at the electrode surface during the redox processes of these two species.

Subcellular topological effect of particle monolayers on cell shapes and functions.

Science.gov (United States)

Miura, Manabu; Fujimoto, Keiji

2006-12-01

We studied topological effects of subcellular roughness displayed by a closely packed particle monolayer on adhesion and growth of endothelial cells. Poly(styrene-co-acrylamide) (SA) particles were prepared by soap-free emulsion copolymerization. Particle monolayers were prepared by Langmuir-Blodgett deposition using particles, which were 527 (SA053) and 1270 nm (SA127) in diameter. After 24-h incubation, cells tightly adhered on a tissue culture polystyrene dish and randomly spread. On the other hand, cells attached on particle monolayers were stretched into a narrow stalk-like shape. Lamellipodia spread from the leading edge of cells attached on SA053 monolayer to the top of the particles and gradually gathered to form clusters. This shows that cell-cell adhesion became stronger than cell-substrate interaction. Cells attached to SA127 monolayer extended to the reverse side of a particle monolayer and engulfed particles. They remained immobile without migration 24h after incubation. This shows that the inhibition of extensions on SA127 monolayer could inhibit cell migration and cell proliferation. Cell growth on the particle monolayers was suppressed compared with a flat TCPS dish. The number of cells on SA053 gradually increased, whereas that on SA127 decreased with time. When the cell seeding density was increased to 200,000 cells cm(-2), some adherent cells gradually became into contact with adjacent cells. F-actin condensations were formed at the frame of adherent cells and the thin filaments grew from the edges to connect each other with time. For the cell culture on SA053 monolayer, elongated cells showed a little alignment. Cells showed not arrangement of actin stress fibers but F-actin condensation at the contact regions with neighboring cells. Interestingly, the formed cell monolayer could be readily peeled from the particle monolayer. These results indicate that endothelial cells could recognize the surface roughness displayed by particle monolayers and

Low-Temperature PM IRRAS of a Monolayer on Au: Spectra of C18D37SH

Czech Academy of Sciences Publication Activity Database

Mašát, Milan; Wen, Jin; Sofer, Z.; Michl, Josef

2017-01-01

Roč. 33, č. 23 (2017), s. 5613-5616 ISSN 0743-7463 R&D Projects: GA ČR GA14-02337S Institutional support: RVO:61388963 Keywords : self-assembled monolayers * gold surface * electrodes Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 3.833, year: 2016

Protective Effects of Bifidobacterium on Intestinal Barrier Function in LPS-Induced Enterocyte Barrier Injury of Caco-2 Monolayers and in a Rat NEC Model.

Science.gov (United States)

Ling, Xiang; Linglong, Peng; Weixia, Du; Hong, Wei

2016-01-01

Zonulin protein is a newly discovered modulator which modulates the permeability of the intestinal epithelial barrier by disassembling intercellular tight junctions (TJ). Disruption of TJ is associated with neonatal necrotizing enterocolitis (NEC). It has been shown bifidobacterium could protect the intestinal barrier function and prophylactical administration of bifidobacterium has beneficial effects in NEC patients and animals. However, it is still unknown whether the zonulin is involved in the gut barrier dysfunction of NEC, and the protective mechanisms of bifidobacterium on intestinal barrier function are also not well understood. The present study aims to investigate the effects of bifidobacterium on intestinal barrier function, zonulin regulation, and TJ integrity both in LPS-induced enterocyte barrier injury of Caco-2 monolayers and in a rat NEC model. Our results showed bifidobacterium markedly attenuated the decrease in transepithelial electrical resistance and the increase in paracellular permeability in the Caco-2 monolayers treated with LPS (P zonulin release (P zonulin (P zonulin protein release and improvement of intestinal TJ integrity.

Modeling the photosensitizing properties of thiolate-protected gold nanoclusters.

Science.gov (United States)

Azarias, Cloé; Adamo, Carlo; Perrier, Aurélie

2016-03-21

An accurate computational strategy for studying the structural, redox and optical properties of thiolated gold nanoclusters (GNCs) using (Time-Dependent) Density Functional Theory is proposed. The influence of the pseudopotential/basis set, solvent description and the choice of the functional has been investigated to model the structural and electronic properties of the Au25(SR)18(-) system, with R being an organic ligand. This study aims to describe with a comparable precision both the GNC and the organic ligands and rationalize the effect of coating on different GNC properties. Two differently coated GNCs have been considered: the system with R = CH2CH2Ph and the GNC coated with 17 alkyl chains (C6H13) and functionalized by one fluorophore pyrene derivative (CH2CH2(NH)(CO)Py). The computational protocol we propose should then be used to design more efficient metal cluster-sensitized solar cells.

Microcontact printing of self-assembled monolayers to pattern the light-emission of polymeric light-emitting diodes

Energy Technology Data Exchange (ETDEWEB)

Brondijk, J.J.; Li, X.; Akkerman, H.B.; Blom, P.W.M.; Boer, B. de [University of Groningen, Molecular Electronics, Zernike Institute for Advanced Materials, Groningen (Netherlands)

2009-04-15

By patterning a self-assembled monolayer (SAM) of thiolated molecules with opposing dipole moments on a gold anode of a polymer light-emitting diode (PLED), the charge injection and, therefore, the light-emission of the device can be controlled with a micrometer-scale resolution. Gold surfaces were modified with SAMs based on alkanethiols and perfluorinated alkanethiols, applied by microcontact printing, and their work functions have been measured. The molecules form a chemisorbed monolayer of only {proportional_to}1.5 nm on the gold surface, thereby locally changing the work function of the metal. Kelvin probe measurements show that the local work function can be tuned from 4.3 to 5.5 eV, which implies that this anode can be used as a hole blocking electrode or as a hole injecting electrode, respectively, in PLEDs based on poly(p-phenylene vinylene) (PPV) derivatives. By microcontact printing of SAMs with opposing dipole moments, the work function was locally modified and the charge injection in the PLED could be controlled down to the micrometer length scale. Consequently, the local light-emission exhibits a high contrast. Microcontact printing of SAMs is a simple and inexpensive method to pattern, with micrometer resolution, the light-emission for low-end applications like static displays. (orig.)

Microcontact printing of self-assembled monolayers to pattern the light-emission of polymeric light-emitting diodes

Science.gov (United States)

Brondijk, J. J.; Li, X.; Akkerman, H. B.; Blom, P. W. M.; de Boer, B.

2009-04-01

By patterning a self-assembled monolayer (SAM) of thiolated molecules with opposing dipole moments on a gold anode of a polymer light-emitting diode (PLED), the charge injection and, therefore, the light-emission of the device can be controlled with a micrometer-scale resolution. Gold surfaces were modified with SAMs based on alkanethiols and perfluorinated alkanethiols, applied by microcontact printing, and their work functions have been measured. The molecules form a chemisorbed monolayer of only ˜1.5 nm on the gold surface, thereby locally changing the work function of the metal. Kelvin probe measurements show that the local work function can be tuned from 4.3 to 5.5 eV, which implies that this anode can be used as a hole blocking electrode or as a hole injecting electrode, respectively, in PLEDs based on poly( p-phenylene vinylene) (PPV) derivatives. By microcontact printing of SAMs with opposing dipole moments, the work function was locally modified and the charge injection in the PLED could be controlled down to the micrometer length scale. Consequently, the local light-emission exhibits a high contrast. Microcontact printing of SAMs is a simple and inexpensive method to pattern, with micrometer resolution, the light-emission for low-end applications like static displays.

Systematic Study of Au6 to Au12 Gold Clusters on MgO(100) F Centers Using Density-Functional Theory

DEFF Research Database (Denmark)

Vilhelmsen, Lasse; Hammer, Bjørk

2012-01-01

We present an optimized genetic algorithm used in conjunction with density-functional theory in the search for stable gold clusters and O2 adsorption ensembles in F centers at MgO(100). For Au8 the method recovers known structures and identifies several more stable ones. When O2 adsorption...

Theoretical study of oxygen adsorption on pure Au-n+1(+) and doped MAun+ cationic gold clusters for M = Ti, Fe and n=3-7

DEFF Research Database (Denmark)

Torres, M. Begona; Fernandez Sanchez, Eva; Balbas, Luis C.

2008-01-01

A comparative study of the adsorption of an O-2 molecule on pure Au-n+1(+) and doped MAun+ cationic gold clusters for n = 3-7 and M = Ti, Fe is presented. The simultaneous adsorption of two oxygen atoms also was studied. This work was performed by means of first principles calculations based...... with adsorption energies of 0.56 and 0.69 eV, respectively. The ground-state geometry of Au-n(+) is almost unperturbed after O-2 adsorption. The electronic charge flows towards O-2 when the molecule is adsorbed in bridge positions and towards the gold cluster when O-2 is adsorbed on top of An atoms, and both...... with size n are rationalized in terms of O-O and O-M bond distances, as well as charge transfer between oxygen and cluster substrates. The spin multiplicity of those (MAunO2+)(ad) complexes with the highest O-2 adsorption energy is a maximum (minimum) for M = Fe (Ti), corresponding to parallel (anti...

Impedimetric Urea Biosensor Based on Modified Gold Electrode with Urease Immobilized on Glutathione Layer

OpenAIRE

Houcine BARHOUMI; Abderrazak MAAREF; Nicole JAFFREZIC-RENAULT

2014-01-01

In this work, a glutathione (GSH) modified gold microelectrode was used for the covalent immobilization of urease biomolecules via the glutaraldehyde-coupling agent. The self- assembled monolayers (SAMs) onto the gold surface was investigated by using the electrochemical impedance spectroscopy measurements (EIS). Before urease grafting, a significant interaction was noticed between urea and the glutathione layer by forming hydrogen bonds. The H-NMR analysis was carried out to highlight the po...

Water adsorption by a sensitive calibrated gold plasmonic nanosensor.

Science.gov (United States)

Demirdjian, Benjamin; Bedu, Frédéric; Ranguis, Alain; Ozerov, Igor; Henry, Claude R

2018-04-20

We demonstrate in this work that using nanoplasmonic sensing it is possible to follow the adsorption/desorption of water molecules on gold nanodisks nanofabricated by electron beam lithography. This quantitative method is highly sensitive allowing the detection of a few hundredths of adsorbed monolayers. Disk parameters (height, diameter, inter-disk distance) have been optimized after finite-difference time-domain (FDTD) simulations in order to obtain the best localized surface plasmon resonance (LSPR) signal-to-noise ratio. Finally, we have precisely measured the adsorption kinetics of water on gold as a function of the relative humidity of the surrounding medium.

Extracellular biosynthesis of monodispersed gold nanoparticles by a SAM capping route

International Nuclear Information System (INIS)

Wen Li; Lin Zhonghua; Gu Pingying; Zhou Jianzhang; Yao Bingxing; Chen Guoliang; Fu Jinkun

2009-01-01

Monodispersed gold nanoparticles capped with a self-assembled monolayer of dodecanethiol were biosynthesized extracellularly by an efficient, simple, and environmental friendly procedure, which involved the use of Bacillus megatherium D01 as the reducing agent and the use of dodecanethiol as the capping ligand at 26 o C. The kinetics of gold nanoparticle formation was followed by transmission electron microscope (TEM) and UV-vis spectroscopy. It was shown that reaction time was an important parameter in controlling the morphology of gold nanoparticles. The effect of thiol on the shape, size, and dispersity of gold nanoparticles was also studied. The results showed that the presence of thiol during the biosynthesis could induce the formation of small size gold nanoparticles (<2.5 nm), hold the shape of spherical nanoparticles, and promote the monodispersity of nanoparticles. Through the modulation of reaction time and the use of thiol, monodispersed spherical gold nanoparticles capped with thiol of 1.9 ± 0.8 nm size were formed by using Bacillus megatherium D01.

Extracellular biosynthesis of monodispersed gold nanoparticles by a SAM capping route

Energy Technology Data Exchange (ETDEWEB)

Wen Li [Xiamen University, Department of Chemistry, College of Chemistry and Chemical Engineering (China); Lin Zhonghua [Xiamen University, State Key Laboratory of Physical Chemistry of Solid Surfaces (China); Gu Pingying [Xiamen University, Department of Chemistry, College of Chemistry and Chemical Engineering (China); Zhou Jianzhang [Xiamen University, State Key Laboratory of Physical Chemistry of Solid Surfaces (China); Yao Bingxing [Xiamen University, School of Life Sciences (China); Chen Guoliang; Fu Jinkun, E-mail: wenli_1976@163.co [Xiamen University, Department of Chemistry, College of Chemistry and Chemical Engineering (China)

2009-02-15

Monodispersed gold nanoparticles capped with a self-assembled monolayer of dodecanethiol were biosynthesized extracellularly by an efficient, simple, and environmental friendly procedure, which involved the use of Bacillus megatherium D01 as the reducing agent and the use of dodecanethiol as the capping ligand at 26 {sup o}C. The kinetics of gold nanoparticle formation was followed by transmission electron microscope (TEM) and UV-vis spectroscopy. It was shown that reaction time was an important parameter in controlling the morphology of gold nanoparticles. The effect of thiol on the shape, size, and dispersity of gold nanoparticles was also studied. The results showed that the presence of thiol during the biosynthesis could induce the formation of small size gold nanoparticles (<2.5 nm), hold the shape of spherical nanoparticles, and promote the monodispersity of nanoparticles. Through the modulation of reaction time and the use of thiol, monodispersed spherical gold nanoparticles capped with thiol of 1.9 {+-} 0.8 nm size were formed by using Bacillus megatherium D01.

Measurement of discrete energy-level spectra in individual chemically synthesized gold nanoparticles

DEFF Research Database (Denmark)

Kuemmeth, Ferdinand; Bolotin, Kirill I; Shi, Su-Fei

2008-01-01

We form single-electron transistors from individual chemically synthesized gold nanoparticles, 5-15 nm in diameter, with monolayers of organic molecules serving as tunnel barriers. These devices allow us to measure the discrete electronic energy levels of individual gold nanoparticles that are......, by virtue of chemical synthesis, well-defined in their composition, size and shape. We show that the nanoparticles are nonmagnetic and have spectra in good accord with random-matrix-theory predictions taking into account strong spin-orbit coupling....

Determining the thickness of aliphatic alcohol monolayers covalently attached to silicon oxide surfaces using angle-resolved X-ray photoelectron spectroscopy

Science.gov (United States)

Lee, Austin W. H.; Kim, Dongho; Gates, Byron D.

2018-04-01

The thickness of alcohol based monolayers on silicon oxide surfaces were investigated using angle-resolved X-ray photoelectron spectroscopy (ARXPS). Advantages of using alcohols as building blocks for the formation of monolayers include their widespread availability, ease of handling, and stability against side reactions. Recent progress in microwave assisted reactions demonstrated the ease of forming uniform monolayers with alcohol based reagents. The studies shown herein provide a detailed investigation of the thickness of monolayers prepared from a series of aliphatic alcohols of different chain lengths. Monolayers of 1-butanol, 1-hexanol, 1-octanol, 1-decanol, and 1-dodecanol were each successfully formed through microwave assisted reactions and characterized by ARXPS techniques. The thickness of these monolayers consistently increased by ∼1.0 Å for every additional methylene (CH2) within the hydrocarbon chain of the reagents. Tilt angles of the molecules covalently attached to silicon oxide surfaces were estimated to be ∼35° for each type of reagent. These results were consistent with the observations reported for thiol based or silane based monolayers on either gold or silicon oxide surfaces, respectively. The results of this study also suggest that the alcohol based monolayers are uniform at a molecular level.

A new route to gold nanoflowers

Science.gov (United States)

Liebig, Ferenc; Henning, Ricky; Sarhan, Radwan M.; Prietzel, Claudia; Bargheer, Matias; Koetz, Joachim

2018-05-01

Catanionic vesicles spontaneously formed by mixing the anionic surfactant bis(2-ethylhexyl) sulfosuccinate sodium salt with the cationic surfactant cetyltrimethylammonium bromide were used as a reducing medium to produce gold clusters, which are embedded and well-ordered into the template phase. The gold clusters can be used as seeds in the growth process that follows by adding ascorbic acid as a mild reducing component. When the ascorbic acid was added very slowly in an ice bath round-edged gold nanoflowers were produced. When the same experiments were performed at room temperature in the presence of Ag+ ions, sharp-edged nanoflowers could be synthesized. The mechanism of nanoparticle formation can be understood to be a non-diffusion-limited Ostwald ripening process of preordered gold nanoparticles embedded in catanionic vesicle fragments. Surface-enhanced Raman scattering experiments show an excellent enhancement factor of 1.7 · 105 for the nanoflowers deposited on a silicon wafer.

Polymorphism of Ag29(BDT)12(TPP)43- cluster: interactions of secondary ligands and their effect on solid state luminescence.

Science.gov (United States)

Nag, Abhijit; Chakraborty, Papri; Bodiuzzaman, Mohammad; Ahuja, Tripti; Antharjanam, Sudhadevi; Pradeep, Thalappil

2018-05-31

We present the first example of polymorphism (cubic & trigonal) in single crystals of an atomically precise monolayer protected cluster, Ag29(BDT)12(TPP)43-. We demonstrate that C-Hπ interactions of the secondary ligands (TPP) are dominant in a cubic lattice compared to a trigonal lattice, resulting in a greater rigidity of the structure, which in turn, results in a higher luminescence efficiency in it.

Natural Deposition Strategy for Interfacial, Self-Assembled, Large-Scale, Densely Packed, Monolayer Film with Ligand-Exchanged Gold Nanorods for In Situ Surface-Enhanced Raman Scattering Drug Detection.

Science.gov (United States)

Mao, Mei; Zhou, Binbin; Tang, Xianghu; Chen, Cheng; Ge, Meihong; Li, Pan; Huang, Xingjiu; Yang, Liangbao; Liu, Jinhuai

2018-03-15

Liquid interfacial self-assembly of metal nanoparticles holds great promise for its various applications, such as in tunable optical devices, plasmonics, sensors, and catalysis. However, the construction of large-area, ordered, anisotropic, nanoparticle monolayers and the acquisition of self-assembled interface films are still significant challenges. Herein, a rapid, validated method to fabricate large-scale, close-packed nanomaterials at the cyclohexane/water interface, in which hydrophilic cetyltrimethylammonium bromide coated nanoparticles and gold nanorods (AuNRs) self-assemble into densely packed 2D arrays by regulating the surface ligand and suitable inducer, is reported. Decorating AuNRs with polyvinylpyrrolidone not only extensively decreases the charge of AuNRs, but also diminishes repulsive forces. More importantly, a general, facile, novel technique to transfer an interfacial monolayer through a designed in situ reaction cell linked to a microfluidic chip is revealed. The self-assembled nanofilm can then automatically settle on the substrate and be directly detected in the reaction cell in situ by means of a portable Raman spectrometer. Moreover, a close-packed monolayer of self-assembled AuNRs provides massive, efficient hotspots to create great surface-enhanced Raman scattering (SERS) enhancement, which provides high sensitivity and reproducibility as the SERS-active substrate. Furthermore, this strategy was exploited to detect drug molecules in human urine for cyclohexane-extracted targets acting as the oil phase to form an oil/water interface. A portable Raman spectrometer was employed to detect methamphetamine down to 100 ppb levels in human urine, exhibiting excellent practicability. As a universal platform, handy tool, and fast pretreatment method with a good capability for drug detection in biological systems, this technique shows great promise for rapid, credible, and on-spot drug detection. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-assembled organic monolayers on gold nanoparticles: A study by sum-frequency generation combined with UV-vis spectroscopy

International Nuclear Information System (INIS)

Humbert, C.; Busson, B.; Abid, J.-P.; Six, C.; Girault, H.H.; Tadjeddine, A.

2005-01-01

We use sum-frequency generation spectroscopy (SFG) in the infrared 2800-3000 cm -1 spectral range and UV-vis spectroscopy (transmission) in the 450-650 nm spectral range in order to characterize vibrational and electronic properties of various interfaces composed of organic monolayers adsorbed on gold nanoparticles (AuNPs) with 19 nm average diameter. SFG signal is observed for AuNPs films deposited on glass substrates using the following silane intermediates: 3-(aminopropyl) triethoxysilane and 3-(mercaptopropyl) trimethoxysilane. The density of AuNPs and their aggregates are measured with a scanning electron microscope. For the samples showing a strong well-defined surface plasmon resonance (SPR), we also observe an enhancement of their non-linear optical properties. Furthermore, the SFG measurements show that 1-dodecanethiol films are rather well ordered on specific AuNPs substrates. In this way, the presence of the SFG signal, which comes from both the bulk electronic s-d interband transition and the vibrational states of the adsorbed molecules, depends on a SPR process. This phenomenon is evidenced on the AuNPs by the incident visible beam located at 532 nm, i.e. near the SPR energy maximum of these interfaces. These results open the door to experiments involving macromolecular and biological materials networks deposited on ultrathin metal electrodes in a controlled electrochemical environment

Self-assembled organic monolayers on gold nanoparticles: A study by sum-frequency generation combined with UV-vis spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Humbert, C. [LURE, CNRS-UMR 130, Centre Universitaire Paris-Sud, Ba-hat t. 209D, B.P. 34, 91898 Orsay Cedex (France) and Laboratoire de Spectroscopie Moleculaire de Surface, University of Namur, 61 Rue de Bruxelles, B-5000 Namur (Belgium)]. E-mail: christophe.humbert@fundp.ac.be; Busson, B. [LURE, CNRS-UMR 130, Centre Universitaire Paris-Sud, Ba-hat t. 209D, B.P. 34, 91898 Orsay Cedex (France); Abid, J.-P. [Ecole Polytechnique Federale de Lausanne, Laboratoire d' Electrochimie Physique et Analytique, CH-1015 Lausanne (Switzerland); Six, C. [LURE, CNRS-UMR 130, Centre Universitaire Paris-Sud, Ba-hat t. 209D, B.P. 34, 91898 Orsay Cedex (France); Girault, H.H. [Ecole Polytechnique Federale de Lausanne, Laboratoire d' Electrochimie Physique et Analytique, CH-1015 Lausanne (Switzerland); Tadjeddine, A. [LURE, CNRS-UMR 130, Centre Universitaire Paris-Sud, Ba-hat t. 209D, B.P. 34, 91898 Orsay Cedex (France)

2005-05-20

We use sum-frequency generation spectroscopy (SFG) in the infrared 2800-3000 cm{sup -1} spectral range and UV-vis spectroscopy (transmission) in the 450-650 nm spectral range in order to characterize vibrational and electronic properties of various interfaces composed of organic monolayers adsorbed on gold nanoparticles (AuNPs) with 19 nm average diameter. SFG signal is observed for AuNPs films deposited on glass substrates using the following silane intermediates: 3-(aminopropyl) triethoxysilane and 3-(mercaptopropyl) trimethoxysilane. The density of AuNPs and their aggregates are measured with a scanning electron microscope. For the samples showing a strong well-defined surface plasmon resonance (SPR), we also observe an enhancement of their non-linear optical properties. Furthermore, the SFG measurements show that 1-dodecanethiol films are rather well ordered on specific AuNPs substrates. In this way, the presence of the SFG signal, which comes from both the bulk electronic s-d interband transition and the vibrational states of the adsorbed molecules, depends on a SPR process. This phenomenon is evidenced on the AuNPs by the incident visible beam located at 532 nm, i.e. near the SPR energy maximum of these interfaces. These results open the door to experiments involving macromolecular and biological materials networks deposited on ultrathin metal electrodes in a controlled electrochemical environment.

Highly active engineered-enzyme oriented monolayers: formation, characterization and sensing applications

Directory of Open Access Journals (Sweden)

Patolsky Fernando

2011-06-01

Full Text Available Abstract Background The interest in introducing ecologically-clean, and efficient enzymes into modern industry has been growing steadily. However, difficulties associated with controlling their orientation, and maintaining their selectivity and reactivity is still a significant obstacle. We have developed precise immobilization of biomolecules, while retaining their native functionality, and report a new, fast, easy, and reliable procedure of protein immobilization, with the use of Adenylate kinase as a model system. Methods Self-assembled monolayers of hexane-1,6-dithiol were formed on gold surfaces. The monolayers were characterized by contact-angle measurements, Elman-reagent reaction, QCM, and XPS. A specifically designed, mutated Adenylate kinase, where cysteine was inserted at the 75 residue, and the cysteine at residue 77 was replaced by serine, was used for attachment to the SAM surface via spontaneously formed disulfide (S-S bonds. QCM, and XPS were used for characterization of the immobilized protein layer. Curve fitting in XPS measurements used a Gaussian-Lorentzian function. Results and Discussion Water contact angle (65-70°, as well as all characterization techniques used, confirmed the formation of self-assembled monolayer with surface SH groups. X-ray photoelectron spectroscopy showed clearly the two types of sulfur atom, one attached to the gold (triolate and the other (SH/S-S at the ω-position for the hexane-1,6-dithiol SAMs. The formation of a protein monolayer was confirmed using XPS, and QCM, where the QCM-determined amount of protein on the surface was in agreement with a model that considered the surface area of a single protein molecule. Enzymatic activity tests of the immobilized protein confirmed that there is no change in enzymatic functionality, and reveal activity ~100 times that expected for the same amount of protein in solution. Conclusions To the best of our knowledge, immobilization of a protein by the method

Sulfonic acid-functionalized golf nanoparticles: A colloid-bound catalyst for soft lithographic application on self-assembled monolayers

NARCIS (Netherlands)

Li, X.; Paraschiv, V.; Huskens, Jurriaan; Reinhoudt, David

2003-01-01

In this report, we present a new lithographic approach to prepare patterned surfaces. Self-assembled monolayers (SAMs) of the acid-labile trimethylsilyl ether (TMS-OC11H22S)2 (TMS adsorbate) was formed on gold. 5-Mercapto-2-benzimidazole sulfonic acid sodium salt (MBS-Na+) was used as a ligand for

Patterned self-assembled monolayers of alkanethiols on copper nanomembranes by submerged laser ablation

Science.gov (United States)

Rhinow, Daniel; Hampp, Norbert A.

2012-06-01

Self-assembled monolayers (SAMs) of alkanethiols are major building blocks for nanotechnology. SAMs provide a functional interface between electrodes and biomolecules, which makes them attractive for biochip fabrication. Although gold has emerged as a standard, copper has several advantages, such as compatibility with semiconductors. However, as copper is easily oxidized in air, patterning SAMs on copper is a challenging task. In this work we demonstrate that submerged laser ablation (SLAB) is well-suited for this purpose, as thiols are exchanged in-situ, avoiding air exposition. Using different types of ω-substituted alkanethiols we show that alkanethiol SAMs on copper surfaces can be patterned using SLAB. The resulting patterns were analyzed by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Both methods indicate that the intense laser beam promotes the exchange of thiols at the copper surface. Furthermore, we present a procedure for the production of free-standing copper nanomembranes, oxidation-protected by alkanethiol SAMs. Incubation of copper-coated mica in alkanethiol solutions leads to SAM formation on both surfaces of the copper film due to intercalation of the organic molecules. Corrosion-protected copper nanomembranes were floated onto water, transferred to electron microscopy grids, and subsequently analyzed by electron energy loss spectroscopy (EELS).

Novel determination of cadmium ions using an enzyme self-assembled monolayer with surface plasmon resonance

International Nuclear Information System (INIS)

May May, Lee; Russell, David A.

2003-01-01

The activity of the enzyme urease is known to be inhibited by the heavy metal cadmium. The binding of cadmium to urease and the consequent changes of the enzyme structure are the basis of the surface plasmon resonance (SPR) biosensing system reported herein. To facilitate the formation of a self-assembled monolayer (SAM) of the urease on gold-coated glass SPR sensor disks, the enzyme has been modified with N-succinimidyl 3-(2-pyridyldithiol) propionate (SPDP). The urease monolayer was exposed to trace levels of cadmium ions and monitored by SPR. From circular dichroism (CD) data, it is believed that the conformation of the active nickel site of the urease changes upon binding of the cadmium ions. It is this change of the enzyme monolayer, measured by SPR, which has been related to the cadmium ion concentration in the range of 0-10 mg l -1 . These data are the first report of a SPR biosensor capable of detecting metal ions

Proton and hydrogen transport through two-dimensional monolayers

International Nuclear Information System (INIS)

Seel, Max; Pandey, Ravindra

2016-01-01

Diffusion of protons and hydrogen atoms in representative two-dimensional materials is investigated. Specifically, density functional calculations were performed on graphene, hexagonal boron nitride (h-BN), phosphorene, silicene, and molybdenum disulfide (MoS 2 ) monolayers to study the surface interaction and penetration barriers for protons and hydrogen atoms employing finite cluster models. The calculated barrier heights correlate approximately with the size of the opening formed by the three-fold open sites in the monolayers considered. They range from 1.56 eV (proton) and 4.61 eV (H) for graphene to 0.12 eV (proton) and 0.20 eV (H) for silicene. The results indicate that only graphene and h-BN monolayers have the potential for membranes with high selective permeability. The MoS 2 monolayer behaves differently: protons and H atoms become trapped between the outer S layers in the Mo plane in a well with a depth of 1.56 eV (proton) and 1.5 eV (H atom), possibly explaining why no proton transport was detected, suggesting MoS 2 as a hydrogen storage material instead. For graphene and h-BN, off-center proton penetration reduces the barrier to 1.38 eV for graphene and 0.11 eV for h-BN. Furthermore, Pt acting as a substrate was found to have a negligible effect on the barrier height. In defective graphene, the smallest barrier for proton diffusion (1.05 eV) is found for an oxygen-terminated defect. Therefore, it seems more likely that thermal protons can penetrate a monolayer of h-BN but not graphene and defects are necessary to facilitate the proton transport in graphene. (paper)

Proton and hydrogen transport through two-dimensional monolayers

Science.gov (United States)

Seel, Max; Pandey, Ravindra

2016-06-01

Diffusion of protons and hydrogen atoms in representative two-dimensional materials is investigated. Specifically, density functional calculations were performed on graphene, hexagonal boron nitride (h-BN), phosphorene, silicene, and molybdenum disulfide (MoS2) monolayers to study the surface interaction and penetration barriers for protons and hydrogen atoms employing finite cluster models. The calculated barrier heights correlate approximately with the size of the opening formed by the three-fold open sites in the monolayers considered. They range from 1.56 eV (proton) and 4.61 eV (H) for graphene to 0.12 eV (proton) and 0.20 eV (H) for silicene. The results indicate that only graphene and h-BN monolayers have the potential for membranes with high selective permeability. The MoS2 monolayer behaves differently: protons and H atoms become trapped between the outer S layers in the Mo plane in a well with a depth of 1.56 eV (proton) and 1.5 eV (H atom), possibly explaining why no proton transport was detected, suggesting MoS2 as a hydrogen storage material instead. For graphene and h-BN, off-center proton penetration reduces the barrier to 1.38 eV for graphene and 0.11 eV for h-BN. Furthermore, Pt acting as a substrate was found to have a negligible effect on the barrier height. In defective graphene, the smallest barrier for proton diffusion (1.05 eV) is found for an oxygen-terminated defect. Therefore, it seems more likely that thermal protons can penetrate a monolayer of h-BN but not graphene and defects are necessary to facilitate the proton transport in graphene.

XAS and XMCD investigation of Mn12 monolayers on gold.

Science.gov (United States)

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.

The modification of glassy carbon and gold electrodes with aryl diazonium salt: The impact of the electrode materials on the rate of heterogeneous electron transfer

International Nuclear Information System (INIS)

Liu Guozhen; Liu Jingquan; Boecking, Till; Eggers, Paul K.; Gooding, J. Justin

2005-01-01

The heterogeneous electron-transfer properties of ferrocenemethylamine coupled to a series of mixed 4-carboxyphenyl/phenyl monolayers on glassy carbon (GC) and gold electrodes were investigated, by cyclic voltammetry, in aqueous buffer solutions. The electrodes were derivatized in a step-wise process. Electrochemical reduction of mixtures of 4-carboxyphenyl and phenyl diazonium salts on the electrode surfaces yielded stable monolayers. The introduction of carboxylic acid moieties onto the surfaces was verified by X-ray photoelectron spectroscopy. Subsequently the 4-carboxyphenyl moieties were activated using water-soluble carbodiimide and N-hydroxysuccinimide and reacted with ferrocenemethylamine. The rate constants of electron transfer through the monolayer systems were determined from cyclic voltammograms using the Marcus theory for electron transfer and were found to be an order of magnitude higher for the ferrocene-modified monolayer systems on gold than those on GC electrodes. The results suggest the electrode material has an important influence on the rate of electron transfer

Voltage-dependent cluster expansion for electrified solid-liquid interfaces: Application to the electrochemical deposition of transition metals

Science.gov (United States)

Weitzner, Stephen E.; Dabo, Ismaila

2017-11-01

The detailed atomistic modeling of electrochemically deposited metal monolayers is challenging due to the complex structure of the metal-solution interface and the critical effects of surface electrification during electrode polarization. Accurate models of interfacial electrochemical equilibria are further challenged by the need to include entropic effects to obtain accurate surface chemical potentials. We present an embedded quantum-continuum model of the interfacial environment that addresses each of these challenges and study the underpotential deposition of silver on the gold (100) surface. We leverage these results to parametrize a cluster expansion of the electrified interface and show through grand canonical Monte Carlo calculations the crucial need to account for variations in the interfacial dipole when modeling electrodeposited metals under finite-temperature electrochemical conditions.

Single molecular switch based on thiol tethered iron(II)clathrochelate on gold

Energy Technology Data Exchange (ETDEWEB)

Viswanathan, Subramanian [Institute of Animal Reproduction and Food Research of the Polish Academy of Sciences, Tuwima 10, 10-747 Olsztyn (Poland); Voloshin, Yan Z. [Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 119991 Moscow (Russian Federation); Radecka, Hanna [Institute of Animal Reproduction and Food Research of the Polish Academy of Sciences, Tuwima 10, 10-747 Olsztyn (Poland); Radecki, Jerzy [Institute of Animal Reproduction and Food Research of the Polish Academy of Sciences, Tuwima 10, 10-747 Olsztyn (Poland)], E-mail: radecki@pan.olsztyn.pl

2009-09-30

Molecular electronics has been associated with high density nano-electronic devices. Developments of molecular electronic devices were based on reversible switching of molecules between the two conductive states. In this paper, self-assembled monolayers of dodecanethiol (DDT) and thiol tethered iron(II)clathrochelate (IC) have been prepared on gold film. The electrochemical and electronic properties of IC molecules inserted into the dodecanethiol monolayer (IC-DDT SAM) were investigated using voltammetric, electrochemical impedance spectroscopy (EIS), scanning tunneling microscopy (STM) and cross-wire tunneling measurements. The voltage triggered switching behaviour of IC molecules on mixed SAM was demonstrated. Deposition of polyaniline on the redox sites of IC-DDT SAM using electrochemical polymerization of aniline was performed in order to confirm that this monolayer acts as nano-patterned semiconducting electrode surface.

Restraint deformation and corrosion protection of gold deposited aluminum mirrors for cold optics of mid-infrared instruments

Science.gov (United States)

Uchiyama, Mizuho; Miyata, Takashi; Sako, Shigeyuki; Kamizuka, Takafumi; Nakamura, Tomohiko; Asano, Kentaro; Okada, Kazushi; Onaka, Takashi; Sakon, Itsuki; Kataza, Hirokazu; Sarugaku, Yuki; Kirino, Okiharu; Nakagawa, Hiroyuki; Okada, Norio; Mitsui, Kenji

2014-07-01

We report the restraint deformation and the corrosion protection of gold deposited aluminum mirrors for mid-infrared instruments. To evaluate the deformation of the aluminum mirrors by thermal shrinkage, monitoring measurement of the surface of a mirror has been carried out in the cooling cycles from the room temperature to 100 K. The result showed that the effect of the deformation was reduced to one fourth if the mirror was screwed with spring washers. We have explored an effective way to prevent the mirror from being galvanically corroded. A number of samples have been prepared by changing the coating conditions, such as inserting an insulation layer, making a multi-layer and overcoating water blocking layer, or carrying out precision cleaning before coating. Precision cleaning before the deposition and protecting coat with SiO over the gold layer seemed to be effective in blocking corrosion of the aluminum. The SiO over-coated mirror has survived the cooling test for the mid-infrared use and approximately 1 percent decrease in the reflectance has been detected at 6-25 microns compared to gold deposited mirror without coating.

Comprehensive cluster analysis with Transitivity Clustering.

Science.gov (United States)

Wittkop, Tobias; Emig, Dorothea; Truss, Anke; Albrecht, Mario; Böcker, Sebastian; Baumbach, Jan

2011-03-01

Transitivity Clustering is a method for the partitioning of biological data into groups of similar objects, such as genes, for instance. It provides integrated access to various functions addressing each step of a typical cluster analysis. To facilitate this, Transitivity Clustering is accessible online and offers three user-friendly interfaces: a powerful stand-alone version, a web interface, and a collection of Cytoscape plug-ins. In this paper, we describe three major workflows: (i) protein (super)family detection with Cytoscape, (ii) protein homology detection with incomplete gold standards and (iii) clustering of gene expression data. This protocol guides the user through the most important features of Transitivity Clustering and takes ∼1 h to complete.

XPS and NEXAFS study of tyrosine-terminated propanethiol assembled on gold

CERN Document Server

Petoral, R M

2003-01-01

Tyrosine-terminated propanethiol (TPT), tyrosine linked to 3-mercaptopropionic acid through an amide bond, is adsorbed to gold surfaces. The adsorbates are characterized by means of X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure spectroscopy (NEXAFS). XPS is used to investigate the chemical binding and electronic structure of the monolayer. Strong molecular binding of the tyrosine derivative on the gold surface through the sulfur atom is attained. Angle-dependent XPS results shows that TPT molecules are oriented with the sulfur atoms molecularly oriented close to the gold surface and that the phenol moiety is oriented away from the gold surface. Average orientation of the adsorbate on gold is deduced using the NEXAFS results. It shows that the main molecular axis is tilted approximately 38 deg. relative to the Au surface normal. The ring plane of the phenol moiety exhibits a preferential orientation with an average tilt angle of the normal of the ring plane from the surfa...

Au70S20(PPh3)12: an intermediate sized metalloid gold cluster stabilized by the Au4S4 ring motif and Au-PPh3 groups.

Science.gov (United States)

Kenzler, Sebastian; Schrenk, Claudio; Frojd, Andrew R; Häkkinen, Hannu; Clayborne, Andre Z; Schnepf, Andreas

2018-01-02

Reducing (Ph 3 P)AuSC(SiMe 3 ) 3 with l-Selectride® gives the medium-sized metalloid gold cluster Au 70 S 20 (PPh 3 ) 12 . Computational studies show that the phosphine bound Au-atoms not only stabilize the electronic structure of Au 70 S 20 (PPh 3 ) 12 , but also behave as electron acceptors leading to auride-like gold atoms on the exterior.

Surface enhanced infrared spectroscopy using interacting gold nanowires

Energy Technology Data Exchange (ETDEWEB)

Neubrech, Frank; Weber, Daniel; Pucci, Annemarie [Kirchhoff-Institut fuer Physik, Heidelberg (Germany); Shen, Hong [Universite Troyes, Troyes (France); Lamy de la Chapelle, Marc [Universite Paris 13, Bobigny (France)

2009-07-01

We performed surface enhanced infrared spectroscopy (SEIRS) of molecules adsorbed on gold nanowires using synchrotron light of the ANKA IR-beamline at the Forschungszentrum Karlsruhe (Germany). Arrays of gold nanowires with interparticle spacings down to 30nm were prepared by electron beam lithography. The interparticle distance was reduced further by wet-chemically increasing the size of the gold nanowires. The growth of the wires was proofed using IR spectroscopy as well as scanning electron microscopy. After this preparation step, appropriate arrays of nanowires with an interparticle distance down to a few nanometers were selected to demonstrate the surface enhanced infrared spectroscopy of one monolayer octadecanthiol (ODT). As know from SEIRS studies using single gold nanowires, the spectral position of the antenna-like resonance in relation to the absorption bands of ODT (2850cm-1 and 2919cm-1) is crucial for both, the lineshape of the molecular vibration and the signal enhancement. In contrast to single nanowires studies, a further increase of the enhanced signals is expected due to the interaction of the electromagnetic fields of the close-by nanowires.

Geometric, stable and electronic properties of Aun–2Y2 (n = 3–8) clusters

International Nuclear Information System (INIS)

Kai-Tian, Qi; Yong, Sheng; Hua-Ping, Mao; Hong-Yan, Wang

2010-01-01

Employing first-principles methods, based on the density function theory, and using the LANL2DZ basis sets, the ground-state geometric, the stable and the electronic properties of Au n–2 Y 2 clusters are investigated in this paper. Meanwhile, the differences in property among pure gold clusters, pure yttrium clusters, gold clusters doped with one yttrium atom, and gold clusters doped with two yttrium atoms are studied. We find that when gold clusters are doped by two yttrium atoms, the odd-even oscillatory behaviours of Au n–1 Y and Au n disappear. The properties of Au n–2 Y 2 clusters are close to those of pure yttrium clusters

A comparative study for Hydrogen storage in metal decorated graphyne nanotubes and graphyne monolayers

International Nuclear Information System (INIS)

Lu, Jinlian; Guo, Yanhua; Zhang, Yun; Tang, Yingru; Cao, Juexian

2015-01-01

A comparative study for hydrogen storage in metal decorated graphyne nanotubes and graphyne monolayers has been investigated within the framework of first-principle calculations. Our results show that the binding energies of Li, Ca, Sc, Ti on graphyne nanotubes are stronger than that on graphyne monolayers. Such strong binding would prevent the formation of metal clusters on graphyne nanotubes. From the charge transfer and partial density of states, it is found that the curvature effect of nanotubes plays an important role for the strong binding strength of metal on graphyne nanotubes. And the hydrogen storage capacity is 4.82 wt%, 5.08 wt%, 4.88 wt%, 4.76 wt% for Li, Ca, Sc, Ti decorated graphyne nanotubes that promise a potential material for storing hydrogen. - Graphical abstract: Metal atoms (Li, Ca, Sc and Ti) can strongly bind to graphyne nanotubes to avoid the formation of metal clusters, and a capacity of Ca@graphyne nanotube is 5.08 wt% which is close to the requirement of DOE in 2015. Twenty-four hydrogen molecules absorb to Ti-decorated graphyne nanotube. - Highlights: • The binding strength for metal on graphyne nanotubes is much stronger than that on γ-graphyne monolayer. • Metal atoms can strongly bind to the curving triangle acetylenes rings to avoid the formation of metal clusters. • A capacity of Ca@graphyne nanotube is 5.08 wt% which is close to the requirement of DOE in 2015.

Nonlinear optical studies of single gold nanoparticles

NARCIS (Netherlands)

Dijk, Meindert Alexander van

2007-01-01

Gold nanoparticles are spherical clusters of gold atoms, with diameters typically between 1 and 100 nanometers. The applications of these particles are rather diverse, from optical labels for biological experiments to data carrier for optical data storage. The goal of my project was to develop new

Size selected metal clusters

Indian Academy of Sciences (India)

First page Back Continue Last page Overview Graphics. The Optical Absorption Spectra of Small Silver Clusters (5-11) ... Soft Landing and Fragmentation of Small Clusters Deposited in Noble-Gas Films. Harbich, W.; Fedrigo, S.; Buttet, J. Phys. Rev. B 1998, 58, 7428. CO combustion on supported gold clusters. Arenz M ...

DNA-mediated self-assembly of tetrahedral plasmonic clusters for metafluids

Science.gov (United States)

Schade, Nicholas; Sun, Li; Lee, You-Jin; Fan, Jonathan; Capasso, Federico; Yi, Gi-Ra; Manoharan, Vinothan

2014-03-01

We direct the self-assembly of clusters of gold nanospheres with the goal of creating a bulk, isotropic, optical metafluid. We use spherical gold nanoparticles that are exceptionally smooth, monocrystalline, and monodisperse. These particles exhibit highly reproducible scattering spectra compared with commercially available gold colloids. We label them with DNA sequences and mix them together to self-assemble small clusters. By controlling the particle sizes and the interactions between them, we maximize the yield of tetrahedral clusters, the ideal structures for isotropic metamaterials.

Computer simulation of the vertical growth of subsurface cobalt nanoclusters in gold

NARCIS (Netherlands)

Kulikov, D.V.; Kurnosikov, O.; Sicot, M.V.; Trushin, Yu.V.

2009-01-01

The vertical growth of nanodimensional cobalt clusters buried under the surface of a gold substrate has been studied using computer simulation methods with allowance for the interdiffusion of Au and Co atoms and the fields of elastic stresses generated by cobalt clusters in the gold matrix. The

Effect of humic acid on the underpotential deposition-stripping voltammetry of copper in acetic acid soil extract solutions at mercaptoacetic acid-modified gold electrodes

Energy Technology Data Exchange (ETDEWEB)

Herzog, Gregoire; Beni, Valerio; Dillon, Patrick H.; Barry, Thomas; Arrigan, Damien W.M

2004-05-24

Electrochemical measurements were undertaken for the investigation of the underpotential deposition-stripping process of copper at bare and modified gold electrodes in 0.11 M acetic acid, the first fraction of the European Union's Bureau Communautaire de References (BCR) sequential extraction procedure for fractionating metals within soils and sediments. Gold electrodes modified with mercaptoacetic acid showed higher sensitivity for the detection of copper than bare gold electrodes, both in the absence and in the presence of humic acid in acetic acid solutions, using the underpotential deposition-stripping voltammetry (UPD-SV) method. In the presence of 50 mg l{sup -1} of humic acid, the mercaptoacetic acid modified electrode proved to be 1.5 times more sensitive than the bare gold electrode. The mercaptoacetic acid monolayer formed on the gold surface provided efficient protection against the adsorption of humic acid onto the gold electrode surface. Variation of the humic acid concentration in the solution showed little effect on the copper stripping signal at the modified electrode. UPD-SV at the modified electrode was applied to the analysis of soil extract samples. Linear correlation of the electrochemical results with atomic spectroscopic results yielded the straight-line equation y ({mu}g l{sup -1}) = 1.10x - 44 (ppb) (R=0.992, n=6), indicating good agreement between the two methods.

Conductometric gas sensors based on metal oxides modified with gold nanoparticles: a review

International Nuclear Information System (INIS)

Korotcenkov, Ghenadii; Cho, Beong K.; Brinzari, Vladimir

2016-01-01

This review (with 170 refs.) discusses approaches towards surface functionalizaton of metal oxides by gold nanoparticles, and the application of the resulting nanomaterials in resistive gas sensors. The articles is subdivided into sections on (a) methods for modification of metal oxides with gold nanoparticles; (b) the response of gold nanoparticle-modified metal oxide sensors to gaseous species, (c) a discussion of the limitations of such sensors, and (d) a discussion on future tasks and trends along with an outlook. It is shown that, in order to achieve significant improvements in sensor parameters, it is necessary to warrant a good control the size and density of gold nanoparticles on the surface of metal oxide crystallites, the state of gold in the cluster, and the properties of the metal oxide support. Current challenges include an improved reproducibility of sensor preparation, better long-term stabilities, and a better resistance to sintering and poisoning of gold clusters during operation. Additional research focused on better understanding the role of gold clusters and nanoparticles in gas-sensing effects is also required. (author)

Spatial Rearrangement and Mobility Heterogeneity of an Anionic Lipid Monolayer Induced by the Anchoring of Cationic Semiflexible Polymer Chains

Directory of Open Access Journals (Sweden)

Xiaozheng Duan

2016-06-01

Full Text Available We use Monte Carlo simulations to investigate the interactions between cationic semiflexible polymer chains and a model fluid lipid monolayer composed of charge-neutral phosphatidyl-choline (PC, tetravalent anionic phosphatidylinositol 4,5-bisphosphate (PIP2, and univalent anionic phosphatidylserine (PS lipids. In particular, we explore how chain rigidity and polymer concentration influence the spatial rearrangement and mobility heterogeneity of the monolayer under the conditions where the cationic polymers anchor on the monolayer. We find that the anchored cationic polymers only sequester the tetravalent PIP2 lipids at low polymer concentrations, where the interaction strength between the polymers and the monolayer exhibits a non-monotonic dependence on the degree of chain rigidity. Specifically, maximal anchoring occurs at low polymer concentrations, when the polymer chains have an intermediate degree of rigidity, for which the PIP2 clustering becomes most enhanced and the mobility of the polymer/PIP2 complexes becomes most reduced. On the other hand, at sufficiently high polymer concentrations, the anchoring strength decreases monotonically as the chains stiffen—a result that arises from the pronounced competitions among polymer chains. In this case, the flexible polymers can confine all PIP2 lipids and further sequester the univalent PS lipids, whereas the stiffer polymers tend to partially dissociate from the monolayer and only sequester smaller PIP2 clusters with greater mobilities. We further illustrate that the mobility gradient of the single PIP2 lipids in the sequestered clusters is sensitively modulated by the cooperative effects between anchored segments of the polymers with different rigidities. Our work thus demonstrates that the rigidity and concentration of anchored polymers are both important parameters for tuning the regulation of anionic lipids.

Thermal stability of thiol and silane monolayers: A comparative study

International Nuclear Information System (INIS)

Chandekar, Amol; Sengupta, Sandip K.; Whitten, James E.

2010-01-01

The stability of self-assembled monolayers (SAMs) at elevated temperatures is of considerable technological importance. The thermal stability of 1-octadecanethiol (ODT), 16-mercaptohexadecanoic acid (MHDA) and 1H,1H,2H,2H-perfluorodecanethiol (PFDT) SAMs on gold surfaces, and of 4-aminobutyltriethoxysilane (ABTES) and 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane (PFDS) assembled on hydroxylated silicon surfaces, was studied by X-ray photoelectron spectroscopy (XPS). The samples were heated in ultrahigh vacuum to temperatures in excess of that required for SAM degradation. ODT monolayers were stable to ca. 110 deg. C, while MHDA and PFDT SAMs were stable to ca. 145 deg. C. ABTES SAMs were found to be indefinitely stable to 250 deg. C, while PFDS SAMs were stable to 350 deg. C. These studies demonstrate the advantages of using silane monolayers for moderate to high temperature applications and illustrate differences that arise due to the nature of the tail group. To demonstrate the feasibility of silanes for template-directed patterning, a hydroxylated silicon oxide surface containing microcontact-printed PFDS patterns was spin-coated with a mainly hydrophilic block copolymer. Annealing the surface at 90 deg. C for 2 h caused the block copolymer to dewet the hydrophobic PFDS-patterned regions and adsorb exclusively on the unpatterned regions of the surface.

Controlled adsorption of cytochrome c to nanostructured gold surfaces

International Nuclear Information System (INIS)

Gomes, Inês; Feio, Maria J.; Santos, Nuno C.; Eaton, Peter; Serro, Ana Paula; Saramago, Benilde; Pereira, Eulália; Franco, Ricardo

2012-01-01

Controlled electrostatic physisorption of horse heart cytochrome c (Cyt c) onto nanostructured gold surfaces was investigated using Quartz-Crystal Microbalance measurements in planar gold surfaces with or without functionalization using a self-assembled monolayer (SAM) of the alkanethiol mercaptoundecanoic acid (MUA). MUA is a useful functionalization ligand for gold surfaces, shedding adsorbed biomolecules from the excessive electron density of the metal. A parallel analysis was conducted in the corresponding curved surfaces of 15 nm gold nanoparticles (AuNPs), using zeta-potential and UV– visible spectroscopy. Atomic Force Microscopy of both types of functionalized gold surfaces with a MUA SAM, allowed for visualization of Cyt c deposits on the nanostructured gold surface. The amount of Cyt c adsorbed onto the gold surface could be controlled by the solution pH. For the assays conducted at pH 4.5, when MUA SAM- functionalized planar gold surfaces are positive or neutral, and Cyt c has a positive net charge, only 13 % of the planar gold surface area was coated with protein. In contrast, at pH 7.4, when MUA SAM-functionalized planar gold surfaces and Cyt c have opposite charges, a protein coverage of 28 % could be observed implying an adsorption process strongly governed by electrostatic forces. Cyt c adsorption on planar and curved gold surfaces are found to be greatly favored by the presence of a MUA-capping layer. In particular, on the AuNPs, the binding constant is three times larger than the binding constant obtained for the original citrate-capped AuNPs.

Controlled adsorption of cytochrome c to nanostructured gold surfaces

Energy Technology Data Exchange (ETDEWEB)

Gomes, Ines [Faculdade de Ciencias e Tecnologia, Universidade Nova de Lisboa, REQUIMTE, Departamento de Quimica (Portugal); Feio, Maria J. [Faculdade de Ciencias da Universidade do Porto, REQUIMTE, Departamento de Quimica e Bioquimica (Portugal); Santos, Nuno C. [Faculdade de Medicina da Universidade de Lisboa, Instituto de Medicina Molecular (Portugal); Eaton, Peter [Faculdade de Ciencias da Universidade do Porto, REQUIMTE, Departamento de Quimica e Bioquimica (Portugal); Serro, Ana Paula; Saramago, Benilde [Centro de Quimica Estrutural, Instituto Superior Tecnico (Portugal); Pereira, Eulalia [Faculdade de Ciencias da Universidade do Porto, REQUIMTE, Departamento de Quimica e Bioquimica (Portugal); Franco, Ricardo, E-mail: ricardo.franco@fct.unl.pt [Faculdade de Ciencias e Tecnologia, Universidade Nova de Lisboa, REQUIMTE, Departamento de Quimica (Portugal)

2012-12-15

Controlled electrostatic physisorption of horse heart cytochrome c (Cyt c) onto nanostructured gold surfaces was investigated using Quartz-Crystal Microbalance measurements in planar gold surfaces with or without functionalization using a self-assembled monolayer (SAM) of the alkanethiol mercaptoundecanoic acid (MUA). MUA is a useful functionalization ligand for gold surfaces, shedding adsorbed biomolecules from the excessive electron density of the metal. A parallel analysis was conducted in the corresponding curved surfaces of 15 nm gold nanoparticles (AuNPs), using zeta-potential and UV- visible spectroscopy. Atomic Force Microscopy of both types of functionalized gold surfaces with a MUA SAM, allowed for visualization of Cyt c deposits on the nanostructured gold surface. The amount of Cyt c adsorbed onto the gold surface could be controlled by the solution pH. For the assays conducted at pH 4.5, when MUA SAM- functionalized planar gold surfaces are positive or neutral, and Cyt c has a positive net charge, only 13 % of the planar gold surface area was coated with protein. In contrast, at pH 7.4, when MUA SAM-functionalized planar gold surfaces and Cyt c have opposite charges, a protein coverage of 28 % could be observed implying an adsorption process strongly governed by electrostatic forces. Cyt c adsorption on planar and curved gold surfaces are found to be greatly favored by the presence of a MUA-capping layer. In particular, on the AuNPs, the binding constant is three times larger than the binding constant obtained for the original citrate-capped AuNPs.

Polycyclic aromatic hydrocarbons in model bacterial membranes - Langmuir monolayer studies.

Science.gov (United States)

Broniatowski, Marcin; Binczycka, Martyna; Wójcik, Aneta; Flasiński, Michał; Wydro, Paweł

2017-12-01

High molecular weight polycyclic aromatic hydrocarbons (HMW-PAHs) are persistent organic pollutants which due to their limited biodegradability accumulate in soils where their increased presence can lead to the impoverishment of the decomposer organisms. As very hydrophobic PAHs easily penetrate cellular membranes of soil bacteria and can be incorporated therein, changing the membrane fluidity and other functions which in consequence can lead to the death of the organism. The structure and size of PAH molecule can be crucial for its membrane activity; however the correlation between PAH structure and its interaction with phospholipids have not been investigated so far. In our studies we applied phospholipid Langmuir monolayers as model bacterial membranes and investigated how the incorporation of six structurally different PAH molecules change the membrane texture and physical properties. In our studies we registered surface pressure and surface potential isotherms upon the monolayer compression, visualized the monolayer texture with the application of Brewster angle microscopy and searched the ordering of the film-forming molecules with molecular resolution with the application of grazing incidence X-ray diffraction (GIXD) method. It turned out that the phospholipid-PAH interactions are strictly structure dependent. Four and five-ring PAHs of the angular or cluster geometry can be incorporated into the model membranes changing profoundly their textures and fluidity; whereas linear or large cluster PAHs cannot be incorporated and separate from the lipid matrix. The observed phenomena were explained based on structural similarities of the applied PAHs with membrane steroids and hopanoids. Copyright © 2017. Published by Elsevier B.V.

CO oxidation on gold nanoparticles: Theoretical studies

DEFF Research Database (Denmark)

Remediakis, Ioannis; Lopez, Nuria; Nørskov, Jens Kehlet

2005-01-01

We present a summary of our theoretical results regarding CO oxidation on both oxide-supported and isolated gold nanoparticles. Using Density Functional Theory we have studied the adsorption of molecules and the oxidation reaction of CO on gold clusters. Low-coordinated sites on the gold...... nanoparticles can adsorb small inorganic molecules such as O2 and CO, and the presence of these sites is the key factor for the catalytic properties of supported gold nanoclusters. Other contributions, induced by the presence of the support, can provide parallel channels for the reaction and modulate the final...

Discrete quantum dot like emitters in monolayer MoSe{sub 2}: Spatial mapping, magneto-optics, and charge tuning

Energy Technology Data Exchange (ETDEWEB)

Branny, Artur; Kumar, Santosh; Gerardot, Brian D., E-mail: b.d.gerardot@hw.ac.uk [Institute of Photonics and Quantum Sciences, SUPA, Heriot-Watt University, Edinburgh EH14 4AS (United Kingdom); Wang, Gang; Robert, Cedric; Lassagne, Benjamin; Marie, Xavier; Urbaszek, Bernhard, E-mail: urbaszek@insa-toulouse.fr [Université de Toulouse, INSA-CNRS-UPS, LPCNO, 135 Av. Rangueil, 31077 Toulouse (France)

2016-04-04

Transition metal dichalcogenide monolayers such as MoSe{sub 2}, MoS{sub 2}, and WSe{sub 2} are direct bandgap semiconductors with original optoelectronic and spin-valley properties. Here we report on spectrally sharp, spatially localized emission in monolayer MoSe{sub 2}. We find this quantum dot-like emission in samples exfoliated onto gold substrates and also suspended flakes. Spatial mapping shows a correlation between the location of emitters and the existence of wrinkles (strained regions) in the flake. We tune the emission properties in magnetic and electric fields applied perpendicular to the monolayer plane. We extract an exciton g-factor of the discrete emitters close to −4, as for 2D excitons in this material. In a charge tunable sample, we record discrete jumps on the meV scale as charges are added to the emitter when changing the applied voltage.

Position and Orientation Control of a Photo- and Electrochromic Dithienylethene Using a Tripodal Anchor on Gold Surfaces

NARCIS (Netherlands)

Pijper, Thomas C.; Ivashenko, Oleksii; Walko, Martin; Rudolf, Petra; Browne, Wesley R.; Feringa, Ben L.

2015-01-01

A tripodal system for anchoring photochromic dithienylethenes on gold surfaces is reported. The self-assembled monolayers of a tripod-functionalized dithienylethene were characterized by cyclic voltammetry, surface-enhanced Raman spectroscopy (SERS), and X-ray photoelectron spectroscopy (XPS). These

Gold core@silver semishell Janus nanoparticles prepared by interfacial etching

Science.gov (United States)

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

Ultrasensitive interdigitated capacitance immunosensor using gold nanoparticles

Science.gov (United States)

Alizadeh Zeinabad, Hojjat; Ghourchian, Hedayatollah; Falahati, Mojtaba; Fathipour, Morteza; Azizi, Marzieh; Boutorabi, Seyed Mehdi

2018-06-01

Immunosensors based on interdigitated electrodes (IDEs), have recently demonstrated significant improvements in the sensitivity of capacitance detection. Herein, a novel type of highly sensitive, compact and portable immunosensor based on a gold interdigital capacitor has been designed and developed for the rapid detection of hepatitis B surface antigen (HBsAg). To improve the efficiency of antibody immobilization and time-saving, a self-assembled monolayer (SAM) of 2-mercaptoethylamine film was coated on IDEs. Afterwards, carboxyl groups on primary antibodies were activated through 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and were immobilized on amino-terminated SAM for better control of the oriented immobilization of antibodies on gold IDEs. In addition, gold nanoparticles conjugated with a secondary antibody were used to enhance the sensitivity. Under optimal conditions, the immunosensor exhibited the sensitivity of 0.22 nF.pg ml–1, the linear range from 5 pg ml‑1 to 1 ng ml–1 and the detection limit of 1.34 pg ml‑1, at a signal-to-noise ratio of 3.

Differences in the Aspect Ratio of Gold Nanorods that Induce Defects in Cell Membrane Models.

Science.gov (United States)

Lins, Paula M P; Marangoni, Valéria S; Uehara, Thiers M; Miranda, Paulo B; Zucolotto, Valtencir; Cancino-Bernardi, Juliana

2017-12-19

Understanding the interactions between biomolecules and nanomaterials is of great importance for many areas of nanomedicine and bioapplications. Although studies in this area have been performed, the interactions between cell membranes and nanoparticles are not fully understood. Here, we investigate the interactions that occur between the Langmuir monolayers of dipalmitoylphosphatidyl glycerol (DPPG) and dipalmitoylphosphatidyl choline (DPPC) with gold nanorods (NR)-with three aspect ratios-and gold nanoparticles. Our results showed that the aspect ratio of the NRs influenced the interactions with both monolayers, which suggest that the physical morphology and electrostatic forces govern the interactions in the DPPG-NR system, whereas the van der Waals interactions are predominant in the DPPC-NR systems. Size influences the expansion isotherms in both systems, but the lipid tails remain conformationally ordered upon expansion, which suggests phase separation between the lipids and nanomaterials at the interface. The coexistence of lipid and NP regions affects the elasticity of the monolayer. When there is coexistence between two phases, the elasticity does not reflect the lipid packaging state but depends on the elasticity of the NP islands. Therefore, the results corroborate that nanomaterials influence the packing and the phase behavior of the mimetic cell membranes. For this reason, developing a methodology to understand the membrane-nanomaterial interactions is of great importance.

An Electrochemical Immunosensor for Detection of Staphylococcus aureus Bacteria Based on Immobilization of Antibodies on Self-Assembled Monolayers-Functionalized Gold Electrode

Directory of Open Access Journals (Sweden)

Abderrazak Maaref

2012-10-01

Full Text Available The detection of pathogenic bacteria remains a challenge for the struggle against biological weapons, nosocomial diseases, and for food safety. In this research, our aim was to develop an easy-to-use electrochemical immunosensor for the detection of pathogenic Staphylococcus aureus ATCC25923. The biosensor was elaborated by the immobilization of anti-S. aureus antibodies using a self-assembled monolayer (SAMs of 3-Mercaptopropionic acid (MPA. These molecular assemblies were spontaneously formed by the immersion of the substrate in an organic solvent containing the SAMs that can covalently bond to the gold surface. The functionalization of the immunosensor was characterized using two electrochemical techniques: cyclic voltammetry (CV and electrochemical impedance spectroscopy (EIS. Here, the analysis was performed in phosphate buffer with ferro/ferricyanide as the redox probe. The EIS technique was used for affinity assays: antibody-cell binding. A linear relationship between the increment in the electron transfer resistance (RCT and the logarithmic value of S. aureus concentration was observed between 10 and 106 CFU/mL. The limit of detection (LOD was observed at 10 CFU/mL, and the reproducibility was calculated to 8%. Finally, a good selectivity versus E. coli and S. epidermidis was obtained for our developed immunosensor demonstrating its specificity towards only S. aureus.

Transport properties in monolayer-bilayer-monolayer graphene planar junctions

Institute of Scientific and Technical Information of China (English)

Kai-Long Chu; Zi-Bo Wang; Jiao-Jiao Zhou; Hua Jiang

2017-01-01

The transport study of graphene based junctions has become one of the focuses in graphene research.There are two stacking configurations for monolayer-bilayer-monolayer graphene planar junctions.One is the two monolayer graphene contacting the same side of the bilayer graphene,and the other is the two-monolayer graphene contacting the different layers of the bilayer graphene.In this paper,according to the Landauer-Büttiker formula,we study the transport properties of these two configurations.The influences of the local gate potential in each part,the bias potential in bilayer graphene,the disorder and external magnetic field on conductance are obtained.We find the conductances of the two configurations can be manipulated by all of these effects.Especially,one can distinguish the two stacking configurations by introducing the bias potential into the bilayer graphene.The strong disorder and the external magnetic field will make the two stacking configurations indistinguishable in the transport experiment.

Active sites of ligand-protected Au25 nanoparticle catalysts for CO2 electroreduction to CO

Science.gov (United States)

Alfonso, Dominic R.; Kauffman, Douglas; Matranga, Christopher

2016-05-01

Recent experimental studies have reported the electrochemical reduction of carbon dioxide (CO2) into CO at atomically precise negatively charged Au25- nanoclusters. The studies showed CO2 conversion at remarkably low overpotentials, but the exact mechanisms and nature of the active sites remain unclear. We used first-principles density functional theory and continuum solvation models to examine the role of the cluster during electrochemical CO2 reduction and analyze the free energies of proposed intermediate species. Contrary to previous assumptions, our results show that the fully ligand protected cluster is not an active CO2 reduction catalyst because formation of the crucial carboxyl intermediate required very high electrochemical potentials. Instead, our calculations suggest that the reduction process likely occurs on a dethiolated gold site, and adsorbed carboxyl intermediate formation was significantly stabilized at dethiolated gold sites. These findings point to the crucial role of exposed metal sites during electrochemical CO2 reduction at gold nanocluster catalysts.

TiO2/Gold nanocomposite as an extremely sensitive molecule sensor for NO2 detection: A DFT study

Directory of Open Access Journals (Sweden)

Amirali Abbasi

2016-07-01

Full Text Available First-principles calculations within density functional theory (DFT have been performed to investigate the interactions of NO2 molecules with TiO2/Gold nanocomposites in order to completely exploit the adsorption properties of these nanostructures. Given the need to further comprehend the behavior of the NO2 molecules positioned between the TiO2 nanoparticle and Au monolayer, we have geometrically optimized the complex systems consisting of the NO2 molecule oriented at appropriate positions between the nanoparticle and Au monolayer. The structural properties such as bond lengths, bond angles, adsorption energies and Mulliken population analysis and the electronic properties including the density of states and molecular orbitals have been also analyzed in detail. The results indicate that the interaction between NO2 and undoped TiO2-N/Gold nanocomposites is stronger than that between gas molecules and N-doped TiO2/Gold nanocomposites, which reveals that the pristine nanocomposite can react with NO2 molecule more efficiently. Therefore, the obtained results also suggest a theoretical basis for the potential applications of TiO2/Gold nanocomposites in gas sensing, which could help in the developing of novel TiO2 based advanced sensor devices.

Atomic force microscopy studies of lateral phase separation in mixed monolayers of dipalmitoylphosphatidylcholine and dilauroylphosphatidylcholine

Energy Technology Data Exchange (ETDEWEB)

Sanchez, Jacqueline; Badia, Antonella

2003-09-01

Atomic force microscopy imaging of dipalmitoylphosphatidylcholine (DPPC)/dilauroylphosphatidylcholine (DLPC) monolayers deposited onto alkanethiol modified-gold surfaces by the Langmuir-Schaefer technique was used to investigate domain formation in a binary system where phase separation arises from a difference in the alkyl chain lengths of the lipids. We have established how the condensed domain structure (shape and size) in DPPC/DLPC monolayers depends on the surface pressure and lipid composition. The mixed monolayers exhibit a positive deviation from an ideal mixing behavior at surface pressures of {<=}32 mN/m. Lateral compression to pressures greater than the liquid-expanded-to-liquid-condensed (LE-to-LC) phase transition pressure of the mixed monolayer ({approx}8-16 mN/m) induces extensive separation into condensed DPPC-rich domains and a fluid DLPC matrix. The condensed structures observed at a few milliNeutons per meter above the LE-to-LC transition pressure resemble those reported for pure DPPC monolayers in the LE/LC co-existence region. At a bilayer equivalence pressure of 32 mN/m and 20 deg. C, condensed domains exist between x{sub DPPC} {approx}0.25 and {approx}0.80, analogous to aqueous DPPC/DLPC dispersions. Compression from 32 to 40 mN/m results in either a striking distortion of the DPPC domain shape or a break-up of the microscopic DPPC domains into a network of nanoscopic islands (at higher DPPC mol fractions), possibly reflecting a critical mixing behavior. The results of this study provide a fundamental framework for understanding and controlling the formation of lateral domain structures in mixed phospholipid monolayers.

Electrochemical and morphological characterization of gold nanoparticles deposited on boron-doped diamond electrode

Energy Technology Data Exchange (ETDEWEB)

Limat, Meriadec; El Roustom, Bahaa [Ecole Polytechnique Federale de Lausanne (EPFL), Institute of Chemical Sciences and Engineering, CH-1015 Lausanne (Switzerland); Jotterand, Henri [Ecole Polytechnique Federale de Lausanne (EPFL), Institute of Physics of the Complex Matter, CH-1015 Lausanne (Switzerland); Foti, Gyoergy [Ecole Polytechnique Federale de Lausanne (EPFL), Institute of Chemical Sciences and Engineering, CH-1015 Lausanne (Switzerland)], E-mail: gyorgy.foti@epfl.ch; Comninellis, Christos [Ecole Polytechnique Federale de Lausanne (EPFL), Institute of Chemical Sciences and Engineering, CH-1015 Lausanne (Switzerland)

2009-03-30

A novel two-step method was employed to synthesize gold nanoparticles dispersed on boron-doped diamond (BDD) electrode. It consisted of sputter deposition at ambient temperature of maximum 15 equivalent monolayers of gold, followed by a heat treatment in air at 600 deg. C. Gold nanoparticles with an average diameter between 7 and 30 nm could be prepared by this method on polycrystalline BDD film electrode. The obtained Au/BDD composite electrode appeared stable under conditions of electrochemical characterization performed using ferri-/ferrocyanide and benzoquinone/hydroquinone redox couples in acidic medium. The electrochemical behavior of Au/BDD was compared to that of bulk Au and BDD electrodes. Finally, the Au/BDD composite electrode was regarded as an array of Au microelectrodes dispersed on BDD substrate.

Electrochemical and morphological characterization of gold nanoparticles deposited on boron-doped diamond electrode

International Nuclear Information System (INIS)

Limat, Meriadec; El Roustom, Bahaa; Jotterand, Henri; Foti, Gyoergy; Comninellis, Christos

2009-01-01

A novel two-step method was employed to synthesize gold nanoparticles dispersed on boron-doped diamond (BDD) electrode. It consisted of sputter deposition at ambient temperature of maximum 15 equivalent monolayers of gold, followed by a heat treatment in air at 600 deg. C. Gold nanoparticles with an average diameter between 7 and 30 nm could be prepared by this method on polycrystalline BDD film electrode. The obtained Au/BDD composite electrode appeared stable under conditions of electrochemical characterization performed using ferri-/ferrocyanide and benzoquinone/hydroquinone redox couples in acidic medium. The electrochemical behavior of Au/BDD was compared to that of bulk Au and BDD electrodes. Finally, the Au/BDD composite electrode was regarded as an array of Au microelectrodes dispersed on BDD substrate

Constructing of DNA vectors with controlled nanosize and single dispersion by block copolymer coating gold nanoparticles as template assembly

Energy Technology Data Exchange (ETDEWEB)

Li, Junbo, E-mail: Lijunbo@haust.edu.cn [Henan University of Science and Technology, School of Chemical Engineering and Pharmaceutics (China); Wu, Wenlan [Henan University of Science and Technology, School of Medicine (China); Gao, Jiayu; Liang, Ju; Zhou, Huiyun; Liang, Lijuan [Henan University of Science and Technology, School of Chemical Engineering and Pharmaceutics (China)

2017-03-15

Synthesized vectors with nanoscale size and stable colloid dispersion are highly desirable for improving gene delivery efficiency. Here, a core-shell template particle was constructed with polyethylene glycol-b-poly1-(3-aminopropyl)-3-(2-methacryloyloxy propylimidazolium bromine) (PEG-b-PAMPImB) coating gold nanoparticles (PEG-b-PAMPImB-@-Au NPs) for loading DNA and delivering in vitro. Data from transmission electron microscopy (TEM) and dynamic light scattering (DLS) suggest that these nanoplexes, by forming an electrostatic complex with DNA at the inner PAMPImB shell, offer steric protection for the outer PEG corona leading to single dispersion and small size. Notably, higher colloid stability and lower cytotoxicity were achieved with these nanoplexes when compared with PAMPImB monolayer-coated gold nanoparticles (Au NPs). Confocal laser scanning microscopy and intracellular trafficking TEM further indicate that the nanoplexes can translocate across the cell membrane and partly enter the nucleus for high efficient expression. Thus, template assembly represents a promising approach to control the size and colloid stability of gene vectors and ensure safety and efficiency of DNA delivery.

Constructing of DNA vectors with controlled nanosize and single dispersion by block copolymer coating gold nanoparticles as template assembly

Science.gov (United States)

Li, Junbo; Wu, Wenlan; Gao, Jiayu; Liang, Ju; Zhou, Huiyun; Liang, Lijuan

2017-03-01

Synthesized vectors with nanoscale size and stable colloid dispersion are highly desirable for improving gene delivery efficiency. Here, a core-shell template particle was constructed with polyethylene glycol- b-poly1-(3-aminopropyl)-3-(2-methacryloyloxy propylimidazolium bromine) (PEG- b-PAMPImB) coating gold nanoparticles (PEG- b-PAMPImB-@-Au NPs) for loading DNA and delivering in vitro. Data from transmission electron microscopy (TEM) and dynamic light scattering (DLS) suggest that these nanoplexes, by forming an electrostatic complex with DNA at the inner PAMPImB shell, offer steric protection for the outer PEG corona leading to single dispersion and small size. Notably, higher colloid stability and lower cytotoxicity were achieved with these nanoplexes when compared with PAMPImB monolayer-coated gold nanoparticles (Au NPs). Confocal laser scanning microscopy and intracellular trafficking TEM further indicate that the nanoplexes can translocate across the cell membrane and partly enter the nucleus for high efficient expression. Thus, template assembly represents a promising approach to control the size and colloid stability of gene vectors and ensure safety and efficiency of DNA delivery.

Emergence of complex chemistry on an organic monolayer.

Science.gov (United States)

Prins, Leonard J

2015-07-21

In many origin-of-life scenarios, inorganic materials, such as FeS or mineral clays, play an important role owing to their ability to concentrate and select small organic molecules on their surface and facilitate their chemical transformations into new molecules. However, considering that life is made up of organic matter, at a certain stage during the evolution the role of the inorganic material must have been taken over by organic molecules. How this exactly happened is unclear, and, indeed, a big gap separates the rudimentary level of organization involving inorganic materials and the complex organization of cells, which are the building blocks of life. Over the past years, we have extensively studied the interaction of small molecules with monolayer-protected gold nanoparticles (Au NPs) for the purpose of developing innovative sensing and catalytic systems. During the course of these studies, we realized that the functional role of this system is very similar to that typically attributed to inorganic surfaces in the early stages of life, with the important being difference that the functional properties (molecular recognition, catalysis, signaling, adaptation) originate entirely from the organic monolayer rather than the inorganic support. This led us to the proposition that this system may serve as a model that illustrates how the important role of inorganic surfaces in dictating chemical processes in the early stages of life may have been taken over by organic matter. Here, we reframe our previously obtained results in the context of the origin-of-life question. The following functional roles of Au NPs will be discussed: the ability to concentrate small molecules and create different local populations, the ability to catalyze the chemical transformation of bound molecules, and, finally, the ability to install rudimentary signaling pathways and display primitive adaptive behavior. In particular, we will show that many of the functional properties of the system

Diamondoid monolayers as electron emitters

Science.gov (United States)

Yang, Wanli [El Cerrito, CA; Fabbri, Jason D [San Francisco, CA; Melosh, Nicholas A [Menlo Park, CA; Hussain, Zahid [Orinda, CA; Shen, Zhi-Xun [Stanford, CA

2012-04-10

Provided are electron emitters based upon diamondoid monolayers, preferably self-assembled higher diamondoid monolayers. High intensity electron emission has been demonstrated employing such diamondoid monolayers, particularly when the monolayers are comprised of higher diamondoids. The application of such diamondoid monolayers can alter the band structure of substrates, as well as emit monochromatic electrons, and the high intensity electron emissions can also greatly improve the efficiency of field-effect electron emitters as applied to industrial and commercial applications.

Screening of self-assembled monolayer for aflatoxin B1 detection using immune-capacitive sensor

Directory of Open Access Journals (Sweden)

Alvaro V. Gutierrez R

2015-12-01

Full Text Available A capacitive biosensor was used for detection of aflatoxin B1. Two different methods for cleaning gold electrodes were evaluated using cyclic voltammetry in the presence of ferricyanide as redox couple. The methods involve use of a sequence of cleaning steps avoiding the use of Piranha solution and plasma cleaner. Anti-aflatoxin B1 was immobilized on self-assembled monolayers (SAM. The immune-capacitive biosensor is able to detect aflatoxin B1 concentrations in a linear range of 3.2 × 10−12 M to 3.2 × 10−9 M when thiourea was used to form the SAM; 3.2 × 10−9 M to 3.2 × 10−7 M when thioctic acid was used. When the gold surface was isolated with tyramine-electropolymerization linear ranges of 3.2 × 10−13 M to 3.2 × 10−7 M and 3.2 × 10−9 M to 3.2 × 10−7 M where obtained, respectively. The results obtained show the difference in linear range, limit of detection, and limit of quantification when different self-assembled monolayers are used for aflatoxin B1 detection.

Robust gold nanoparticles stabilized by trithiol for application in chemiresistive sensors

International Nuclear Information System (INIS)

Garg, Niti; Mohanty, Ashok; Jin, Rongchao; Lazarus, Nathan; Santhanam, Suresh; Fedder, Gary K; Schultz, Lawrence; Weiss, Lee; Rozzi, Tony R; Snyder, Jay L

2010-01-01

The use of gold nanoparticles coated with an organic monolayer of thiol for application in chemiresistive sensors was initiated in the late 1990s; since then, such types of sensors have been widely pursued due to their high sensitivities and reversible responses to volatile organic compounds (VOCs). However, a major issue for chemical sensors based on thiol-capped gold nanoparticles is their poor long-term stability as a result of slow degradation of the monothiol-to-gold bonds. We have devised a strategy to overcome this limitation by synthesizing a more robust system using Au nanoparticles capped by trithiol ligands. Compared to its monothiol counterpart, the new system is significantly more stable and also shows improved sensitivity towards different types of polar or non-polar VOCs. Thus, the trithiol-Au nanosensor shows great promise for use in real world applications.

Robust gold nanoparticles stabilized by trithiol for application in chemiresistive sensors

Energy Technology Data Exchange (ETDEWEB)

Garg, Niti; Mohanty, Ashok; Jin, Rongchao [Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213 (United States); Lazarus, Nathan; Santhanam, Suresh; Fedder, Gary K [Department of Electrical and Computer Engineering, Carnegie Mellon University, Pittsburgh, PA 15213 (United States); Schultz, Lawrence; Weiss, Lee [Robotics Institute, Carnegie Mellon University, Pittsburgh, PA 15213 (United States); Rozzi, Tony R; Snyder, Jay L, E-mail: zpx5@cdc.gov, E-mail: fedder@ece.cmu.edu, E-mail: rongchao@andrew.cmu.edu [National Institute for Occupational Safety and Health (NIOSH), Pittsburgh, PA 15236 (United States)

2010-10-08

The use of gold nanoparticles coated with an organic monolayer of thiol for application in chemiresistive sensors was initiated in the late 1990s; since then, such types of sensors have been widely pursued due to their high sensitivities and reversible responses to volatile organic compounds (VOCs). However, a major issue for chemical sensors based on thiol-capped gold nanoparticles is their poor long-term stability as a result of slow degradation of the monothiol-to-gold bonds. We have devised a strategy to overcome this limitation by synthesizing a more robust system using Au nanoparticles capped by trithiol ligands. Compared to its monothiol counterpart, the new system is significantly more stable and also shows improved sensitivity towards different types of polar or non-polar VOCs. Thus, the trithiol-Au nanosensor shows great promise for use in real world applications.

Photocarrier dynamics in monolayer phosphorene and bulk black phosphorus.

Science.gov (United States)

Zereshki, Peymon; Wei, Yaqing; Ceballos, Frank; Bellus, Matthew Z; Lane, Samuel D; Pan, Shudi; Long, Run; Zhao, Hui

2018-06-13

We report a combined theoretical and experimental study on photocarrier dynamics in monolayer phosphorene and bulk black phosphorus. Samples of monolayer phosphorene and bulk black phosphorus were fabricated by mechanical exfoliation, identified according to their reflective contrasts, and protected by covering them with hexagonal boron nitride layers. Photocarrier dynamics in these samples was studied by an ultrafast pump-probe technique. The photocarrier lifetime of monolayer phosphorene was found to be about 700 ps, which is about 9 times longer than that of bulk black phosphorus. This trend was reproduced in our calculations based on ab initio nonadiabatic molecular dynamics combined with time-domain density functional theory in the Kohn-Sham representation, and can be attributed to the smaller bandgap and stronger nonadiabatic coupling in bulk. The transient absorption response was also found to be dependent on the sample orientation with respect to the pump polarization, which is consistent with the previously reported anisotropic absorption of phosphorene. In addition, an oscillating component of the differential reflection signal at early probe delays was observed in the bulk sample and was attributed to the layer-breathing phonon mode with an energy of about 1 meV and a decay time of about 1.35 ps. These results provide valuable information for application of monolayer phosphorene in optoelectronics.

Transformation of thiolated chitosan-templated gold nanoparticles to huge microcubes

International Nuclear Information System (INIS)

Sun, Yudie; Liu, Honglin; Yang, Liangbao; Sun, Bai; Liu, Jinhuai

2014-01-01

Graphical abstract: - Highlights: • Mercapto groups were grafted to chitosan molecule by a reactive amine reduction. • Functional polymer with well-defined monomer units controls AuNPs assembly. • Assembled morphologies depend on the ratio of AuNPs to thiolate groups. • Microcubes with side length of ∼20 μm was synthesized through a dialysis step. • A edge-to-middle growth mechanism of gold microcubes was observed. - Abstract: The L-cysteine molecules were successfully grafted to the 2-amino group of chitosan by a reactive amine reduction, and the as-synthesized thiolated chitosan (TC) molecules were used as the templates to direct the self-assembly of gold nanoparticles and induce the transformation of these assemblies to gold microcubes through a deep-going dialysis. We found that the ratio of gold nanoparticles to TC molecules could greatly affect the shape of the assembled clusters. Different stages of these clusters and microstructures during the dialysis process were characterized by scanning electron microscope (SEM), and the microcubes with average side length of about 20 μm were successfully synthesized. According to the morphology evolution of the assembly, it could be concluded that the microcubes were formed from external to internal. The SERS area mapping images of microcubes and some clusters were also collected to study the formation mechanism of gold microcubes. Our work demonstrates a simple and highly effective way to assemble gold nanoparticles into microcubes with unique properties

Transformation of thiolated chitosan-templated gold nanoparticles to huge microcubes

Energy Technology Data Exchange (ETDEWEB)

Sun, Yudie [School of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026 (China); Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031 (China); Liu, Honglin, E-mail: hlliu@iim.ac.cn [Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031 (China); Yang, Liangbao, E-mail: lbyang@iim.ac.cn [Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031 (China); Sun, Bai; Liu, Jinhuai [Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031 (China)

2014-05-01

Graphical abstract: - Highlights: • Mercapto groups were grafted to chitosan molecule by a reactive amine reduction. • Functional polymer with well-defined monomer units controls AuNPs assembly. • Assembled morphologies depend on the ratio of AuNPs to thiolate groups. • Microcubes with side length of ∼20 μm was synthesized through a dialysis step. • A edge-to-middle growth mechanism of gold microcubes was observed. - Abstract: The L-cysteine molecules were successfully grafted to the 2-amino group of chitosan by a reactive amine reduction, and the as-synthesized thiolated chitosan (TC) molecules were used as the templates to direct the self-assembly of gold nanoparticles and induce the transformation of these assemblies to gold microcubes through a deep-going dialysis. We found that the ratio of gold nanoparticles to TC molecules could greatly affect the shape of the assembled clusters. Different stages of these clusters and microstructures during the dialysis process were characterized by scanning electron microscope (SEM), and the microcubes with average side length of about 20 μm were successfully synthesized. According to the morphology evolution of the assembly, it could be concluded that the microcubes were formed from external to internal. The SERS area mapping images of microcubes and some clusters were also collected to study the formation mechanism of gold microcubes. Our work demonstrates a simple and highly effective way to assemble gold nanoparticles into microcubes with unique properties.

Detection of aniline oligomers on polyaniline-gold interface using resonance Raman scattering.

Science.gov (United States)

Trchová, Miroslava; Morávková, Zuzana; Dybal, Jiří; Stejskal, Jaroslav

2014-01-22

In situ deposited conducting polyaniline films prepared by the oxidation of aniline with ammonium peroxydisulfate in aqueous media of various acidities on gold and silicon supports were characterized by Raman spectroscopy. Enhanced Raman bands were found in the spectra of polyaniline films produced in the solutions of weak acids or in water on gold surface. These bands were weak for the films prepared in solutions of a strong acid on a gold support. The same bands are present in the Raman spectra of the reaction intermediates deposited during aniline oxidation in water or aqueous solutions of weak or strong acids on silicon removed from the reaction mixture at the beginning of the reaction. Such films are formed by aniline oligomers adsorbed on the surface. They were detected on the polyaniline-gold interface using resonance Raman scattering on the final films deposited on gold. The surface resonance Raman spectroscopy of the monolayer of oligomers found in the bulk polyaniline film makes this method advantageous in surface science, with many applications in electrochemistry, catalysis, and biophysical, polymer, or analytical chemistry.

Characterization of gold nanoparticle pentacene memory device with polymer dielectric layer

International Nuclear Information System (INIS)

Kim, Hyung-Jun; Jung, Sung Mok; Kim, Yo-Han; Kim, Bong-Jin; Ha, Sanghyub; Kim, Yong-Sang; Yoon, Tae-Sik; Lee, Hyun Ho

2011-01-01

We report on the electrical behavior of gold nanoparticles (Au NPs) intervened metal-pentacene-insulator-semiconductor structures. The structure adopts polyvinyl alcohol (PVA) and pentacene as gate insulator and semiconductor, respectively. On the PVA (250 nm) film which was spin-coated and UV cross-linked, 3-aminopropyl triethoxysilane was functionalized for self assembling of the Au NPs monolayer. The devices exhibited clockwise hysteresis in their capacitance-voltage characteristics, with a memory window depending on the range of the voltage sweep. A relatively large memory window of about 4.7 V, which was deduced from control devices, was achieved with voltage sweep of (-/+)7 V. Formation of the monolayered Au NPs was confirmed by field effect scanning electron microscopy and atomic force microscopy.

Failure mechanism of monolayer graphene under hypervelocity impact of spherical projectile

Science.gov (United States)

Xia, Kang; Zhan, Haifei; Hu, De'An; Gu, Yuantong

2016-09-01

The excellent mechanical properties of graphene have enabled it as appealing candidate in the field of impact protection or protective shield. By considering a monolayer graphene membrane, in this work, we assessed its deformation mechanisms under hypervelocity impact (from 2 to 6 km/s), based on a serial of in silico studies. It is found that the cracks are formed preferentially in the zigzag directions which are consistent with that observed from tensile deformation. Specifically, the boundary condition is found to exert an obvious influence on the stress distribution and transmission during the impact process, which eventually influences the penetration energy and crack growth. For similar sample size, the circular shape graphene possesses the best impact resistance, followed by hexagonal graphene membrane. Moreover, it is found the failure shape of graphene membrane has a strong relationship with the initial kinetic energy of the projectile. The higher kinetic energy, the more number the cracks. This study provides a fundamental understanding of the deformation mechanisms of monolayer graphene under impact, which is crucial in order to facilitate their emerging future applications for impact protection, such as protective shield from orbital debris for spacecraft.

Electrochemistry of the Self-Assembled Monolayers of Dyads Consisting of Tripod-Shaped Trithiol and Bithiophene on Gold

Directory of Open Access Journals (Sweden)

Toshikazu Kitagawa

2014-09-01

Full Text Available Self-assembled monolayers (SAMs of tripod-shaped trithiols, consisting of an adamantane core with three CH2SH legs and a bithiophene group, were prepared on a Au(111 surface. Adsorption in a tripod-like fashion was supported by polarization modulation-infrared reflection absorption spectroscopy (PM-IRRAS of the SAMs, which indicated the absence of free SH groups. Cyclic voltammetry showed an irreversible cathodic wave due to reductive desorption. The SAM also showed an anodic wave due to the single-electron oxidation of the bithiophene moiety without concomitant desorption of the molecules. Although oxidation was irreversible in the absence of a protecting group, it became reversible with the introduction of a terminal phenyl group. The charge of the oxidation was one-third that of the reductive desorption, confirming a three-point adsorption. The surface coverage was ca. 50% of that expected for the anti bithiophene conformation, which suggested that an increase in the surface area per molecule had been caused by the presence of an energetically high-lying syn conformer. In accordance with this, the line shape of the oxidation wave suggested an electrostatic repulsive interaction between neighboring molecules.

Protein-gold clusters-capped mesoporous silica nanoparticles for high drug loading, autonomous gemcitabine/doxorubicin co-delivery, and in-vivo tumor imaging

KAUST Repository

Croissant, Jonas G.; Zhang, Dingyuan; Alsaiari, Shahad K.; Lu, Jie; Deng, Lin; Tamanoi, Fuyuhiko; Zink, Jeffrey I.; Khashab, Niveen M.

2016-01-01

Functional nanocarriers capable of transporting high drug contents without premature leakage and to controllably deliver several drugs are needed for better cancer treatments. To address this clinical need, gold cluster bovine serum albumin (AuNC@BSA) nanogates were engineered on mesoporous silica nanoparticles (MSN) for high drug loadings and co-delivery of two different anticancer drugs. The first drug, gemcitabine (GEM, 40 wt%), was loaded in positively-charged ammonium-functionalized MSN (MSN-NH3+). The second drug, doxorubicin (DOX, 32 wt%), was bound with negatively-charged AuNC@BSA electrostatically-attached onto MSN-NH3+, affording highly loaded pH-responsive MSN-AuNC@BSA nanocarriers. The co-delivery of DOX and GEM was achieved for the first time via an inorganic nanocarrier, possessing a zero-premature leakage behavior as well as drug loading capacities seven times higher than polymersome NPs. Besides, unlike the majority of strategies used to cap the pores of MSN, AuNC@BSA nanogates are biotools and were applied for targeted red nuclear staining and in-vivo tumor imaging. The straightforward non-covalent combination of MSN and gold-protein cluster bioconjugates thus leads to a simple, yet multifunctional nanotheranostic for the next generation of cancer treatments.

Protein-gold clusters-capped mesoporous silica nanoparticles for high drug loading, autonomous gemcitabine/doxorubicin co-delivery, and in-vivo tumor imaging

KAUST Repository

Croissant, Jonas G.

2016-03-23

Functional nanocarriers capable of transporting high drug contents without premature leakage and to controllably deliver several drugs are needed for better cancer treatments. To address this clinical need, gold cluster bovine serum albumin (AuNC@BSA) nanogates were engineered on mesoporous silica nanoparticles (MSN) for high drug loadings and co-delivery of two different anticancer drugs. The first drug, gemcitabine (GEM, 40 wt%), was loaded in positively-charged ammonium-functionalized MSN (MSN-NH3+). The second drug, doxorubicin (DOX, 32 wt%), was bound with negatively-charged AuNC@BSA electrostatically-attached onto MSN-NH3+, affording highly loaded pH-responsive MSN-AuNC@BSA nanocarriers. The co-delivery of DOX and GEM was achieved for the first time via an inorganic nanocarrier, possessing a zero-premature leakage behavior as well as drug loading capacities seven times higher than polymersome NPs. Besides, unlike the majority of strategies used to cap the pores of MSN, AuNC@BSA nanogates are biotools and were applied for targeted red nuclear staining and in-vivo tumor imaging. The straightforward non-covalent combination of MSN and gold-protein cluster bioconjugates thus leads to a simple, yet multifunctional nanotheranostic for the next generation of cancer treatments.

Modified gold surfaces by 6-(ferrocenyl)hexanethiol/dendrimer/gold nanoparticles as a platform for the mediated biosensing applications

Energy Technology Data Exchange (ETDEWEB)

Karadag, Murat; Geyik, Caner; Demirkol, Dilek Odaci [Ege University, Faculty of Science, Biochemistry Department, 35100 Bornova-Izmir (Turkey); Ertas, F. Nil [Ege University, Faculty of Science, Chemistry Department, 35100, Bornova-Izmir (Turkey); Timur, Suna, E-mail: suna.timur@ege.edu.tr [Ege University, Faculty of Science, Biochemistry Department, 35100 Bornova-Izmir (Turkey)

2013-03-01

An electrochemical biosensor mediated by using 6-(Ferrocenyl) hexanethiol (FcSH) was fabricated by construction of gold nanoparticles (AuNPs) on the surface of polyamidoamine dendrimer (PAMAM) modified gold electrode. Glucose oxidase (GOx) was used as a model enzyme and was immobilized onto the gold surface forming a self assembled monolayer via FcSH and cysteamine. Cyclic voltammetry and amperometry were used for the characterization of electrochemical response towards glucose substrate. Following the optimization of medium pH, enzyme loading, AuNP and FcSH amount, the linear range for the glucose was studied and found as 1.0 to 5.0 mM with the detection limit (LOD) of 0.6 mM according to S/N = 3. Finally, the proposed Au/AuNP/(FcSH + Cyst)/PAMAM/GOx biosensor was successfully applied for the glucose analysis in beverages, and the results were compared with those obtained by HPLC. Highlights: Black-Right-Pointing-Pointer Immobilized mediator in SAM layer and dendrimeric structure to expand surface area. Black-Right-Pointing-Pointer Au nanoparticles for enhanced electron transfer. Black-Right-Pointing-Pointer Satisfactory Limit of Detection with 0.6 mM.

Sandwiched gold/PNIPAm/gold microstructures for smart plasmonics application: towards the high detection limit and Raman quantitative measurements.

Science.gov (United States)

Elashnikov, R; Mares, D; Podzimek, T; Švorčík, V; Lyutakov, O

2017-08-07

A smart plasmonic sensor, comprising a layer of a stimuli-responsive polymer sandwiched between two gold layers, is reported. As a stimuli-responsive material, a monolayer of poly(N-isopropylacrylamide) (PNIPAm) crosslinked globules is used. A quasi-periodic structure of the top gold layer facilitates efficient excitation and serves as a support for plasmon excitation and propagation. The intermediate layer of PNIPAm efficiently entraps targeted molecules from solutions. The sensor structure was optimized for efficient light focusing in the "active" PNIPAm layer. The optimization was based on the time-resolved finite-element simulations, which take into account the thickness of gold layers, size of PNIPAm globules and Raman excitation wavelength (780 nm). The prepared structures were characterized using SEM, AFM, UV-Vis refractometry and goniometry. Additional AFM scans were performed in water at two temperatures corresponding to the collapsed and swollen PNIPAm states. The Raman measurements demonstrate a high detection limit and perfect reproducibility of the Raman scattering signal for the prepared sensor. In addition, the use of created SERS structures for the detection of relevant molecules in the medical, biological and safety fields was demonstrated.

Kinetic Assembly of Near-IR Active Gold Nanoclusters using Weakly Adsorbing Polymers to Control Size

Science.gov (United States)

Tam, Jasmine M.; Murthy, Avinash K.; Ingram, Davis R.; Nguyen, Robin; Sokolov, Konstantin V.; Johnston, Keith P.

2013-01-01

Clusters of metal nanoparticles with an overall size less than 100 nm and high metal loadings for strong optical functionality, are of interest in various fields including microelectronics, sensors, optoelectronics and biomedical imaging and therapeutics. Herein we assemble ~5 nm gold particles into clusters with controlled size, as small as 30 nm and up to 100 nm, which contain only small amounts of polymeric stabilizers. The assembly is kinetically controlled with weakly adsorbing polymers, PLA(2K)-b-PEG(10K)-b-PLA(2K) or PEG (MW = 3350), by manipulating electrostatic, van der Waals (VDW), steric, and depletion forces. The cluster size and optical properties are tuned as a function of particle volume fractions and polymer/gold ratios to modulate the interparticle interactions. The close spacing between the constituent gold nanoparticles and high gold loadings (80–85% w/w gold) produce a strong absorbance cross section of ~9×10−15 m2 in the NIR at 700 nm. This morphology results from VDW and depletion attractive interactions that exclude the weakly adsorbed polymeric stabilizer from the cluster interior. The generality of this kinetic assembly platform is demonstrated for gold nanoparticles with a range of surface charges from highly negative to neutral, with the two different polymers. PMID:20361735

Investigation of the effects of cell model and subcellular location of gold nanoparticles on nuclear dose enhancement factors using Monte Carlo simulation

Energy Technology Data Exchange (ETDEWEB)

Cai, Zhongli; Chattopadhyay, Niladri; Kwon, Yongkyu Luke [Department of Pharmaceutical Sciences, University of Toronto, Toronto, Ontario M5S 3M2 (Canada); Pignol, Jean-Philippe [Department of Radiation Oncology, University of Toronto, Toronto, Ontario M4N 3M5, Canada and Department of Medical Biophysics, University of Toronto, Toronto, Ontario M4N 3M5 (Canada); Lechtman, Eli [Department of Medical Biophysics, University of Toronto, Toronto, Ontario M4N 3M5 (Canada); Reilly, Raymond M. [Department of Pharmaceutical Sciences, University of Toronto, Toronto, Ontario M5S 3M2 (Canada); Department of Medical Imaging, University of Toronto, Toronto, Ontario M5S 3E2 (Canada); Toronto General Research Institute, University Health Network, Toronto, Ontario M5G 2C4 (Canada)

2013-11-15

Purpose: The authors’ aims were to model how various factors influence radiation dose enhancement by gold nanoparticles (AuNPs) and to propose a new modeling approach to the dose enhancement factor (DEF).Methods: The authors used Monte Carlo N-particle (MCNP 5) computer code to simulate photon and electron transport in cells. The authors modeled human breast cancer cells as a single cell, a monolayer, or a cluster of cells. Different numbers of 5, 30, or 50 nm AuNPs were placed in the extracellular space, on the cell surface, in the cytoplasm, or in the nucleus. Photon sources examined in the simulation included nine monoenergetic x-rays (10–100 keV), an x-ray beam (100 kVp), and {sup 125}I and {sup 103}Pd brachytherapy seeds. Both nuclear and cellular dose enhancement factors (NDEFs, CDEFs) were calculated. The ability of these metrics to predict the experimental DEF based on the clonogenic survival of MDA-MB-361 human breast cancer cells exposed to AuNPs and x-rays were compared.Results: NDEFs show a strong dependence on photon energies with peaks at 15, 30/40, and 90 keV. Cell model and subcellular location of AuNPs influence the peak position and value of NDEF. NDEFs decrease in the order of AuNPs in the nucleus, cytoplasm, cell membrane, and extracellular space. NDEFs also decrease in the order of AuNPs in a cell cluster, monolayer, and single cell if the photon energy is larger than 20 keV. NDEFs depend linearly on the number of AuNPs per cell. Similar trends were observed for CDEFs. NDEFs using the monolayer cell model were more predictive than either single cell or cluster cell models of the DEFs experimentally derived from the clonogenic survival of cells cultured as a monolayer. The amount of AuNPs required to double the prescribed dose in terms of mg Au/g tissue decreases as the size of AuNPs increases, especially when AuNPs are in the nucleus and the cytoplasm. For 40 keV x-rays and a cluster of cells, to double the prescribed x-ray dose (NDEF = 2

FEATURES OF ISLET-LIKE CLUSTERS GENERATION IN PANCREATIC DUCTAL CELL MOLOLAYER CULTURING

Directory of Open Access Journals (Sweden)

L. A. Kirsanova

2012-01-01

Full Text Available Newborn rabbit pancreatic cell monolayer was obtained as we described earlier.The cultivated epithelial cells were shown by immunofluorescence to express special ductal marker CK19 and were insulin-and glucagon- negative for 10–15 days. A few fusiforms of nestin-positive cells were found in monolayer. Over 2 weeks in serum-free medium the plaques of epithelial cells became crowded and formed 3-dimentional structures – islet- like clusters. Islet-like clusters contain some insulin- and glucagon-positive cells recognized by immunohysto- chemistry staining. Pancreatic endocrine cell generation in 3-dimentional structures is discussed. 

Interaction between benzenedithiolate and gold: Classical force field for chemical bonding

Science.gov (United States)

Leng, Yongsheng; Krstić, Predrag S.; Wells, Jack C.; Cummings, Peter T.; Dean, David J.

2005-06-01

We have constructed a group of classical potentials based on ab initio density-functional theory (DFT) calculations to describe the chemical bonding between benzenedithiolate (BDT) molecule and gold atoms, including bond stretching, bond angle bending, and dihedral angle torsion involved at the interface between the molecule and gold clusters. Three DFT functionals, local-density approximation (LDA), PBE0, and X3LYP, have been implemented to calculate single point energies (SPE) for a large number of molecular configurations of BDT-1, 2 Au complexes. The three DFT methods yield similar bonding curves. The variations of atomic charges from Mulliken population analysis within the molecule/metal complex versus different molecular configurations have been investigated in detail. We found that, except for bonded atoms in BDT-1, 2 Au complexes, the Mulliken partial charges of other atoms in BDT are quite stable, which significantly reduces the uncertainty in partial charge selections in classical molecular simulations. Molecular-dynamics (MD) simulations are performed to investigate the structure of BDT self-assembled monolayer (SAM) and the adsorption geometry of S adatoms on Au (111) surface. We found that the bond-stretching potential is the most dominant part in chemical bonding. Whereas the local bonding geometry of BDT molecular configuration may depend on the DFT functional used, the global packing structure of BDT SAM is quite independent of DFT functional, even though the uncertainty of some force-field parameters for chemical bonding can be as large as ˜100%. This indicates that the intermolecular interactions play a dominant role in determining the BDT SAMs global packing structure.

Water-Soluble N-Heterocyclic Carbene-Protected Gold Nanoparticles: Size-Controlled Synthesis, Stability, and Optical Properties

OpenAIRE

Salorinne, Kirsi; Man, Renee W.Y.; Li, Chien-Hung; Taki, Masayasu; Nambo, Masakazu; Crudden, Cathleen M.

2017-01-01

NHC-Au(I) complexes were used to prepare stable, water-soluble, NHC-protected gold nanoparticles. The water-soluble, charged nature of the nanoparticles permitted analysis by polyacrylamide gel electrophoresis (PAGE), which showed that the nanoparticles were highly monodisperse, with tunable core diameters between 2.0 and 3.3 nm depending on the synthesis conditions. Temporal, thermal, and chemical stability of the nanoparticles were determined to be high. Treatment with thiols caused etching...

Ballbot-type motion of N-heterocyclic carbenes on gold surfaces

Science.gov (United States)

Wang, Gaoqiang; Rühling, Andreas; Amirjalayer, Saeed; Knor, Marek; Ernst, Johannes Bruno; Richter, Christian; Gao, Hong-Jun; Timmer, Alexander; Gao, Hong-Ying; Doltsinis, Nikos L.; Glorius, Frank; Fuchs, Harald

2017-02-01

Recently, N-heterocyclic carbenes (NHCs) were introduced as alternative anchors for surface modifications and so offered many attractive features, which might render them superior to thiol-based systems. However, little effort has been made to investigate the self-organization process of NHCs on surfaces, an important aspect for the formation of self-assembled monolayers (SAMs), which requires molecular mobility. Based on investigations with scanning tunnelling microscopy and first-principles calculations, we provide an understanding of the microscopic mechanism behind the high mobility observed for NHCs. These NHCs extract a gold atom from the surface, which leads to the formation of an NHC-gold adatom complex that displays a high surface mobility by a ballbot-type motion. Together with their high desorption barrier this enables the formation of ordered and strongly bound SAMs. In addition, this mechanism allows a complementary surface-assisted synthesis of dimeric and hitherto unknown trimeric NHC gold complexes on the surface.

Electrical characterizations of biomimetic molecular layers on gold and silicon substrates

International Nuclear Information System (INIS)

Chilcott, T C; Wong, E L S; Coster, H G L; Böcking, T

2008-01-01

Electrical impedance technology was used to characterize DNA recognition in a monolayer containing single-stranded DNA probes immobilized on a gold substrate using thiol self-assembly chemistry. Recognition of targeted complementary DNA was principally correlated with an eight-fold increase in the conductance of the monolayer and attributed to electron conduction through double helices formed upon the binding of the DNA targets to the probes. The high recognitive sensitivity was possible without the use of the redox labels or large bias voltages required for recognition using cyclic and Osteryoung square wave voltammetry. The impedance technology also provided atomic resolution of a hybrid bimolecular lipid membrane formed by deposition of a phospholipid:cholesterol monolayer onto a hydrophobic alkyl monolayer covalently attached to a silicon substrate via silicon–carbon bonds. Atomic resolution was achieved through preparation of membranes on surfaces approaching atomic flatness and the performance of impedance measurements over precisely defined areas of the surface in contact with solutions. Principally capacitive properties distinguished between the immobilized (octadecyl) and more fluidic (lipid:cholesterol) leaflets of the hybrid membrane. The lipid:cholesterol leaflets were structurally similar to those leaflets in free-standing bimolecular lipid membranes. The hybrid membrane therefore provides a highly stable and physiologically relevant surface for studying biomolecular interactions with membrane surfaces

Formation of supported lipid bilayers of charged E. coli lipids on modified gold by vesicle fusion

Directory of Open Access Journals (Sweden)

Ileana F. Márquez

2017-01-01

Full Text Available We describe a simple way of fusing E. coli lipid vesicles onto a gold surface. Supported lipid bilayers on metal surfaces are interesting for several reasons: transducing a biological signal to an electric readout, using surface analytical tools such as Surface Plasmon Resonance (SPR, Infrared Reflection Absorption Spectroscopy, Neutron Reflectivity or Electrochemistry. The most widely used method to prepare supported lipid membranes is fusion of preexisting liposomes. It is quite efficient on hydrophilic surfaces such as glass, mica or SiO2, but vesicle fusion on metals and metal oxide surfaces (as gold, titanium oxide or indium tin oxide, remains a challenge, particularly for vesicles containing charged lipids, as is the case of bacterial lipids. We describe a simple method based on modifying the gold surface with a charged mercaptopropionic acid self-assembled monolayer and liposomes partially solubilized with detergent. The formed bilayers were characterized using a Quartz Crystal Microbalance with dissipation (QCM-D and Atomic Force Microscopy (AFM. Some advantages of this protocol are that the stability of the self-assembled monolayer allows for repeated use of the substrate after detergent removal of the bilayer and that the amount of detergent required for optimal fusion can be determined previously using the lipid-detergent solubility curve.

Monolayer-by-monolayer growth of platinum films on complex carbon fiber paper structure

Energy Technology Data Exchange (ETDEWEB)

Pang, Liuqing; Zhang, Yunxia [Key Laboratory of Applied Surface and Colloid Chemistry, National Ministry of Education, Shaanxi Key Laboratory for Advanced Energy Devices, Shaanxi Engineering Lab for Advanced Energy Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710119 (China); Liu, Shengzhong, E-mail: szliu@dicp.ac.cn [Key Laboratory of Applied Surface and Colloid Chemistry, National Ministry of Education, Shaanxi Key Laboratory for Advanced Energy Devices, Shaanxi Engineering Lab for Advanced Energy Technology, School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710119 (China); Dalian National Laboratory for Clean Energy, iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)

2017-06-15

Graphical abstract: A controlled monolayer-by-monolayer deposition process has been developed to fabricate Pt coating on carbon fiber paper with complex network structures using a dual buffer strategy. This development may pave a way to fabricate superior Pt catalysts with the minimal Pt usage. In fact, the present Pt group metal loading is 25 times lower than the U.S. DOE 2017 target value. - Highlights: • Developed a controlled monolayer-by-monolayer Pt deposition using a dual buffer strategy. • The present Pt group metal loading is 25 times lower than the U.S. DOE 2017 target value. • This development may pave a way to fabricate superior Pt catalysts with the minimal Pt usage. - Abstract: A controlled monolayer-by-monolayer deposition process has been developed to fabricate Pt coating on carbon fiber paper with complex network structures using a dual buffer (Au/Ni) strategy. The X-ray diffraction, electrochemical quartz crystal microbalance, current density analyses, and X-ray photoelectron spectroscopy results conclude that the monolayer deposition process accomplishes full coverage on the substrate and that the thickness of the deposition layer can be controlled on a single atom scale. This development may pave a way to fabricate superior Pt catalysts with the minimal Pt usage. In fact, the present Pt group metal loading is 25 times lower than the U.S. DOE 2017 target value.

Selective determination of dopamine using quantum-sized gold nanoparticles protected with charge selective ligands

Science.gov (United States)

Kwak, Kyuju; Kumar, S. Senthil; Lee, Dongil

2012-06-01

We report here the selective determination of dopamine (DA) using quantum-sized gold nanoparticles coated with charge selective ligands. Glutathione protected gold nanoparticles (GS-Au25) were synthesized and immobilized into a sol-gel matrix via thiol linkers. The GS-Au25 modified sol-gel electrode was found to show excellent electrocatalytic activity towards the oxidation of DA but no activity towards the oxidation of ascorbic acid. The role of electrostatic charge in the selective electrocatalytic activity of GS-Au25 was verified by voltammetry of redox markers carrying opposite charges. The pH dependent sensitivity for the determination of DA further confirmed the charge screening effect of GS-Au25. Mechanistic investigation revealed that the selectivity is attained by the selective formation of an electrostatic complex between the negatively charged GS-Au25 and DA cation. The GS-Au25 modified sol-gel electrode also showed excellent selectivity for DA in the presence of an interferent, ascorbic acid.We report here the selective determination of dopamine (DA) using quantum-sized gold nanoparticles coated with charge selective ligands. Glutathione protected gold nanoparticles (GS-Au25) were synthesized and immobilized into a sol-gel matrix via thiol linkers. The GS-Au25 modified sol-gel electrode was found to show excellent electrocatalytic activity towards the oxidation of DA but no activity towards the oxidation of ascorbic acid. The role of electrostatic charge in the selective electrocatalytic activity of GS-Au25 was verified by voltammetry of redox markers carrying opposite charges. The pH dependent sensitivity for the determination of DA further confirmed the charge screening effect of GS-Au25. Mechanistic investigation revealed that the selectivity is attained by the selective formation of an electrostatic complex between the negatively charged GS-Au25 and DA cation. The GS-Au25 modified sol-gel electrode also showed excellent selectivity for DA in the

Facile preparation of surface-exchangeable core@shell iron oxide@gold nanoparticles for magnetic solid-phase extraction: Use of gold shell as the intermediate platform for versatile adsorbents with varying self-assembled monolayers

Energy Technology Data Exchange (ETDEWEB)

Li, Yaping [Beijing National Laboratory of Molecular Sciences, Key Laboratory of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); Graduate School, University of Chinese Academy of Sciences, Beijing 100049 (China); Qi, Li, E-mail: qili@iccas.ac.cn [Beijing National Laboratory of Molecular Sciences, Key Laboratory of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); Shen, Ying [Beijing National Laboratory of Molecular Sciences, Key Laboratory of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); Graduate School, University of Chinese Academy of Sciences, Beijing 100049 (China); Ma, Huimin [Beijing National Laboratory of Molecular Sciences, Key Laboratory of Analytical Chemistry for Living Biosystems, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China)

2014-02-06

Graphical abstract: -- Highlights: •The core@shell Fe{sub 3}O{sub 4}@Au nanoparticles functionalized with SAMs were successfully constructed. •The SAMs could be transformed from one kind to another via thiol exchange process. •The developed nanomaterials could be applied in mode switching MSPE. -- Abstract: The core@shell Fe{sub 3}O{sub 4}@Au nanoparticles (NPs) functionalized with exchangeable self-assembled monolayers have been developed for mode switching magnetic solid-phase extraction (MSPE) using high performance liquid chromatography with ultraviolet detection. The adsorbents were synthesized by chemical coprecipitation to prepare magnetic cores followed by sonolysis to produce gold shells. Functionalization of Fe{sub 3}O{sub 4}@Au NPs surface was realized through self-assembly of commercially available low molecular weight thiol-containing ligands using gold shells as intermediate platform and the dynamic nature of Au–S chemistry allowed substituent of one thiol-containing ligand with another simply by thiol exchange process. The resultant adsorbents were characterized by transmission electronic microscopy, Fourier transform infrared spectroscopy, elemental analysis, contact angle measurement, and vibrating sample magnetometry. To evaluate the versatile performance of the developed MSPE adsorbents, they were applied for normal-phase SPE followed by reversed-phase SPE. A few kinds of diphenols and polycyclic aromatic hydrocarbons (PAHs) were employed as model analytes, respectively. The predominant parameters affecting extraction efficiency were investigated and optimized. Under the optimum experimental conditions, wide dynamic linear range (6.25–1600 μg L{sup −1} for diphenols and 1.56–100 μg L{sup −1} for PAHs) with good linearity (r{sup 2} ≥ 0.989) and low detection limits (0.34–16.67 μg L{sup −1} for diphenols and 0.26–0.52 μg L{sup −1} for PAHs) were achieved. The advantage of the developed method is that the Fe{sub 3}O

Catalytic enhancement of gold nanocages induced by undercoordination-charge-polarization

Directory of Open Access Journals (Sweden)

Xi Zhang

2017-05-01

Full Text Available Principle behind the highest catalytic ability of the least coordinated gold remains a puzzle. With the aid of density functional theory calculations, we show that in 3-coordinated gold cages (i the Au–Au bond contracts by ∼5% in average, (ii the valance density-of-states shift up to Fermi level when the Au55 cluster turns into an Au12 cage, and (iii the activation energy for CO oxidation drops in sequence, Au55 cluster (13.6 Kcal/mol, Au42 cage (8.0 Kcal/mol, Au13(6.5 Kcal/mol, and Au12 cage (5.1 Kcal/mol, with comparing the reaction paths and spin states. The principle clarified here paves the way for the design of gold nanocatalyst.

Metal Enhanced Fluorescence on Super-Hydrophobic Clusters of Gold Nanoparticles

KAUST Repository

Battista, Edmondo; Coluccio, Maria Laura; Alabastri, Alessandro; Barberio, Marianna; Causa, Filippo; Netti, Paolo Antonio; Di Fabrizio, Enzo M.; Gentile, Francesco

2016-01-01

We used optical lithography, electroless deposition and deep reactive ion etching techniques to realize arrays of super-hydrophobic gold nanoparticles arranged in a hierarchical structure. At the micro-scale, silicon-micro pillars in the chip permit to manipulate and concentrate biological solutions, at the nano-scale, gold nanoparticles enable metal enhanced fluorescence (MEF) effects, whereby fluorescence signal of fluorophores in close proximity to a rough metal surface is amplified by orders of magnitude. Here, we demonstrated the device in the analysis of fluorescein derived gold-binding peptides (GBP-FITC). While super-hydrophobic schemes and MEF effects have been heretofore used in isolation, their integration in a platform may advance the current state of fluorescence-based sensing technology in medical diagnostics and biotechnology. This scheme may be employed in protein microarrays where the increased sensitivity of the device may enable the early detection of cancer biomarkers or other proteins of biomedical interest.

Metal Enhanced Fluorescence on Super-Hydrophobic Clusters of Gold Nanoparticles

KAUST Repository

Battista, Edmondo

2016-12-15

We used optical lithography, electroless deposition and deep reactive ion etching techniques to realize arrays of super-hydrophobic gold nanoparticles arranged in a hierarchical structure. At the micro-scale, silicon-micro pillars in the chip permit to manipulate and concentrate biological solutions, at the nano-scale, gold nanoparticles enable metal enhanced fluorescence (MEF) effects, whereby fluorescence signal of fluorophores in close proximity to a rough metal surface is amplified by orders of magnitude. Here, we demonstrated the device in the analysis of fluorescein derived gold-binding peptides (GBP-FITC). While super-hydrophobic schemes and MEF effects have been heretofore used in isolation, their integration in a platform may advance the current state of fluorescence-based sensing technology in medical diagnostics and biotechnology. This scheme may be employed in protein microarrays where the increased sensitivity of the device may enable the early detection of cancer biomarkers or other proteins of biomedical interest.

Thermodynamic and structural studies of mixed monolayers: Mutual mixing of DPPC and DPPG with DoTAP at the air-water interface

International Nuclear Information System (INIS)

Panda, Amiya Kumar; Vasilev, Krasimir; Orgeig, Sandra; Prestidge, Clive A.

2010-01-01

Phospholipid monomolecular films at the air-water interface are useful model membranes to understand miscibility among various components. Surface pressure (π)-area (A) isotherms of pure and mixed monolayers of dioleoyltrimethylammonium propane (DoTAP)-dipalmitoylphosphatidylcholine (DPPC) and DoTAP-dipalmitoyphosphatidylglycerol (DPPG) were constructed using a surface balance. DPPC and DPPG produced isotherms as expected and reported earlier. DoTAP, an unsaturated lipid, demonstrated a continuous π-A isotherm. Associative interactions were identified in DPPC-DoTAP mixtures compared to the pure components, while DPPG-DoTAP mixtures showed repulsive interaction up to an equimolar ratio. Compression moduli of the monolayers revealed that DPPC-DoTAP mixtures had increasing stability with increasing surface pressure, but addition of DoTAP to DPPG showed instability at low and intermediate concentrations. In both cases increased stability was returned at higher X DoTAP values and surface pressures. Lipid monolayer film thickness values, determined on a gold coated glass substrate by surface plasmon resonance spectroscopy (SPR), indicated a systematic change in height profile for DPPC-DoTAP mixtures with increasing X DoTAP . However, DPPG-DoTAP mixed monolayer systems demonstrated a biphasic response. The SPR data were in excellent agreement with our interpretation of the structure of solid supported lipid monolayers.

Thermodynamic and structural studies of mixed monolayers: Mutual mixing of DPPC and DPPG with DoTAP at the air-water interface

Energy Technology Data Exchange (ETDEWEB)

Panda, Amiya Kumar, E-mail: akpanda1@yahoo.com [Department of Chemistry, University of North Bengal, Darjeeling-734 013, West Bengal (India); Vasilev, Krasimir [Mawson Institute for Advanced Manufacturing, Mawson Lakes, University of South Australia, SA-5095 (Australia); Orgeig, Sandra [Sansom Institute for Health Research and School of Pharmacy and Medical Sciences, University of South Australia, Adelaide, SA 5000 (Australia); Prestidge, Clive A. [Ian Wark Research Institute, University of South Australia, Mawson Lakes, SA 5095 (Australia)

2010-05-10

Phospholipid monomolecular films at the air-water interface are useful model membranes to understand miscibility among various components. Surface pressure ({pi})-area (A) isotherms of pure and mixed monolayers of dioleoyltrimethylammonium propane (DoTAP)-dipalmitoylphosphatidylcholine (DPPC) and DoTAP-dipalmitoyphosphatidylglycerol (DPPG) were constructed using a surface balance. DPPC and DPPG produced isotherms as expected and reported earlier. DoTAP, an unsaturated lipid, demonstrated a continuous {pi}-A isotherm. Associative interactions were identified in DPPC-DoTAP mixtures compared to the pure components, while DPPG-DoTAP mixtures showed repulsive interaction up to an equimolar ratio. Compression moduli of the monolayers revealed that DPPC-DoTAP mixtures had increasing stability with increasing surface pressure, but addition of DoTAP to DPPG showed instability at low and intermediate concentrations. In both cases increased stability was returned at higher X{sub DoTAP} values and surface pressures. Lipid monolayer film thickness values, determined on a gold coated glass substrate by surface plasmon resonance spectroscopy (SPR), indicated a systematic change in height profile for DPPC-DoTAP mixtures with increasing X{sub DoTAP}. However, DPPG-DoTAP mixed monolayer systems demonstrated a biphasic response. The SPR data were in excellent agreement with our interpretation of the structure of solid supported lipid monolayers.

First-principles studies of Te line-ordered alloys in a MoS2 monolayer

Science.gov (United States)

Andriambelaza, N. F.; Mapasha, R. E.; Chetty, N.

2018-04-01

The thermodynamic stability, structural and electronic properties of Te line-ordered alloys are investigated using density functional theory (DFT) methods. Thirty four possible Te line-ordered alloy configurations are found in a 5×5 supercell of a MoS2 monolayer. The calculated formation energies show that the Te line-ordered alloy configurations are thermodynamically stable at 0 K and agree very well with the random alloys. The lowest energy configurations at each concentration correspond to the configuration where the Te atom rows are far apart from each other (avoiding clustering) within the supercell. The variation of the lattice constant at different concentrations obey Vegard's law. The Te line-ordered alloys fine tune the band gap of a MoS2 monolayer although deviating from linearity behavior. Our results suggest that the Te line-ordered alloys can be an effective way to modulate the band gap of a MoS2 monolayer for nanoelectronic, optoelectronic and nanophotonic applications.

Growth of pentacene on clean and modified gold surfaces

International Nuclear Information System (INIS)

Kaefer, Daniel; Ruppel, Lars; Witte, Gregor

2007-01-01

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

Reducing HAuCl4 by the C60 dianion: C60-directed self-assembly of gold nanoparticles into novel fullerene bound gold nanoassemblies

International Nuclear Information System (INIS)

Liu Wei; Gao Xiang

2008-01-01

The C 60 dianion is used to reduce tetrachloroauric acid (HAuCl 4 ) for the first time; three-dimensional C 60 bound gold (Au-C 60 ) nanoclusters are obtained from C 60 -directed self-assembly of gold nanoparticles due to the strong affinities of Au-C 60 and C 60 -C 60 . The process was monitored in situ by UV-vis-NIR spectroscopy. The resulting Au-C 60 nanoclusters were characterized using transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy-dispersive spectroscopy (EDS), x-ray powder diffraction (XRD), x-ray photoelectron spectroscopy (XPS), and FT-IR and Raman spectroscopies. TEM demonstrates the formation of 3D nanonetwork aggregates, which are composed of discrete gold nanocores covered with a C 60 monolayer. The SAED and XRD patterns indicate that the gold nanocores inside the capped C 60 molecules belong to the face-centred cubic crystal structure, while the C 60 molecules are amorphous. The EDS and XPS measurements validate that the Au-C 60 nanoclusters contain only Au and C elements and Au 3+ is reduced to Au 0 . FT-IR spectroscopy shows the chemiadsorption of C 60 to the gold nanocores, while Raman spectroscopy demonstrates the electron transfer from the gold nanocores to the chemiadsorbed C 60 molecules. Au-C 60 nanoclusters embedded in tetraoctyl-n-ammonium bromide (TOAB) on glassy carbon electrodes (GCEs) have been fabricated and have shown stable and well-defined electrochemical responses in aqueous solution

On the utility of vacancies and tensile strain-induced quality factor enhancement for mass sensing using graphene monolayers

International Nuclear Information System (INIS)

Kim, Sung Youb; Park, Harold S

2010-01-01

We have utilized classical molecular dynamics to investigate the mass sensing potential of graphene monolayers, using gold as the model adsorbed atom. In doing so, we report two key findings. First, we find that while perfect graphene monolayers are effective mass sensors at very low (T < 10 K) temperatures, their mass sensing capability is lost at higher temperatures due to diffusion of the adsorbed atom at elevated temperatures. We demonstrate that even if the quality (Q) factors are significantly elevated through the application of tensile mechanical strain, the mass sensing resolution is still lost at elevated temperatures, which demonstrates that high Q-factors alone are insufficient to ensure the mass sensing capability of graphene. Second, we find that while the introduction of single vacancies into the graphene monolayer prevents the diffusion of the adsorbed atom, the mass sensing resolution is still lost at higher temperatures, again due to Q-factor degradation. We finally demonstrate that if the Q-factors of the graphene monolayers with single vacancies are kept acceptably high through the application of tensile strain, then the high Q-factors, in conjunction with the single atom vacancies to stop the diffusion of the adsorbed atom, enable graphene to maintain its mass sensing capability across a range of technologically relevant operating temperatures.

Fibrinogen Motif Discriminates Platelet and Cell Capture in Peptide-Modified Gold Micropore Arrays.

Science.gov (United States)

Adamson, Kellie; Spain, Elaine; Prendergast, Una; Moran, Niamh; Forster, Robert J; Keyes, Tia E

2018-01-16

Human blood platelets and SK-N-AS neuroblastoma cancer-cell capture at spontaneously adsorbed monolayers of fibrinogen-binding motifs, GRGDS (generic integrin adhesion), HHLGGAKQAGDV (exclusive to platelet integrin α IIb β 3 ), or octanethiol (adhesion inhibitor) at planar gold and ordered 1.6 μm diameter spherical cap gold cavity arrays were compared. In all cases, arginine/glycine/aspartic acid (RGD) promoted capture, whereas alkanethiol monolayers inhibited adhesion. Conversely only platelets adhered to alanine/glycine/aspartic acid (AGD)-modified surfaces, indicating that the AGD motif is recognized preferentially by the platelet-specific integrin, α IIb β 3 . Microstructuring of the surface effectively eliminated nonspecific platelet/cell adsorption and dramatically enhanced capture compared to RGD/AGD-modified planar surfaces. In all cases, adhesion was reversible. Platelets and cells underwent morphological change on capture, the extent of which depended on the topography of the underlying substrate. This work demonstrates that both the nature of the modified interface and its underlying topography influence the capture of cancer cells and platelets. These insights may be useful in developing cell-based cancer diagnostics as well as in identifying strategies for the disruption of platelet cloaks around circulating tumor cells.

Random Surface Texturing of Silicon Dioxide Using Gold Agglomerates

Science.gov (United States)

2016-07-01

a visual indicator of the formation of gold clusters on the SiO2 . The glass would make observing a color change in the gold film easier later in the...unlimited. 13. SUPPLEMENTARY NOTES 14. ABSTRACT A fabrication process for creating a silicon dioxide ( SiO2 ) light-trapping structure as part of...even distribution of irregular agglomerates, also known as “complete islanding”. By using these gold agglomerations as a metal mask, the SiO2 can be

Electronic structure and optical properties of the thiolate-protected Au28(SMe)20 cluster.

Science.gov (United States)

Knoppe, Stefan; Malola, Sami; Lehtovaara, Lauri; Bürgi, Thomas; Häkkinen, Hannu

2013-10-10

The recently reported crystal structure of the Au28(TBBT)20 cluster (TBBT: p-tert-butylbenzenethiolate) is analyzed with (time-dependent) density functional theory (TD-DFT). Bader charge analysis reveals a novel trimeric Au3(SR)4 binding motif. The cluster can be formulated as Au14(Au2(SR)3)4(Au3(SR)4)2. The electronic structure of the Au14(6+) core and the ligand-protected cluster were analyzed, and their stability can be explained by formation of distorted eight-electron superatoms. Optical absorption and circular dichroism (CD) spectra were calculated and compared to the experiment. Assignment of handedness of the intrinsically chiral cluster is possible.

Molecular dynamics of contact behavior of self-assembled monolayers on gold using nanoindentation

Energy Technology Data Exchange (ETDEWEB)

Fang, Te-Hua [Institute of Mechanical and Electromechanical Engineering National Formosa University, Yunlin 632, Taiwan (China); Chang, Win-Jin, E-mail: changwj@mail.ksu.edu.tw [Department of Mechanical Engineering Kun Shan University, Tainan 710, Taiwan (China); Fan, Yu-Cheng [Institute of Mechanical and Electromechanical Engineering National Formosa University, Yunlin 632, Taiwan (China); Weng, Cheng-I [Department of Mechanical Engineering National Cheng Kung University, Tainan, 710, Taiwan (China)

2009-08-15

Molecular dynamics simulation is used to study nanoindentation of the self-assembled monolayers (SAMs) on an Au surface. The interaction of SAM atoms is described by a general universal force field (UFF), the tight-binding second-moment approximation (TB-SMA) is used for Au substrate, and the Lennard-Jones potential function is employed to describe interaction among the indenter, the SAMs, and the Au substrate atoms. The model consists of a planar Au substrate with n-hexadecanethiol SAM chemisorbed to the substrate. The simulation results show that the contact pressure increases as the SAMs temperature increases. In addition, the contact pressure also increases as the depth and velocity of indentation increase.

Molecular dynamics of contact behavior of self-assembled monolayers on gold using nanoindentation

International Nuclear Information System (INIS)

Fang, Te-Hua; Chang, Win-Jin; Fan, Yu-Cheng; Weng, Cheng-I

2009-01-01

Molecular dynamics simulation is used to study nanoindentation of the self-assembled monolayers (SAMs) on an Au surface. The interaction of SAM atoms is described by a general universal force field (UFF), the tight-binding second-moment approximation (TB-SMA) is used for Au substrate, and the Lennard-Jones potential function is employed to describe interaction among the indenter, the SAMs, and the Au substrate atoms. The model consists of a planar Au substrate with n-hexadecanethiol SAM chemisorbed to the substrate. The simulation results show that the contact pressure increases as the SAMs temperature increases. In addition, the contact pressure also increases as the depth and velocity of indentation increase.

Subcellular localization of alkaline phosphatase in Bacillus licheniformis 749/C by immunoelectron microscopy with colloidal gold

International Nuclear Information System (INIS)

Tinglu, G.; Ghosh, A.; Ghosh, B.K.

1984-01-01

Subcellular distribution of the alkaline phosphatase of Bacillus licheniformis 749/C was determined by an immunoelectron microscopy method. Anti-alkaline phosphatase antibody labeled with 15- to 18-nm colloidal gold particles (gold-immunoglobulin G [IgG] complex) were used for the study. Both the plasma membrane and cytoplasmic material were labeled with the gold-IgG particles. These particles formed clusters in association with the plasma membrane; in contrast, in the cytoplasm the particles were largely dispersed, and only a few clusters were found. The gold-IgG binding was quantitatively estimated by stereological analysis of labeled, frozen thin sections. This estimation of a variety of control samples showed that the labeling was specific for the alkaline phosphatase. Cluster formation of the gold -IgG particles in association with the plasma membrane suggests that existence of specific alkaline phosphatase binding sites (receptors) in the plasma membrane of B. licheniformis 749/C. 27 references, 6 figures, 1 table

Adaptive chemistry of bifunctional gold nanoparticles at the air/water interface. A synchrotron X-ray study of giant amphiphiles

DEFF Research Database (Denmark)

Nørgaard, K.; Weygand, M.J.; Kjær, K.

2004-01-01

A series of ligand stabilized gold nanoparticles with diameters close to 3 nm were studied as Langmuir monolayers at the air/water interface by synchrotron X-ray diffraction and reflectivity. Alkylthiols with different length and/or terminal functional group (hydrophilic or hydrophobic) were intr...

Packing of ganglioside-phospholipid monolayers

DEFF Research Database (Denmark)

Majewski, J.; Kuhl, T.L.; Kjær, K.

2001-01-01

Using synchrotron grazing-incidence x-ray diffraction (GIXD) and reflectivity, the in-plane and out-of-plane structure of mixed ganglioside-phospholipid monolayers was investigated at the air-water interface. Mixed monolayers of 0, 5, 10, 20, and 100 mol% ganglioside GM, and the phospholipid...... monolayers did not affect hydrocarbon tail packing (fluidization or condensation of the hydrocarbon region). This is in contrast to previous investigations of lipopolymer-lipid mixtures, where the packing structure of phospholipid monolayers was greatly altered by the inclusion of lipids bearing hydrophilic...

Influence of the graphene substrate on morphology of the gold thin film. Spectroscopic ellipsometry study

International Nuclear Information System (INIS)

Kostruba, A.M.

2013-01-01

In metal optics gold assumes a special status because of its practical importance in optoelectronic and nanooptical devices, and its role huge increases when occurs combination of gold with two-dimension materials. We performed spectroscopic ellipsometry measurements on evaporated gold, and gold–graphene nanostructures to determine the optical dielectric function across a broad spectral range from 250 to 1000 nm. It was found that the deposition of gold film on the quartz substrate covered by graphene flake leads to significant changes in structural and dielectric properties of thin gold layer. Such changes can be explained by increasing of the gold cluster size. The model fit of the ellipsometric data demonstrates that the bilayer “graphene-gold” nanostructure can be described as a uniform optically homogeneous layer with modified optical properties. We can suggest that graphene flake creates a matrix for epitaxial alignment of the crystalline structure of the gold film during its growing. Effective doping of the graphene by free electrons of the gold clusters tends to decrease the optical contrast at the graphene-gold interface.

Cyclodextrin inclusion complexes with thiocholesterol and their self-assembly on gold: A combined electrochemical and lateral force microscopy analysis

International Nuclear Information System (INIS)

Pandey, Rakesh K.; Lakshminarayanan, V.

2014-01-01

The present study is an attempt to understand the properties of an interesting self-assembled monolayer system composed of inclusion complexes of thiocholesterol and cyclodextrins. Cyclodextrins were used as host compound while thiocholesterol was used as the entrant molecule into the cavity of cyclodextrins. The improved electron transfer barrier property towards a redox couple indicates a sturdy inclusion complex monolayer. A very large R ct value, 64.6 kΩ·cm 2 for a redox system was obtained in the case of methyl-β-cyclodextrin and thiocholesterol inclusion complex self-assembled monolayer. A rather low value of capacitance 1.2 μF cm −2 measured in supporting electrolyte further signifies the fact that inclusion complex monolayer is quite impermeable for ionic species. In addition lateral force microscopy combined with force–distance analysis revealed the presence of an interesting mixed hydrophilic/hydrophobic surface. - Highlights: • Self-assembled monolayer of inclusion complexes on gold surface • Lateral force microscopy study of the regions of varying hydrophilicities • Could find applications in patterning surfaces to be hydrophilic/hydrophobic • Improved electron transfer barrier properties

Phase transitions in surfactant monolayers

International Nuclear Information System (INIS)

Casson, B.D.

1998-01-01

Two-dimensional phase transitions have been studied in surfactant monolayers at the air/water interface by sum-frequency spectroscopy and ellipsometry. In equilibrium monolayers of medium-chain alcohols C n H 2n+1 OH (n = 9-14) a transition from a two-dimensional crystalline phase to a liquid was observed at temperatures above the bulk melting point. The small population of gauche defects in the solid phase increased only slightly at the phase transition. A model of the hydrocarbon chains as freely rotating rigid rods allowed the area per molecule and chain tilt in the liquid phase to be determined. The area per molecule, chain tilt and density of the liquid phase all increased with increasing chain length, but for each chain length the density was higher than in a bulk liquid hydrocarbon. In a monolayer of decanol adsorbed at the air/water interface a transition from a two-dimensional liquid to a gas was observed. A clear discontinuity in the coefficient of ellipticity as a function of temperature showed that the transition is first-order. This result suggests that liquid-gas phase transitions in surfactant monolayers may be more widespread than once thought. A solid-liquid phase transition has also been studied in mixed monolayers of dodecanol with an anionic surfactant (sodium dodecyl sulphate) and with a homologous series of cationic surfactants (alkyltrimethylammonium bromides: C n TABs, n = 12, 14, 16). The composition and structure of the mixed monolayers was studied above and below the phase transition. At low temperatures the mixed monolayers were as densely packed as a monolayer of pure dodecanol in its solid phase. At a fixed temperature the monolayers under-went a first-order phase transition to form a phase that was less dense and more conformationally disordered. The proportion of ionic surfactant in the mixed monolayer was greatest in the high temperature phase. As the chain length of the C n TAB increased the number of conformational defects

Determining the composition of gold nanoparticles: a compilation of shapes, sizes, and calculations using geometric considerations

International Nuclear Information System (INIS)

Mori, Taizo; Hegmann, Torsten

2016-01-01

Size, shape, overall composition, and surface functionality largely determine the properties and applications of metal nanoparticles. Aside from well-defined metal clusters, their composition is often estimated assuming a quasi-spherical shape of the nanoparticle core. With decreasing diameter of the assumed circumscribed sphere, particularly in the range of only a few nanometers, the estimated nanoparticle composition increasingly deviates from the real composition, leading to significant discrepancies between anticipated and experimentally observed composition, properties, and characteristics. We here assembled a compendium of tables, models, and equations for thiol-protected gold nanoparticles that will allow experimental scientists to more accurately estimate the composition of their gold nanoparticles using TEM image analysis data. The estimates obtained from following the routines described here will then serve as a guide for further analytical characterization of as-synthesized gold nanoparticles by other bulk (thermal, structural, chemical, and compositional) and surface characterization techniques. While the tables, models, and equations are dedicated to gold nanoparticles, the composition of other metal nanoparticle cores with face-centered cubic lattices can easily be estimated simply by substituting the value for the radius of the metal atom of interest.Graphical abstract

Determining the composition of gold nanoparticles: a compilation of shapes, sizes, and calculations using geometric considerations

Energy Technology Data Exchange (ETDEWEB)

Mori, Taizo, E-mail: MORI.Taizo@nims.go.jp; Hegmann, Torsten, E-mail: thegmann@kent.edu [Kent State University, Chemical Physics Interdisciplinary Program, Liquid Crystal Institute (United States)

2016-10-15

Size, shape, overall composition, and surface functionality largely determine the properties and applications of metal nanoparticles. Aside from well-defined metal clusters, their composition is often estimated assuming a quasi-spherical shape of the nanoparticle core. With decreasing diameter of the assumed circumscribed sphere, particularly in the range of only a few nanometers, the estimated nanoparticle composition increasingly deviates from the real composition, leading to significant discrepancies between anticipated and experimentally observed composition, properties, and characteristics. We here assembled a compendium of tables, models, and equations for thiol-protected gold nanoparticles that will allow experimental scientists to more accurately estimate the composition of their gold nanoparticles using TEM image analysis data. The estimates obtained from following the routines described here will then serve as a guide for further analytical characterization of as-synthesized gold nanoparticles by other bulk (thermal, structural, chemical, and compositional) and surface characterization techniques. While the tables, models, and equations are dedicated to gold nanoparticles, the composition of other metal nanoparticle cores with face-centered cubic lattices can easily be estimated simply by substituting the value for the radius of the metal atom of interest.Graphical abstract.

On the origin of bonding and vibrational frequency shifts for CO adsorbed on neutral, cationic and anionic gold clusters

International Nuclear Information System (INIS)

Bagus, P S; Pacchioni, G

2008-01-01

We report a detailed analysis of the electronic mechanisms which determine the bond strength and the vibrational frequency of CO molecules adsorbed on neutral or charged gold nanoparticles. To this end we have considered a simple cluster model, Au 5 CO q (q = +1, 0, -1), and decomposed the Au-CO interaction energy into the sum of various contributions according to a Constrained Space Orbital Variation approach. While the adsorption energy is relatively insensitive to the value of q, the C-O stretch frequency, ω e (CO), changes substantially, and allows the use of this molecule as a direct probe of the gold oxidation state. The results show that two major terms contribute to the red or blue shift of ω e (CO) as a function of q: the interaction with the electric field associated to the charged nanoparticle (Stark effect) and the Au → CO Φ back donation. The CO → Au σ donation is about half as important as the Φ back-donation and all other terms are much less important

Molecular dynamics simulation of cascade damage in gold

International Nuclear Information System (INIS)

Alonso, E.; Caturla, M.J.; Tang, M.; Huang, H.; Diaz de la Rubia, T.

1997-01-01

High-energy cascades have been simulated in gold using molecular dynamics with a modified embedded atom method potential. The results show that both vacancy and interstitial clusters form with high probability as a result of intracascade processes. The formation of clusters has been interpreted in terms of the high pressures generated in the core of the cascade during the early stages. The authors provide evidence that correlation between interstitial and vacancy clustering exists

Dynamic monolayer gradients: Active spatiotemporal control of alkanethiol coatings on thin gold films

Energy Technology Data Exchange (ETDEWEB)

Terrill, R.H.; Balss, K.M.; Zhang, Y.; Bohn, P.W.

2000-02-09

The chemical modification of coinage metal surfaces with {omega}-functionalized alkanethiols has proven to be a popular system for studies of wetting, adhesion, chemical affinity, and electron transfer. Varying the composition of binary hydrophilic-hydrophobic self-assembled monolayers (SAMs) can vary the wetting properties of a surface in a continuous manner, a fact that has been exploited to distribute surface-active molecules inhomogeneously under mass-transport control. One goal of these experiments is to create surfaces which permit supermolecular objects to be manipulated under external control, as recently demonstrated at air-liquid interfaces. The authors report chemical potential distributions of alkanethiols, which can be manipulated in both space and time under active electrochemical control.

Vibrational properties of gold nanoparticles obtained by green synthesis

Science.gov (United States)

Alvarez, Ramón A. B.; Cortez-Valadez, M.; Bueno, L. Oscar Neira; Britto Hurtado, R.; Rocha-Rocha, O.; Delgado-Beleño, Y.; Martinez-Nuñez, C. E.; Serrano-Corrales, Luis Ivan; Arizpe-Chávez, H.; Flores-Acosta, M.

2016-10-01

This study reports the synthesis and characterization of gold nanoparticles through an ecological method to obtain nanostructures from the extract of the plant Opuntia ficus-indica. Colloidal nanoparticles show sizes that vary between 10-20 nm, and present various geometric morphologies. The samples were characterized through optical absorption, Raman Spectroscopy and Transmission Electron Microscopy (TEM). Additionally, low energy metallic clusters of Aun (n=2-20 atoms) were modeled by computational quantum chemistry. The theoretical results were obtained with Density Functional Theory (DFT). The predicted results of Au clusters show a tendency and are correlated with the experimental results concerning the optical absorption bands and Raman spectroscopy in gold nanoparticles.

Characterization of silicon-oxide interfaces and organic monolayers by IR-UV ellipsometry and FTIR spectroscopy

Science.gov (United States)

Hess, P.; Patzner, P.; Osipov, A. V.; Hu, Z. G.; Lingenfelser, D.; Prunici, P.; Schmohl, A.

2006-08-01

VUV-laser-induced oxidation of Si(111)-(1×1):H, Si(100):H, and a-Si:H at 157 nm (F II laser) in pure O II and pure H IIO atmospheres was studied between 30°C and 250°C. The oxidation process was monitored in real time by spectroscopic ellipsometry (NIR-UV) and FTIR spectroscopy. The ellipsometric measurements could be simulated with a three-layer model, providing detailed information on the variation of the suboxide interface with the nature of the silicon substrate surface. Besides the silicon-dioxide and suboxide layer, a dense, disordered, roughly monolayer thick silicon layer was included, as found previously by molecular dynamics calculations. The deviations from the classical Deal-Grove mechanism and the self-limited growth of the ultrathin dioxide layers (TMS) groups and n-alkylthiol monolayers on gold-coated silicon. The C-H stretching vibrations of the methylene and methyl groups could be identified by FTIR spectroscopy and IR ellipsometry.

Cysteine adsorption on the Au(111) surface and the electron transfer in configuration of a scanning tunneling microscope: A quantum-chemical approach

DEFF Research Database (Denmark)

Nazmutdinov, R.R.; Manyurov, I.R.; Zinkicheva, T.T.

2007-01-01

Adsorption of two forms, molecule and radical, of amino acid L-cysteine (Cys) on the Au-12 cluster that simulates the (111) face of single-crystal gold is studied in the framework of the density functional theory. Effects of solvation of adsorbed Cys particles and lateral interaction in a monolay...

Near-field photochemical and radiation-induced chemical fabrication of nanopatterns of a self-assembled silane monolayer

Directory of Open Access Journals (Sweden)

Ulrich C. Fischer

2014-09-01

Full Text Available A general concept for parallel near-field photochemical and radiation-induced chemical processes for the fabrication of nanopatterns of a self-assembled monolayer (SAM of (3-aminopropyltriethoxysilane (APTES is explored with three different processes: 1 a near-field photochemical process by photochemical bleaching of a monomolecular layer of dye molecules chemically bound to an APTES SAM, 2 a chemical process induced by oxygen plasma etching as well as 3 a combined near-field UV-photochemical and ozone-induced chemical process, which is applied directly to an APTES SAM. All approaches employ a sandwich configuration of the surface-supported SAM, and a lithographic mask in form of gold nanostructures fabricated through colloidal sphere lithography (CL, which is either exposed to visible light, oxygen plasma or an UV–ozone atmosphere. The gold mask has the function to inhibit the photochemical reactions by highly localized near-field interactions between metal mask and SAM and to inhibit the radiation-induced chemical reactions by casting a highly localized shadow. The removal of the gold mask reveals the SAM nanopattern.

Synthesis and study of catalytic application of l-methionine protected gold nanoparticles

Science.gov (United States)

Raza, Akif; Javed, Safdar; Qureshi, Muhammad Zahid; khan, Muhammad Usman; Khan, Muhammad Saleem

2017-10-01

Gold nanoparticle is growing class of nanotechnology due to large number of uses. We synthesized stable l-methionine protected gold nanoparticles (AuNps) by in situ reduction of HAuCl4 using sodium borohydrate as reducing and l-methionine as stabilizing agent in an aqueous medium. Different parameters (pH, capping agent, precursor salt, and heating time) were optimized to see the effect on the size of particles. Double beam spectrophotometer was used to carry out the spectroscopic studies. It was observed that pH and concentration of reducing salt are deciding factors in controlling the size and morphology of AuNps. Scanning electron microscopy (SEM) verified the formation of AuNPs as predicted by UV-Vis spectra. The interaction of AuNPs with l-methionine was confirmed by Fourier Transform Infrared (FTIR). The reduction of 4-nitrophenol acted as standard of reaction to check the response of AuNps catalyst. Complete reduction of 4-nitrophenol was accomplished by AuNps sol in just 60 s. Fastest reduction rate was observed with smaller spherical particles. This study concluded that size and shape of AuNps can be monitored by controlling the pH, concentration of capping and reducing agent. It also provides an economical solution to aquatic environment in terms of time saving and use of small volume of catalytic solution for reduction of several other toxic organic pollutants.

Vacancy Clusters on Surfaces of Au Nanoparticles Embedded in MgO

International Nuclear Information System (INIS)

Xu, Jun; Mills, A. P. Jr.; Ueda, A.; Henderson, D. O.; Suzuki, R.; Ishibashi, S.

1999-01-01

MeV implantation of gold ions into MgO(100) followed by annealing is a method to form gold nanoparticles for obtaining modified optical properties. We show from variable-energy positron spectroscopy that clusters of 2 Mg and 2 O vacancies (v 4 ) are attached to the gold nanoparticle surfaces within the projected range (R p ) . We also find that v 4 vacancy clusters are created at depths less than R p , and extend into the region greater than R p due to damage induced by knock-on collisions. (c) 1999 The American Physical Society

Understanding the catalytic activity of gold nanoparticles through multi-scale simulations

DEFF Research Database (Denmark)

Brodersen, Simon Hedegaard; Vej-Hansen, Ulrik Grønbjerg; Larsen, Britt Hvolbæk

2011-01-01

We investigate how the chemical reactivity of gold nanoparticles depends on the cluster size and shape using a combination of simulation techniques at different length scales, enabling us to model at the atomic level the shapes of clusters in the size range relevant for catalysis. The detailed......-coordinated active sites is found, and their reactivities are extracted from models based on Density Functional Theory calculations. This enables us to determine the chemical activity of clusters in the same range of particle sizes that is accessible experimentally. The variation of reactivity with particle size...... is in excellent agreement with experiments, and we conclude that the experimentally observed trends are mostly explained by the high reactivity of under-coordinated corner atoms on the gold clusters. Other effects, such as the effect of the substrate, may influence the reactivities significantly, but the presence...

Surface enhanced imaging and IR spectroscopy of the biological cells on the nanostructured gold film

Directory of Open Access Journals (Sweden)

G.I. Dovbeshko

2017-07-01

Full Text Available New approach for optical imaging, structural study and cell cultivation based on the effect of the enhancement of optical signals from biomolecules and biological cells near nanostructured rough gold surface is proposed. The surface enhanced IR absorption (SEIRA spectroscopy and confocal microscopy experiments were made using the culture of SPEV (porcine embryonic kidney epithelium transplantable line and fibroblast cells, cultivated and/or adsorbed on the gold substrate. The SEIRA spectra registered from monolayer of the SPEV cells cultivated on the rough gold showed a low frequency shift of about 2 to 7 cm 1 for the most characteristic IR vibrations, compared with those adsorbed from suspension on the same substrate. An enhancement factor of 15…30 was obtained for different molecular vibrations. The confocal microscopy contrast images of the SPEV cells on rough gold substrate were obtained in laser fluorescence mode. This approach opens new possibilities for visualization of the living cells in vivo without staining. The fluorescence of the rough gold surfaces and effects responsible for our findings have been discussed.

Gold Wire-networks: Particle Array Guided Evaporation Lithograpy

KAUST Repository

Lone, Saifullah

2015-06-29

We exploited the combination of dry deposition of monolayer of 2D (two dimensional) templates, lift-up transfer of 2D template onto flat surfaces and evaporation lithography [1] to fabricate gold micro- and submicron size wire networks. The approach relies upon the defect free dry deposition of 2D monolayer of latex particles [2] on patterned silicon template and flat PDMS-substrate to create square centered and honey-comb wire networks respectively. The process is followed by lift-up transfer of 2D latex crystal on glass substrate. Subsequently, a small amount of AuNP-suspension is doped on top of the transferred crystal; the suspension is allowed to spread instantaneously and dried at low temperature. The liquid evaporates uniformly to the direction perpendicular to glass substrate. During evaporation, AuNPs are de-wetted along with the movement of liquid to self-assemble in-between the inter-particle spaces and therefore, giving rise to liquid-bridge networks which upon delayed evaporation, transforms into wire networks. The approach is used to fabricate both micro- and submicron wire-networks by simply changing the template dimensions. One of the prime motives behind this study is to down-scale the existing particle array template-based evaporation lithography process to fabricate connected gold wire networks at both micro- and submicron scale. Secondly, the idea of combining the patterned silicon wafer with lifted latex particle template creates an opportunity to clean and res-use the patterned wafer more often and thereby, saving fabrication time and resources. Finally, we illustrated the validity of this approach by creating an easy and high-speed approach to develop gold wire networks on a flexible substrate with a thin deposited adhesive. These advances will not only serve as a platform to scale up the production, but also demonstrated that the fabrication method can produce metallic wire networks of different scale and onto a variety of substrates.

Lipid dip-pen nanolithography on self-assembled monolayers

International Nuclear Information System (INIS)

Gavutis, Martynas; Navikas, Vytautas; Rakickas, Tomas; Vaitekonis, Šarūnas; Valiokas, Ramūnas

2016-01-01

Dip-pen nanolithography (DPN) with lipids as an ink enables functional micro/nanopatterning on different substrates at high process speeds. However, only a few studies have addressed the influence of the physicochemical properties of the surface on the structure and phase behavior of DPN-printed lipid assemblies. Therefore, by combining the scanning probe and optical imaging techniques in this work we have analyzed lipid microdomain formation on the self-assembled monolayers (SAMs) on gold as well-defined model surfaces that displayed hydrophilic (protein-repellent) or hydrophobic (protein-adhesive) characteristics. We have found that on the tri(ethylene glycol)-terminated SAM the lipid ink transfer was fast (∼10 –1 μm 3 s −1 ), quasi-linear and it yielded unstable, sparsely packed lipid microspots. Contrary to this, on the methyl-terminated SAM the lipid transfer was ∼20 times slower, nonlinear, and the obtained stable dots of ∼1 μm in diameter consisted of lipid multilayers. Our comparative analysis indicated that the measured lipid transfer was consistent with the previously reported so-called polymer transfer model (Felts et al 2012, Nanotechnology 23 215301). Further on, by employing the observed distinct contrast in the DPN ink behavior we constructed confined lipid microdomains on pre-patterned SAMs, in which the lipids assembled either into monolayer or multilamellar phases. Such microdomains can be further utilized for lipid membrane mimetics in microarray and lab-on-a-chip device formats. (paper)

Integrated electrochemical gluconic acid biosensor based on self-assembled monolayer-modified gold electrodes. Application to the analysis of gluconic acid in musts and wines.

Science.gov (United States)

Campuzano, S; Gamella, M; Serra, B; Reviejo, A J; Pingarrón, J M

2007-03-21

An integrated amperometric gluconic acid biosensor constructed using a gold electrode (AuE) modified with a self-assembled monolayer (SAM) of 3-mercaptopropionic acid (MPA) on which gluconate dehydrogenase (GADH, 0.84 U) and the mediator tetrathiafulvalene (TTF, 1.5 micromol) were coimmobilized by covering the electrode surface with a dialysis membrane is reported. The working conditions selected were Eapp=+0.15 V and 25+/-1 degrees C. The useful lifetime of one single TTF-GADH-MPA-AuE was surprisingly long. After 53 days of continuous use, the biosensor exhibited 86% of the original sensitivity. A linear calibration plot was obtained for gluconic acid over the 6.0x10(-7) to 2.0x10(-5) M concentration range, with a limit of detection of 1.9x10(-7) M. The effect of potential interferents (glucose, fructose, galactose, arabinose, and tartaric, citric, malic, ascorbic, gallic, and caffeic acids) on the biosensor response was evaluated. The behavior of the biosensor in a flow-injection system in connection with amperometric detection was tested. The analytical usefulness of the biosensor was evaluated by determining gluconic acid in wine and must samples, and the results obtained were validated by comparison with those provided by using a commercial enzyme test kit.

Protective Effects of Bifidobacterium on Intestinal Barrier Function in LPS-Induced Enterocyte Barrier Injury of Caco-2 Monolayers and in a Rat NEC Model.

Directory of Open Access Journals (Sweden)

Xiang Ling

Full Text Available Zonulin protein is a newly discovered modulator which modulates the permeability of the intestinal epithelial barrier by disassembling intercellular tight junctions (TJ. Disruption of TJ is associated with neonatal necrotizing enterocolitis (NEC. It has been shown bifidobacterium could protect the intestinal barrier function and prophylactical administration of bifidobacterium has beneficial effects in NEC patients and animals. However, it is still unknown whether the zonulin is involved in the gut barrier dysfunction of NEC, and the protective mechanisms of bifidobacterium on intestinal barrier function are also not well understood. The present study aims to investigate the effects of bifidobacterium on intestinal barrier function, zonulin regulation, and TJ integrity both in LPS-induced enterocyte barrier injury of Caco-2 monolayers and in a rat NEC model. Our results showed bifidobacterium markedly attenuated the decrease in transepithelial electrical resistance and the increase in paracellular permeability in the Caco-2 monolayers treated with LPS (P < 0.01. Compared with the LPS group, bifidobacterium significantly decreased the production of IL-6 and TNF-α (P < 0.01 and suppressed zonulin release (P < 0.05. In addition, bifidobacterium pretreatment up-regulated occludin, claudin-3 and ZO-1 expression (P < 0.01 and also preserved these proteins localization at TJ compared with the LPS group. In the in vivo study, bifidobacterium decreased the incidence of NEC from 88 to 47% (P < 0.05 and reduced the severity in the NEC model. Increased levels of IL-6 and TNF-α in the ileum of NEC rats were normalized in bifidobacterium treated rats (P < 0.05. Moreover, administration of bifidobacterium attenuated the increase in intestinal permeability (P < 0.01, decreased the levels of serum zonulin (P < 0.05, normalized the expression and localization of TJ proteins in the ileum compared with animals with NEC. We concluded that bifidobacterium may

Long-term stability of surfactant-free gold nanostars

Science.gov (United States)

Vega, Marienette Morales; Bonifacio, Alois; Lughi, Vanni; Marsi, Stefano; Carrato, Sergio; Sergo, Valter

2014-11-01

This work investigates the long-term stability of suspensions of surfactant-free gold nanostars with mean diameter of 78 ± 13 nm (measured from tip to tip across the nanostar).We monitored the optical and morphological properties of the nanostars over the course of several days after synthesis by observing the changes in the UV-visible absorption spectra and mean radius of curvature of the nanostar tips. An aging process can be observed, evident in the blunting of the nanostar tips, leading to a blue shift in the absorption maximum. Stability is greatly improved by depositing on the nanostars a monolayer of mercaptopropionic acid (MPA), possibly because of the formation of the gold-sulfur (Au-S) bond that limits the mobility of the Au atoms. Capping the nanostars with MPA is an easy additional step for extending the stability of the nanostars in suspension without significantly affecting the original plasmonic resonance band.

Evaluation of secondary ion yield enhancement from polymer material by using TOF-SIMS equipped with a gold cluster ion source

Energy Technology Data Exchange (ETDEWEB)

Aimoto, K. [Department of Applied Physics, Faculty of Engineering, Seikei University, 3-3-1 Kichijioji-Kitamachi, Musashino-shi, Tokyo 180-8633 (Japan)]. E-mail: dm053502@cc.seikei.ac.jp; Aoyagi, S. [Department of Regional Development, Faculty of Life and Environmental Science, Shimane University, 1060 Nishikawatsu-cho, Matsue-shi, Shimane 690-8504 (Japan); Kato, N. [Department of Applied Physics, Faculty of Engineering, Seikei University, 3-3-1 Kichijioji-Kitamachi, Musashino-shi, Tokyo 180-8633 (Japan); Iida, N. [ULVAC-PHI, Inc., 370 Enzo, Chigasaki, Kanagawa 253-0084 (Japan); Yamamoto, A. [ULVAC-PHI, Inc., 370 Enzo, Chigasaki, Kanagawa 253-0084 (Japan); Kudo, M. [Department of Applied Physics, Faculty of Engineering, Seikei University, 3-3-1 Kichijioji-Kitamachi, Musashino-shi, Tokyo 180-8633 (Japan)

2006-07-30

We investigated the enhancement of the secondary ion intensity in the TOF-SIMS spectra obtained by Au{sup +} and Au{sub 3} {sup +} bombardment in comparison with Ga{sup +} excitation using polymer samples with different molecular weight distributions. Since the polymer samples used in this experiment have a wide molecular weight distribution, the advantages of the gold cluster primary ion source over monoatomic ion could accurately be evaluated. It was observed that the degree of fragmentation decreased by the usage of cluster primary ion beam compared with monoatomic ion beam, which was observed as a shift of the intensity distribution in the spectra. It was also found out that the mass effect of Au{sup +} and Ga{sup +} as monoatomic primary ion, resulted in about 10-60 times of enhancement for both samples with different molecular distributions. On the other hand, the Au{sub 3} {sup +} bombardment caused intensity enhancement about 100-2600 compared with Ga{sup +} bombardment, depending on the mass range of the detected secondary ion species. The cluster primary ion effect of Au{sub 3} {sup +}, compared with Au{sup +}, therefore, was estimated to be about 10-45.

Nanoparticle-based receptors mimic protein-ligand recognition

OpenAIRE

Riccardi, Laura; Gabrielli, Luca; Sun, Xiaohuan; Biasi, Federico De; Rastrelli, Federico; Mancin, Fabrizio; De Vivo, Marco

2017-01-01

Summary The self-assembly of a monolayer of ligands on the surface of noble-metal nanoparticles dictates the fundamental nanoparticle's behavior and its functionality. In this combined computational-experimental study, we analyze the structure, organization, and dynamics of functionalized coating thiols in monolayer-protected gold nanoparticles (AuNPs). We explain how functionalized coating thiols self-organize through a delicate and somehow counterintuitive balance of interactions within the...

Enhanced Light–Matter Interactions in Graphene-Covered Gold Nanovoid Arrays

DEFF Research Database (Denmark)

Zhu, Xiaolong; Shi, Lei; Schmidt, Michael Stenbæk

2013-01-01

The combination of graphene with noble-metal nanostructures is currently being explored for strong light–graphene interactions enhanced by plasmons. We introduce a novel hybrid graphene–metal system for studying light–matter interactions with gold-void nanostructures exhibiting resonances...... in the visible range. Enhanced coupling of graphene to the plasmon modes of the nanovoid arrays results in significant frequency shifts of the underlying plasmon resonances, enabling 30% enhanced absolute light absorption by adding a monolayer graphene and up to 700-fold enhancement of the Raman response...

Toward high value sensing: monolayer-protected metal nanoparticles in multivariable gas and vapor sensors.

Science.gov (United States)

Potyrailo, Radislav A

2017-08-29

For detection of gases and vapors in complex backgrounds, "classic" analytical instruments are an unavoidable alternative to existing sensors. Recently a new generation of sensors, known as multivariable sensors, emerged with a fundamentally different perspective for sensing to eliminate limitations of existing sensors. In multivariable sensors, a sensing material is designed to have diverse responses to different gases and vapors and is coupled to a multivariable transducer that provides independent outputs to recognize these diverse responses. Data analytics tools provide rejection of interferences and multi-analyte quantitation. This review critically analyses advances of multivariable sensors based on ligand-functionalized metal nanoparticles also known as monolayer-protected nanoparticles (MPNs). These MPN sensing materials distinctively stand out from other sensing materials for multivariable sensors due to their diversity of gas- and vapor-response mechanisms as provided by organic and biological ligands, applicability of these sensing materials for broad classes of gas-phase compounds such as condensable vapors and non-condensable gases, and for several principles of signal transduction in multivariable sensors that result in non-resonant and resonant electrical sensors as well as material- and structure-based photonic sensors. Such features should allow MPN multivariable sensors to be an attractive high value addition to existing analytical instrumentation.

Gold nanoparticles for cancer detection and treatment: The role of adhesion

Energy Technology Data Exchange (ETDEWEB)

Oni, Y. [Princeton Institute for Science and Technology of Materials (PRISM), Princeton University, 70 Prospect Street, Princeton, New Jersey 08544 (United States); Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey 08544 (United States); Hao, K. [Department of Civil and Environmental Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States); Dozie-Nwachukwu, S.; Odusanya, O. S. [African University of Science and Technology (AUST), Kilometer 10, Airport Road, Abuja, Federal Capital Territory (Nigeria); Sheda Science and Technology Complex (SHESTCO), Gwagwalada, Abuja, Federal Capital Territory (Nigeria); Obayemi, J.D. [African University of Science and Technology (AUST), Kilometer 10, Airport Road, Abuja, Federal Capital Territory (Nigeria); Anuku, N. [Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey 08544 (United States); Department of Chemistry and Chemical Technology, Bronx Community College, New York, New York 10453 (United States); Soboyejo, W. O. [Princeton Institute for Science and Technology of Materials (PRISM), Princeton University, 70 Prospect Street, Princeton, New Jersey 08544 (United States); Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey 08544 (United States); African University of Science and Technology (AUST), Kilometer 10, Airport Road, Abuja, Federal Capital Territory (Nigeria)

2014-02-28

This paper presents the results of an experimental study of the effects of adhesion between gold nanoparticles and surfaces that are relevant to the potential applications in cancer detection and treatment. Adhesion is measured using a dip coating/atomic force microscopy (DC/AFM) technique. The adhesion forces are obtained for dip-coated gold nanoparticles that interact with peptide or antibody-based molecular recognition units (MRUs) that attach specifically to breast cancer cells. They include MRUs that attach specifically to receptors on breast cancer cells. Adhesion forces between anti-cancer drugs such as paclitaxel, and the constituents of MRU-conjugated Au nanoparticle clusters, are measured using force microscopy techniques. The implications of the results are then discussed for the design of robust gold nanoparticle clusters and for potential applications in localized drug delivery and hyperthermia.

Gold nanoparticles for cancer detection and treatment: The role of adhesion

International Nuclear Information System (INIS)

Oni, Y.; Hao, K.; Dozie-Nwachukwu, S.; Odusanya, O. S.; Obayemi, J.D.; Anuku, N.; Soboyejo, W. O.

2014-01-01

This paper presents the results of an experimental study of the effects of adhesion between gold nanoparticles and surfaces that are relevant to the potential applications in cancer detection and treatment. Adhesion is measured using a dip coating/atomic force microscopy (DC/AFM) technique. The adhesion forces are obtained for dip-coated gold nanoparticles that interact with peptide or antibody-based molecular recognition units (MRUs) that attach specifically to breast cancer cells. They include MRUs that attach specifically to receptors on breast cancer cells. Adhesion forces between anti-cancer drugs such as paclitaxel, and the constituents of MRU-conjugated Au nanoparticle clusters, are measured using force microscopy techniques. The implications of the results are then discussed for the design of robust gold nanoparticle clusters and for potential applications in localized drug delivery and hyperthermia

Superior Valley Polarization and Coherence of 2s Excitons in Monolayer WSe_{2}.

Science.gov (United States)

Chen, Shao-Yu; Goldstein, Thomas; Tong, Jiayue; Taniguchi, Takashi; Watanabe, Kenji; Yan, Jun

2018-01-26

We report the experimental observation of 2s exciton radiative emission from monolayer tungsten diselenide, enabled by hexagonal boron nitride protected high-quality samples. The 2s luminescence is highly robust and persists up to 150 K, offering a new quantum entity for manipulating the valley degree of freedom. Remarkably, the 2s exciton displays superior valley polarization and coherence than 1s under similar experimental conditions. This observation provides evidence that the Coulomb-exchange-interaction-driven valley-depolarization process, the Maialle-Silva-Sham mechanism, plays an important role in valley excitons of monolayer transition metal dichalcogenides.

Superior Valley Polarization and Coherence of 2 s Excitons in Monolayer WSe2

Science.gov (United States)

Chen, Shao-Yu; Goldstein, Thomas; Tong, Jiayue; Taniguchi, Takashi; Watanabe, Kenji; Yan, Jun

2018-01-01

We report the experimental observation of 2 s exciton radiative emission from monolayer tungsten diselenide, enabled by hexagonal boron nitride protected high-quality samples. The 2 s luminescence is highly robust and persists up to 150 K, offering a new quantum entity for manipulating the valley degree of freedom. Remarkably, the 2 s exciton displays superior valley polarization and coherence than 1 s under similar experimental conditions. This observation provides evidence that the Coulomb-exchange-interaction-driven valley-depolarization process, the Maialle-Silva-Sham mechanism, plays an important role in valley excitons of monolayer transition metal dichalcogenides.

A combined strategy for screening a clustered mobile population returning from highly endemic areas for Plasmodium falciparum.

Science.gov (United States)

Li, Mei; Li, Jun; Xia, Zhigui; Xiao, Ning; Jiang, Weikang; Wen, Yongkang

2017-04-30

Early and accurate diagnosis of imported malaria cases in clusters is crucial for protecting the health of patients and local populations, especially confirmed parasitic persons who are asymptomatic. A total of 226 gold miners who had stayed in highly endemic areas of Ghana for more than six months and returned in clusters were selected randomly. Blood samples from them were tested with microscopy, nest polymerase chain reaction, and rapid diagnostic test (RDT). The sensitivity, specificity, predictive values, agreement rate, and Youden's index of each of three diagnostic methods were calculated and compared with the defined gold standard. A quick and efficient way to respond to screening such a clustered mobile population was predicted and analyzed by evaluating two assumed results of combining microscopy and RDT with or without symptoms of illness. The rate of the carriers of malaria parasites in the populations of gold miners was 19.47%, including 39 P. falciparum. Among the three diagnostic methods, the microscopy method showed the highest specificity, while the RDT method showed the highest sensitivity but the lowest specificity in detecting P. falciparum. The assumed results of combining RDT and microscopy with symptoms showed the best results among all the test results in screening P. falciparum. It was too complex and difficult to catch all parasite carriers in a short period of time among populations with such a complicated situation as that in Shanglin County. A strategy of combing microscopy and RDT for diagnosis is highly recommended.

Preparation of porous polymer monoliths featuring enhanced surface coverage with gold nanoparticles

KAUST Repository

Lv, Yongqin

2012-10-01

A new approach to the preparation of porous polymer monoliths with enhanced coverage of pore surface with gold nanoparticles has been developed. First, a generic poly(glycidyl methacrylate-co-ethylene dimethacrylate) monolith was reacted with cystamine followed by the cleavage of its disulfide bonds with tris(2-carboxylethyl)phosphine, which liberated the desired thiol groups. Dispersions of gold nanoparticles with sizes varying from 5 to 40. nm were then pumped through the functionalized monoliths. The materials were then analyzed using both energy dispersive X-ray spectroscopy and thermogravimetric analysis. We found that the quantity of attached gold was dependent on the size of nanoparticles, with the maximum attachment of more than 60. wt% being achieved with 40. nm nanoparticles. Scanning electron micrographs of the cross sections of all the monoliths revealed the formation of a non-aggregated, homogenous monolayer of nanoparticles. The surface of the bound gold was functionalized with 1-octanethiol and 1-octadecanethiol, and these monolithic columns were used successfully for the separations of proteins in reversed phase mode. The best separations were obtained using monoliths modified with 15, 20, and 30. nm nanoparticles since these sizes produced the most dense coverage of pore surface with gold. © 2012 Elsevier B.V.

Pinning of size-selected gold and nickel nanoclusters on graphite

NARCIS (Netherlands)

Di Vece, M.|info:eu-repo/dai/nl/248753355; Paloma, S.; Palmer, R.E.

2005-01-01

Size-selected gold and nickel nanoclusters are of interest from an electronic, catalytic, and biological point of view. These applications require the deposition of the clusters on a surface, and a key challenge is to retain the cluster size. Here controlled energy impact is used to immobilize the

Hut clusters on Ge(001) surfaces studied by STM and synchrotron X-ray diffraction

DEFF Research Database (Denmark)

Nielsen, M.; Smilgies, D.-M.; Feidenhans'l, R.

1996-01-01

Nanoscale hut clusters formed on Ge(001) surfaces by depositing one monolayer of indium and annealing at temperatures between 350 and 500 degrees C were studied by scanning tunnelling microscopy and synchrotron X-ray diffraction. It was found that the hut clusters form regular arrays over...

Gold ions bio-released from metallic gold particles reduce inflammation and apoptosis and increase the regenerative responses in focal brain injury

DEFF Research Database (Denmark)

Larsen, Agnete; Kolind, Kristian; Pedersen, Dan Sonne

2008-01-01

neural stem cell response. We conclude that bio-liberated gold ions possess pronounced anti-inflammatory and neuron-protective capacities in the brain and suggest that metallic gold has clinical potentials. Intra-cerebral application of metallic gold as a pharmaceutical source of gold ions represents......Traumatic brain injury results in loss of neurons caused as much by the resulting neuroinflammation as by the injury. Gold salts are known to be immunosuppressive, but their use are limited by nephrotoxicity. However, as we have proven that implants of pure metallic gold release gold ions which do...... not spread in the body, but are taken up by cells near the implant, we hypothesize that metallic gold could reduce local neuroinflammation in a safe way. Bio-liberation, or dissolucytosis, of gold ions from metallic gold surfaces requires the presence of disolycytes i.e. macrophages and the process...

Disintegration of swift carbon clusters during passage through matter

International Nuclear Information System (INIS)

Koch, K.; Otteken, D.; Tuszynski, W.; Seidl, M.; Voit, H.

2003-01-01

Thin luminescent foils covered upstream with layers of Formvar or gold of various thicknesses were bombarded with C 8 clusters with energies between 5 and 10 MeV. The C 8 induced relative luminescence yield Φ 8 increases with growing layer thickness and approaches smoothly the value 8Φ 1 , i.e., the luminescence yield induced by eight well-separated C 1 cluster constituents. This is a clear demonstration of the gradual separation between the cluster constituents during the passage of the cluster through the layers. The layer thickness necessary to separate cluster constituents far enough to act as independent atomic ions with respect to the luminescence process was calculated. The result is that Formvar layers with a thickness of about 1150 nm or ≅250-nm-thick gold layers are necessary to establish this mutual independence of the cluster constituents. Both calculated values agree roughly with the layer thickness obtained from an extrapolation of the experimental data

Bonding properties of FCC-like Au ₄₄ (SR) ₂₈ clusters from X-ray absorption spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Yang, Rui [Department of Chemistry, Dalhousie University, Halifax, NS B3H 4R2, Canada.; Chevrier, Daniel M. [Department of Chemistry, Dalhousie University, Halifax, NS B3H 4R2, Canada.; Zeng, Chenjie [Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA.; Jin, Rongchao [Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA 15213, USA.; Zhang, Peng [Department of Chemistry, Dalhousie University, Halifax, NS B3H 4R2, Canada.

2017-11-01

Thiolate-protected gold clusters with precisely controlled atomic composition have recently emerged as promising candidates for a variety of applications because of their unique optical, electronic, and catalytic properties. The recent discovery of the Au44(SR)28 total structure is considered as an interesting finding in terms of the face-centered cubic (FCC)-like core structure in small gold-thiolate clusters. Herein, the unique bonding properties of Au44(SR)28 is analyzed using temperature-dependent X-ray absorption spectroscopy (XAS) measurements at the Au L3-edge and compared with other FCC-like clusters such as Au36(SR)24 and Au28(SR)20. A negative thermal expansion was detected for the Au–Au bonds of the metal core (the first Au–Au shell) and was interpreted based on the unique Au core structure consisting of the Au4 units. EXAFS fitting results from Au28(SR)20, Au36(SR)24, and Au44(SR)28 show a size-dependent negative thermal expansion behavior in the first Au–Au shell, further highlighting the importance of the Au4 units in determining the Au core bonding properties and shedding light on the growth mechanism of these FCC-like Au clusters.

Mercury adsorption to gold nanoparticle and thin film surfaces

Science.gov (United States)

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.

Organic surfaces exposed by self-assembled organothiol monolayers: Preparation, characterization, and application

Science.gov (United States)

Kind, Martin; Wöll, Christof

2009-07-01

Organic surfaces play a major role in materials science. Most surfaces that we touch in our daily lives are made from organic materials, e.g., vegetables, fruit, skin, wood, and textiles made from natural fibers. In the context of biology, organic surfaces play a prominent role too, proteins docking onto cell surfaces are a good example. To better understand the characteristics of organic surfaces, including physico-chemical properties like wettability or chemical reactivities and physical properties like friction and lubrication, a structurally well-defined model system that can be investigated with numerous analytical techniques is desirable. In the last two decades, one particular system, self-assembled monolayers or SAMs, have demonstrated their suitability for this purpose. In particular, organothiols consisting of an organic molecule with an attached SH-group are well suited to fabricating structurally well-defined adlayers of monolayer thickness on gold substrates using a simple preparation procedure. These ultrathin monolayers expose an organic surface with properties that can be tailored by varying the type of organothiol employed. After a short introduction into the preparation of SAMs, this article provides an overview of the possibilities and limitations of organic surfaces exposed by Au-thiolate SAMs. Applications are as diverse as the metallization of organic surfaces, a fundamental problem in materials science, and the fabrication of surfaces that resist the adsorption of proteins. In addition to a number of different case studies, we will also discuss the most powerful analytical techniques needed to characterize these important model systems.

Influence of molecular packing on the corrosion inhibition properties of self-assembled octadecyltrichlorosilane monolayers on silicon

International Nuclear Information System (INIS)

Hsieh, Shuchen; Chao, Wei-Jay; Lin, Pei-Ying; Hsieh, Chiung-Wen

2014-01-01

Highlights: •Molecular packing plays an important role in determining SAM film properties. •Loose-packed OTS monolayers on silicon were corroded by exposure to KMnO 4 . •Dense-packed OTS SAM films exhibited excellent corrosion protection efficacy. -- Abstract: The corrosion inhibition properties of octadecyltrichlorosilane (OTS) self-assembled monolayers (SAMs) on silicon were investigated. Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), contact angle (CA), and lateral force microscopy (LFM) were used to determine the OTS film formation time, packing density, and corrosion protection efficacy. The OTS films reached adsorption saturation after 15 s; however, the molecular density continued to increase up to 24 h. The films were exposed to the strong oxidant KMnO 4 , and while 15-s film samples exhibited corrosion after a 1 min exposure, samples with films grown for 24 h were protected even after 24 h

Reactions of mixed silver-gold cluster cations AgmAun+ (m+n=4,5,6) with CO: Radiative association kinetics and density functional theory computations

International Nuclear Information System (INIS)

Neumaier, Marco; Weigend, Florian; Hampe, Oliver; Kappes, Manfred M.

2006-01-01

Near thermal energy reactive collisions of small mixed metal cluster cations Ag m Au n + (m+n=4, 5, and 6) with carbon monoxide have been studied in the room temperature Penning trap of a Fourier transform ion-cyclotron-resonance mass spectrometer as a function of cluster size and composition. The tetrameric species AgAu 3 + and Ag 2 Au 2 + are found to react dissociatively by way of Au or Ag atom loss, respectively, to form the cluster carbonyl AgAu 2 CO + . In contrast, measurements on a selection of pentamers and hexamers show that CO is added with absolute rate constants that decrease with increasing silver content. Experimentally determined absolute rate constants for CO adsorption were analyzed using the radiative association kinetics model to obtain cluster cation-CO binding energies ranging from 0.77 to 1.09 eV. High-level ab initio density functional theory (DFT) computations identifying the lowest-energy cluster isomers and the respective CO adsorption energies are in good agreement with the experimental findings clearly showing that CO binds in a ''head-on'' fashion to a gold atom in the mixed clusters. DFT exploration of reaction pathways in the case of Ag 2 Au 2 + suggests that exoergicities are high enough to access the minimum energy products for all reactive clusters probed

Reactions of mixed silver-gold cluster cations AgmAun+ (m+n=4,5,6) with CO: Radiative association kinetics and density functional theory computations

Science.gov (United States)

Neumaier, Marco; Weigend, Florian; Hampe, Oliver; Kappes, Manfred M.

2006-09-01

Near thermal energy reactive collisions of small mixed metal cluster cations AgmAun+ (m +n=4, 5, and 6) with carbon monoxide have been studied in the room temperature Penning trap of a Fourier transform ion-cyclotron-resonance mass spectrometer as a function of cluster size and composition. The tetrameric species AgAu3+ and Ag2Au2+ are found to react dissociatively by way of Au or Ag atom loss, respectively, to form the cluster carbonyl AgAu2CO+. In contrast, measurements on a selection of pentamers and hexamers show that CO is added with absolute rate constants that decrease with increasing silver content. Experimentally determined absolute rate constants for CO adsorption were analyzed using the radiative association kinetics model to obtain cluster cation-CO binding energies ranging from 0.77to1.09eV. High-level ab initio density functional theory (DFT) computations identifying the lowest-energy cluster isomers and the respective CO adsorption energies are in good agreement with the experimental findings clearly showing that CO binds in a "head-on" fashion to a gold atom in the mixed clusters. DFT exploration of reaction pathways in the case of Ag2Au2+ suggests that exoergicities are high enough to access the minimum energy products for all reactive clusters probed.

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

Science.gov (United States)

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.

Deposition of thin layer (monoatomic layer) of barium on gold single crystal surfaces and studies of its oxidation employing X-ray photoelectron spectroscopy

International Nuclear Information System (INIS)

Ahmad, H.; Ahmad, R.; Khalid, M.; Alvi, R.A.

2007-01-01

Due to the high reactivity of barium with oxygen, some oxygen diffuse into the bulk to form bulk oxide and it is very difficult to differentiate the oxide over layer and the bulk oxide. To study the oxidation of barium surface layer, a thin layer (monolayer) of barium is developed over gold single crystal surface. Gold is selected as support because it is one of the least reactive metal in transition metal group and have very low probability of reaction with oxygen at room temperature (300K). Nitrous oxide (N/sub 2/O) was used as oxidant. Thin layer of barium was deposited on Au(100) surface. The barium coverage on gold surface was calculated that varied from 0.4 to 1.4 monolayer (ML). Photoelectron spectra for O(ls), N(ls), Ba (3d), and Au (4f) have been recorded on X-ray photoelectron spectrometer at different binding energy region specific for each element. The decomposition of nitrous oxide has been observed in all cases. It has found that nitrogen is evolved in the gaseous state and oxygen is adsorbed/chemisorbed on barium over layer. (author)

Plasmon-Organic Fiber Interactions in Diamond-Like Carbon Coated Nanostructured Gold Films

DEFF Research Database (Denmark)

Cielecki, Pawel Piotr; Sobolewska, Elżbieta Karolina; Kostiučenko, Oksana

2017-01-01

Gold is the most commonly used plasmonic material, however soft and prone to mechanical deformations. It has been shown that the durability of gold plasmonic substrates can be improved by applying a protective diamond-like carbon (DLC) coating. In this work, we investigate the influence of such p......Gold is the most commonly used plasmonic material, however soft and prone to mechanical deformations. It has been shown that the durability of gold plasmonic substrates can be improved by applying a protective diamond-like carbon (DLC) coating. In this work, we investigate the influence...

Effects of irradiated biodegradable polymer in endothelial cell monolayer formation

Energy Technology Data Exchange (ETDEWEB)

Arbeitman, Claudia R.; Grosso, Mariela F. del [CONICET – Consejo Nacional de Investigaciones Científicas y Técnicas (Argentina); Gerencia de Investigación y Aplicaciones, TANDAR-CNEA (Argentina); Behar, Moni [Instituto de Física, UFRGS, Porto Alegre, RS (Brazil); García Bermúdez, Gerardo, E-mail: ggb@tandar.cnea.gov.ar [CONICET – Consejo Nacional de Investigaciones Científicas y Técnicas (Argentina); Gerencia de Investigación y Aplicaciones, TANDAR-CNEA (Argentina); Escuela de Ciencia y Tecnología, UNSAM (Argentina)

2013-11-01

In this work we study cell adhesion, proliferation and cell morphology of endothelial cell cultured on poly-L-lactide acid (PLLA) modified by heavy ion irradiation. Thin films of PLLA samples were irradiated with sulfur (S) at energies of 75 MeV and gold (Au) at 18 MeV ion-beams. Ion beams were provided by the Tandar (Buenos Aires, Argentina) and Tandetron (Porto Alegre, Brazil) accelerators, respectively. The growth of a monolayer of bovine aortic endothelial cells (BAEC) onto unirradiated and irradiated surfaces has been studied by in vitro techniques in static culture. Cell viability and proliferation increased on modified substrates. But the results on unirradiated samples, indicate cell death (necrosis/apoptosis) with the consequent decrease in proliferation. We analyzed the correlation between irradiation parameters and cell metabolism and morphology.

Effects of irradiated biodegradable polymer in endothelial cell monolayer formation

International Nuclear Information System (INIS)

Arbeitman, Claudia R.; Grosso, Mariela F. del; Behar, Moni; García Bermúdez, Gerardo

2013-01-01

In this work we study cell adhesion, proliferation and cell morphology of endothelial cell cultured on poly-L-lactide acid (PLLA) modified by heavy ion irradiation. Thin films of PLLA samples were irradiated with sulfur (S) at energies of 75 MeV and gold (Au) at 18 MeV ion-beams. Ion beams were provided by the Tandar (Buenos Aires, Argentina) and Tandetron (Porto Alegre, Brazil) accelerators, respectively. The growth of a monolayer of bovine aortic endothelial cells (BAEC) onto unirradiated and irradiated surfaces has been studied by in vitro techniques in static culture. Cell viability and proliferation increased on modified substrates. But the results on unirradiated samples, indicate cell death (necrosis/apoptosis) with the consequent decrease in proliferation. We analyzed the correlation between irradiation parameters and cell metabolism and morphology

Evaluation of monolayers and mixed monolayers formed from mercaptobenzothiazole and decanethiol as sensing platforms

International Nuclear Information System (INIS)

Mary Vergheese, T.; Berchmans, Sheela

2004-01-01

In this investigation, the characterisation of monolayer and mixed monolayers formed from mercaptobenzothiazole (MBT) and decanethiol (DT) has been carried out with cyclic voltammetry. The SAMs have been tested for their stability and electron transfer blocking properties. The redox probes used in the present study are [Fe(China) 6 ] 4- , [Ru(NH 3 ) 6 ] 2+ and Cu underpotential deposition (upd). The electron transfer kinetics is investigated in acid and neutral pH range. Electron transfer kinetics is altered by the nature of charge on the redox probe and the charge on the monolayer. Electron transfer kinetics of negatively charged redox probes like ferrocyanide ions is blocked when the surface pK a medium and at pK a >pH medium reversible features is observed for negatively charged probes. An exactly reverse effect is observed in the case of positively charged redox species like [Ru(NH 3 ) 6 ] 2+/3+ . Cu under potential deposition studies reflects the structural integrity and compactness of the SAM layer. The utility of these monolayers and mixed monolayer for selective sensing of dopamine is discussed based on their ability to discriminate between positively and negatively charged redox species at different pH

Synthesis of gold nanoclusters: a fluorescent marker for water-soluble TiO2 nanotubes

International Nuclear Information System (INIS)

Ratanatawanate, Chalita; Yu Jing; Zhou Chen; Zheng Jie; Balkus, Kenneth J Jr

2011-01-01

The first example of a water-soluble wrapped titania nanotube (TNT) decorated with fluorescent gold nanoparticles has been prepared. Gold nanoparticles ∼ 1.6 nm in diameter were grown on the TiO 2 nanotubes using a thiolactic acid linker to control the size. The gold clusters emit at 660 nm in water and were imaged using confocal microscopy. The gold decorated TNTs were suspended in water by wrapping the nanotubes with poly-L-arginine.

Surface properties of self-assembled monolayer films of tetra-substituted cobalt, iron and manganese alkylthio phthalocyanine complexes

Energy Technology Data Exchange (ETDEWEB)

Akinbulu, Isaac Adebayo; Khene, Samson [Department of Chemistry, Rhodes University, Grahamstown 6140 (South Africa); Nyokong, Tebello, E-mail: t.nyokong@ru.ac.z [Department of Chemistry, Rhodes University, Grahamstown 6140 (South Africa)

2010-09-30

Self-assembled monolayer (SAM) films of iron (SAM-1), cobalt (SAM-2) and manganese (SAM-3) phthalocyanine complexes, tetra-substituted with diethylaminoethanethio at the non-peripheral positions, were formed on gold electrode in dimethylformamide (DMF). Electrochemical, impedimentary and surface properties of the SAM films were investigated. Cyclic voltammetry was used to investigate the electrochemical properties of the films. Ability of the films to inhibit common faradaic processes on bare gold surface (gold oxidation, solution redox chemistry of [Fe(H{sub 2}O){sub 6}]{sup 3+}/[Fe(H{sub 2}O){sub 6}]{sup 2+} and underpotential deposition (UDP) of copper) was investigated. Electrochemical impedance spectroscopy (EIS), using [Fe(CN){sub 6}]{sup 3-/4-} redox process as a probe, offered insights into the electrical properties of the films/electrode interfaces. Surface properties of the films were probed using atomic force microscopy (AFM) and scanning electron microscopy (SEM). The films were employed for the electrocatalytic oxidation of the pesticide, carbofuran. Electrocatalysis was evidenced from enhanced current signal and less positive oxidation potential of the pesticide on each film, relative to that observed on the bare gold electrode. Mechanism of electrocatalytic oxidation of the pesticide was studied using rotating disc electrode voltammetry.

Amperometric aptasensor for saxitoxin using a gold electrode modified with carbon nanotubes on a self-assembled monolayer, and methylene blue as an electrochemical indicator probe

International Nuclear Information System (INIS)

Hou, Li; Jiang, Lingshan; Song, Yunping; Ding, Yunhua; Wu, Xiaoping; Tang, Dianping; Zhang, Jianhua

2016-01-01

A label-free electrochemical aptasensor was developed for selective detection of saxitoxin (STX). It is taking advantage of target-induced conformational change of an STX-specific aptamer when it binds to the toxin. A monolayer of octadecanethiol was deposited on a gold electrode, and then coated with a film of multiwalled carbon nanotubes (MWCNTs) to which the aptamer was covalently conjugated. Methylene blue (MB) was electrostatically anchored on carboxylated MWCNTs and used as the electrochemical indicator that produced a strong differential pulse voltammetric signal in the absence of target (STX). If, however, STX binds to its aptamer, this triggers a conformational change of the aptamer and results in the establishment of a barrier for heterogeneous electron transfer. The oxidation peak current of MB, acquired at −0.27 V (vs. Ag/AgCl), linearly decreases with increasing concentrations of STX in the 0.9 and 30 nM concentration range. The detection limit is 0.38 nM. Marine toxins that maybe present along with STX do not interfere even if they have a similar chemical structure. The assay was applied to the determination of STX in mussels samples and was found to be acceptably accurate. Hence, the method introduced here provides a rapid and sensitive tool for monitoring red tide pollution. (author)

Structures and shear response of lipid monolayers

International Nuclear Information System (INIS)

Dutta, P.; Ketterson, J.B.

1993-02-01

This report discusses our work during the last 3 years using x-ray diffraction and shear measurements to study lipid monolayers (membranes). The report is divided into: (1) structure: phase diagram of saturated fatty acid Langmuir monolayers, effect of head group interactions, studies of transferred monolayers (LB films); (2) mechanical properties: fiber=optic capillary wave probe and centrosymmetric trough, mechanical behavior of heneicosanoic acid monolayer phases

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

Science.gov (United States)

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.

Effects of hyperthermal proton bombardment on alkanethiol self-assembled monolayer on Au(1 1 1)

Energy Technology Data Exchange (ETDEWEB)

Xi Luan [Surface Science Western, University of Western Ontario, London, Ontario N6A 5B7 (Canada); Zheng Zhi; Lam, N.-S. [Department of Physics, Chinese University of Hong Kong, Shatin, Hong Kong (China); Grizzi, Oscar [Centro Atomico Bariloche, 8400 San Carlos de Bariloche, Rio Negro (Argentina); Lau, W.-M. [Surface Science Western, University of Western Ontario, London, Ontario N6A 5B7 (Canada)], E-mail: llau22@uwo.ca

2007-10-31

The effects of hyperthermal proton bombardment on alkanethiol self-assembled monolayer (SAM) on Au(1 1 1) are studied with scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS). The STM and XPS results show that proton bombardment with proton energy as low as 2 eV can induce cross-linking of the adsorbed alkanethiols and transform the original ordered SAM lattice to an array of nanoclusters of the cross-linked alkanethiols. For a bombardment at 3 eV with a fluence of 3x10{sup 15} cm{sup -2}, the typical cluster size is about 5 nm. In addition, the cluster size distribution is narrow, with no cluster larger than 8 nm. The cluster growth can be promoted by increasing the fluence at a fixed bombardment energy or increasing the energy at a fixed fluence. This indicates that surface diffusion of alkanethiols and cluster growth can be harnessed by the control of the bombardment energy and fluence.

Effects of hyperthermal proton bombardment on alkanethiol self-assembled monolayer on Au(1 1 1)

International Nuclear Information System (INIS)

Xi Luan; Zheng Zhi; Lam, N.-S.; Grizzi, Oscar; Lau, W.-M.

2007-01-01

The effects of hyperthermal proton bombardment on alkanethiol self-assembled monolayer (SAM) on Au(1 1 1) are studied with scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS). The STM and XPS results show that proton bombardment with proton energy as low as 2 eV can induce cross-linking of the adsorbed alkanethiols and transform the original ordered SAM lattice to an array of nanoclusters of the cross-linked alkanethiols. For a bombardment at 3 eV with a fluence of 3x10 15 cm -2 , the typical cluster size is about 5 nm. In addition, the cluster size distribution is narrow, with no cluster larger than 8 nm. The cluster growth can be promoted by increasing the fluence at a fixed bombardment energy or increasing the energy at a fixed fluence. This indicates that surface diffusion of alkanethiols and cluster growth can be harnessed by the control of the bombardment energy and fluence

Mitochondrial nucleoid clusters protect newly synthesized mtDNA during Doxorubicin- and Ethidium Bromide-induced mitochondrial stress

Energy Technology Data Exchange (ETDEWEB)

Alán, Lukáš, E-mail: lukas.alan@fgu.cas.cz; Špaček, Tomáš; Pajuelo Reguera, David; Jabůrek, Martin; Ježek, Petr

2016-07-01

Mitochondrial DNA (mtDNA) is compacted in ribonucleoprotein complexes called nucleoids, which can divide or move within the mitochondrial network. Mitochondrial nucleoids are able to aggregate into clusters upon reaction with intercalators such as the mtDNA depletion agent Ethidium Bromide (EB) or anticancer drug Doxorobicin (DXR). However, the exact mechanism of nucleoid clusters formation remains unknown. Resolving these processes may help to elucidate the mechanisms of DXR-induced cardiotoxicity. Therefore, we addressed the role of two key nucleoid proteins; mitochondrial transcription factor A (TFAM) and mitochondrial single-stranded binding protein (mtSSB); in the formation of mitochondrial nucleoid clusters during the action of intercalators. We found that both intercalators cause numerous aberrations due to perturbing their native status. By blocking mtDNA replication, both agents also prevented mtDNA association with TFAM, consequently causing nucleoid aggregation into large nucleoid clusters enriched with TFAM, co-existing with the normal nucleoid population. In the later stages of intercalation (> 48 h), TFAM levels were reduced to 25%. In contrast, mtSSB was released from mtDNA and freely distributed within the mitochondrial network. Nucleoid clusters mostly contained nucleoids with newly replicated mtDNA, however the nucleoid population which was not in replication mode remained outside the clusters. Moreover, the nucleoid clusters were enriched with p53, an anti-oncogenic gatekeeper. We suggest that mitochondrial nucleoid clustering is a mechanism for protecting nucleoids with newly replicated DNA against intercalators mediating genotoxic stress. These results provide new insight into the common mitochondrial response to mtDNA stress and can be implied also on DXR-induced mitochondrial cytotoxicity. - Highlights: • The mechanism for mitochondrial nucleoid clustering is proposed. • DNA intercalators (Doxorubicin or Ethidium Bromide) prevent TFAM

Gold nanomaterials for the selective capturing and SERS diagnosis of toxins in aqueous and biological fluids

DEFF Research Database (Denmark)

Hassanain, Waleed A.; Izake, Emad L.; Schmidt, Michael Stenbæk

2017-01-01

the extractor nanoparticles within 5min by manipulating the pH environment of the nanoparticles. The regenerated extractor nanoparticles maintained their capture efficiency and, therefore, were re-used to capture of MC-LR from successive samples. The released purified toxin was screened within 10min on gold......A highly sensitive nanosensing method for the combined selective capture and SERS detection of Microcystin-LR (MC-LR) in blood plasma has been developed. The new method utilizes gold coated magnetic nanoparticles that are functionalized with anti MC-LR antibody Fab' fragments for the selective...... capture of MC-LR from aqueous media and blood plasma. Using an oriented immobilization approach, the Fab' fragments are covalently attached to gold surface to form a monolayer with high capture efficiency towards the toxin. After the selective capture, the purified MC-LR molecules were released from...

Nonlinear optical response of a gold surface in the visible range: A study by two-color sum-frequency generation spectroscopy. I. Experimental determination.

Science.gov (United States)

Dalstein, L; Revel, A; Humbert, C; Busson, B

2018-04-07

We experimentally determine the effective nonlinear second-order susceptibility of gold over the visible spectral range. To reach that goal, we probe by vibrational two-color sum-frequency generation spectroscopy the methyl stretching region of a dodecanethiol self-assembled monolayer adsorbed on a gold film. The sum-frequency generation spectra show a remarkable shape reversal when the visible probe wavelength is tuned from 435 to 705 nm. After correcting from Fresnel effects, the methyl stretching vibrations serve as an internal reference, allowing to extract the dispersion of the absolute phase and relative amplitude of the effective nonlinear optical response of gold in the visible range.

Solution-processable septithiophene monolayer transistor

NARCIS (Netherlands)

Defaux, M.; Gholamrezaie, F.; Wang, J.; Kreyes, A.; Ziener, U.; Anokhin, D.V.; Ivanov, D.A.; Moser, A.; Neuhold, A.; Salzmann, I.; Resel, R.; Leeuw, de D.M.; Meskers, S.C.J.; Moeller, M.; Mourran, A.

2012-01-01

Septithiophene with endgroups designed to form liquid crystalline phases and allows controlled deposition of an electrically connected monolayer. Field effect mobilies mobilities of charge carriers and spectroscopic properties of the monolayer provide evidence of sustainable transport and

Solution-Processable Septithiophene Monolayer Transistor

NARCIS (Netherlands)

Defaux, Matthieu; Gholamrezaie, Fatemeh; Wang, Jingbo; Kreyes, Andreas; Ziener, Ulrich; Anokhin, Denis V.; Ivanov, Dimitri A.; Moser, Armin; Neuhold, Alfred; Salzmann, Ingo; Resel, Roland; de Leeuw, Dago M.; Meskers, Stefan C. J.; Moeller, Martin; Mourran, Ahmed

2012-01-01

Septithiophene with endgroups designed to form liquid crystalline phases and allows controlled deposition of an electrically connected monolayer. Field effect mobilies mobilities of charge carriers and spectroscopic properties of the monolayer provide evidence of sustainable transport and

Gold nanoparticles applications in natural polymer modified for UV protection

International Nuclear Information System (INIS)

Silva, Iris O. da; Ladchumananandasivam, Rasiah; Nascimento, Jose H. O. do; Silva, Francisco C. da; Sa, Christiane S. de A.

2015-01-01

The protein-based polymers such as milk, such as polylactic acid (PLA) and soya can be cited as examples of substrates used in various fields of engineering, mainly due to its character of biodegradability, generating low environmental impact when compared to chemical polymers to petroleum-based, which take years to decompose in nature. Among these, soy fiber has great application potential because it is a manufactured material base of a residue obtained from the existing folder in the soybean seeds after oil extraction, using resins and chemicals for structural modification. In this work, soy mesh was used to develop a material with ultraviolet protection properties, through the use of nanotechnology. Thus, to connect the gold nanoparticles (NPAu), the fabric had a surface charge modified with the use of chitosan, using 20% of the weight of the material, followed by nanomaterials exhaust process. The NPAu were synthesized via chemical synthesis with sodium nitrate as reducing and stabilizing agent. The analysis of the solution samples were evaluated by absorbance spectroscopy and solid materials through diffuse reflectance spectroscopy and XRD X-ray diffraction. The size of NPAu was evaluated in equipment Zetasizer nanoseries / nanoZ, finding nanoparticles with an average size of 34.59 nm, and also underlined plasmon resonance phenomenon, with peaks between 530 nm and red coloration, and good results from the soundness washes, compared to conventional dyeing. It was found that soy polymer treated with NPAu presented an excellent property with ultraviolet protection factor (UPF) of +50, considered excellent, proving its potential application in the biomedical field. (author)

Evaluation of monolayers and mixed monolayers formed from mercaptobenzothiazole and decanethiol as sensing platforms

Energy Technology Data Exchange (ETDEWEB)

Mary Vergheese, T.; Berchmans, Sheela

2004-02-15

In this investigation, the characterisation of monolayer and mixed monolayers formed from mercaptobenzothiazole (MBT) and decanethiol (DT) has been carried out with cyclic voltammetry. The SAMs have been tested for their stability and electron transfer blocking properties. The redox probes used in the present study are [Fe(China){sub 6}]{sup 4-}, [Ru(NH{sub 3}){sub 6}]{sup 2+} and Cu underpotential deposition (upd). The electron transfer kinetics is investigated in acid and neutral pH range. Electron transfer kinetics is altered by the nature of charge on the redox probe and the charge on the monolayer. Electron transfer kinetics of negatively charged redox probes like ferrocyanide ions is blocked when the surface pK{sub a}pH{sub medium} reversible features is observed for negatively charged probes. An exactly reverse effect is observed in the case of positively charged redox species like [Ru(NH{sub 3}){sub 6}]{sup 2+/3+}. Cu under potential deposition studies reflects the structural integrity and compactness of the SAM layer. The utility of these monolayers and mixed monolayer for selective sensing of dopamine is discussed based on their ability to discriminate between positively and negatively charged redox species at different pH.

Monolayers of a De Novo Designed 4-Alpha-Helix Bundle Carboprotein and Partial Structures on Au(111)-Surfaces

DEFF Research Database (Denmark)

Brask, Jesper; Wackerbarth, Hainer; Jensen, Knud Jørgen

2002-01-01

on a galactopyranoside derivative with a thiol anchor aglycon suitable for surface immobilization on gold. The galactopyranoside with thiol anchor and the thiol anchor alone were prepared for comparison. Voltammetry of the three molecules on Au(111) showed reductive desorption peaks caused by monolayer adsorption via...... thiolate-Au bonding. In situ STM of the thiol anchor disclosed an ordered adlayer with clear domains and molecular features. This holds promise, broadly for single-molecule voltammetry and the SPM and scanning tunnelling microscopy (STM) of natural and synthetic proteins....

Enhancing the Properties of Carbon and Gold Substrates by Surface Modification

Energy Technology Data Exchange (ETDEWEB)

Harnisch, Jennifer Anne [Iowa State Univ., Ames, IA (United States)

2001-01-01

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

Impedimetric Urea Biosensor Based on Modified Gold Electrode with Urease Immobilized on Glutathione Layer

Directory of Open Access Journals (Sweden)

Houcine BARHOUMI

2014-05-01

Full Text Available In this work, a glutathione (GSH modified gold microelectrode was used for the covalent immobilization of urease biomolecules via the glutaraldehyde-coupling agent. The self- assembled monolayers (SAMs onto the gold surface was investigated by using the electrochemical impedance spectroscopy measurements (EIS. Before urease grafting, a significant interaction was noticed between urea and the glutathione layer by forming hydrogen bonds. The H-NMR analysis was carried out to highlight the possibility of having a covalent link between urea and the GSH deposited layer. In addition, contact angle measurements were carried out to determine the hydrophobic/hydrophilic feature of the modified gold surface electrode. After urease immobilization a stable and high sensitive impedimetric urea biosensors was obtained with a sensitivity of 8.73´10- 8 W-1mM-1 for the low concentrations range and a sensitivity of 7.03´10-9 W-1mM-1 for the high concentrations range.

Structural properties of oligonucleotide monolayers on gold surfaces probed by fluorescence investigations.

Science.gov (United States)

Rant, Ulrich; Arinaga, Kenji; Fujita, Shozo; Yokoyama, Naoki; Abstreiter, Gerhard; Tornow, Marc

2004-11-09

We present optical investigations on the conformation of oligonucleotide layers on Au surfaces. Our studies concentrate on the effect of varying surface coverage densities on the structural properties of layers of 12- and 24mer single-stranded DNA, tethered to the Au surface at one end while being labeled with a fluorescent marker at the opposing end. The distance-dependent energy transfer from the marker dye to the metal surface, which causes quenching of the observed fluorescence, is used to provide information on the orientation of the DNA strands relative to the surface. Variations in the oligonucleotide coverage density, as determined from electrochemical quantification, over 2 orders of magnitude are achieved by employing different preparation conditions. The observed enhancement in fluorescence intensity with increasing DNA coverage can be related to a model involving mutual steric interactions of oligonucleotides on the surface, as well as fluorescence quenching theory. Finally, the applicability of the presented concepts for investigations of heterogeneous monolayers is demonstrated by means of studying the coadsorption of mercaptohexanol onto DNA-modified Au surfaces.

Nano-jewellery: C5Au12--a gold-plated diamond at molecular level.

Science.gov (United States)

Naumkin, F

2006-06-07

A mixed carbon-metal cluster is designed by combining the tetrahedral C(5) radical (with a central atom-the skeleton of the C(5)H(12) molecule) and the spherical Au(12) layer (the external atomic shell of the Au(13) cluster). The C(5)Au(12) cluster and its negative and positive ionic derivatives, C(5)Au(12)(+/-), are investigated ab initio (DFT) in terms of optimized structures and relative energies of a few spin-states, for the icosahedral-like and octahedral-like isomers. The cluster is predicted to be generally more stable in its octahedral shape (similar to C(5)H(12)) which prevails for the negative ion and may compete with the icosahedral shape for the neutral system and positive ion. Adiabatic ionization energies (AIE) and electron affinities (AEA) of C(5)Au(12), vertical electron-detachment (VDE) energies of C(5)Au(12)(-), and vertical ionization and electron-attachment energies (VIE, VEA) of C(5)Au(12) are calculated as well, and compared with those for the corresponding isomers of the Au(13) cluster. The AIE and VIE values are found to be close for the two systems, while the AEA and VDE values are significantly reduced for the radical-based species. A simple fragment-based model is proposed for the decomposition of the total interaction into carbon-gold and gold-gold components.

Assessing the plasmonics of gold nano-triangles with higher order laser modes

Directory of Open Access Journals (Sweden)

Laura E. Hennemann

2012-10-01

Full Text Available Regular arrays of metallic nano-triangles – so called Fischer patterns – are fabricated by nano-sphere lithography. We studied such gold nano-triangle arrays on silicon or glass substrates. A series of different samples was investigated with a parabolic mirror based confocal microscope where the sample is scanned through the laser focus. By employing higher order laser modes (azimuthally and radially polarised laser beams, we can excite the Fischer patterns using either a pure in-plane (x,y electric field or a strongly z-directional (optical axis of the optical microscope electric field. We collected and evaluated the emitted luminescence and thereby investigated the respectively excited plasmonic modes. These varied considerably: firstly with the light polarisation in the focus, secondly with the aspect ratio of the triangles and thirdly with the employed substrate. Moreover, we obtained strongly enhanced Raman spectra of an adenine (sub-monolayer on gold Fischer patterns on glass. We thus showed that gold Fischer patterns are promising surface-enhanced Raman scattering (SERS substrates.

Gold Dispersion and Activation on the Basal Plane of Single-Layer MoS2

KAUST Repository

Merida, Cindy S.; Le, Duy; Echeverrí a, Elena M.; Nguyen, Ariana E.; Rawal, Takat B; Naghibi Alvillar, Sahar; Kandyba, Viktor; Al-Mahboob, Abdullah; Losovyj, Yaroslav B.; Katsiev, Khabiboulakh; Valentin, Michael D.; Huang, Chun-Yu; Gomez, Michael J.; Lu, I-Hsi; Guan, Alison; Barinov, Alexei; Rahman, Talat S; Dowben, Peter A.; Bartels, Ludwig

2017-01-01

Gold islands are typically associated with high binding affinity to adsorbates and catalytic activity. Here we present the growth of such dispersed nanoscale gold islands on single layer MoS2, prepared on an inert SiO2/Si support by chemical vapor deposition (CVD). This study offers a combination of growth process development, optical characterization, photoelectron spectroscopy at sub-micron spatial resolution, and advanced density functional theory modeling for detailed insight into the electronic interaction between gold and single-layer MoS2. In particular, we find the gold density of states in Au/MoS2/SiO2/Si to be far less well-defined than Au islands on other 2-dimensional materials such as graphene, for which we also provide data. We attribute this effect to the presence of heterogeneous Au adatom/MoS2-support interactions within the nanometer-scale gold cluster. As a consequence, theory predicts that CO will exhibit adsorption energies in excess of 1 eV at the Au cluster edges, where the local density of states is dominated by Au 5dz2 symmetry.

Gold Dispersion and Activation on the Basal Plane of Single-Layer MoS2

KAUST Repository

Merida, Cindy S.

2017-12-09

Gold islands are typically associated with high binding affinity to adsorbates and catalytic activity. Here we present the growth of such dispersed nanoscale gold islands on single layer MoS2, prepared on an inert SiO2/Si support by chemical vapor deposition (CVD). This study offers a combination of growth process development, optical characterization, photoelectron spectroscopy at sub-micron spatial resolution, and advanced density functional theory modeling for detailed insight into the electronic interaction between gold and single-layer MoS2. In particular, we find the gold density of states in Au/MoS2/SiO2/Si to be far less well-defined than Au islands on other 2-dimensional materials such as graphene, for which we also provide data. We attribute this effect to the presence of heterogeneous Au adatom/MoS2-support interactions within the nanometer-scale gold cluster. As a consequence, theory predicts that CO will exhibit adsorption energies in excess of 1 eV at the Au cluster edges, where the local density of states is dominated by Au 5dz2 symmetry.

Monolayer-Enriched Production of Au-Decorated WS2 Nanosheets via Defect Engineering

Energy Technology Data Exchange (ETDEWEB)

Dunklin, Jeremy R [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Lafargue, Paul [Ruprecht-Karls University Heidelberg; Higgins, Thomas M. [Ruprecht-Karls University Heidelberg; Forcherio, Gregory T. [U.S. Army Research Laboratory; Benamara, Mourad [University of Arkansas; McEvoy, Niall [Trinity College Dublin; Roper, D. Keith [University of Arkansas; Coleman, Jonathan N. [Trinity College Dublin; Vaynzof, Yana [Ruprecht-Karls University Heidelberg; Backes, Claudia [Ruprecht-Karls University Heidelberg

2018-04-06

Layered transition metal dichalcogenides (TMDs) represent a diverse, emerging source of two-dimensional (2D) nanostructures with broad application in optoelectronics and energy. Chemical functionalization has evolved into a powerful tool to tailor properties of these 2D TMDs; however, functionalization strategies have been largely limited to the metallic 1T-polytype. The work herein illustrates that 2H-semiconducting liquid-exfoliated tungsten disulfide (WS2) undergoes a spontaneous redox reaction with gold (III) chloride (AuCl3). Au nanoparticles (NPs) predominantly nucleate at nanosheet edges with tuneable NP size and density. AuCl3 is preferentially reduced on multi-layer WS2 and resulting large Au aggregates are easily separated from the colloidal dispersion by simple centrifugation. This process may be exploited to enrich the dispersions in laterally large, monolayer nanosheets. It is proposed that thiol groups at edges and defects sides reduce the AuCl3 to Au0 and are in turn oxidized to disulfides. Optical emission, i.e. photoluminescence, of the monolayers remained pristine, while the electrocatalytic activity towards the hydrogen evolution reaction is significantly improved. Taken together, these improvements in functionalization, fabrication, and catalytic activity represent an important advance in the study of these emerging 2D nanostructures.

Click functionalization of phenyl-capped bithiophene on azide-terminated self-assembled monolayers

International Nuclear Information System (INIS)

Zheng, Yijun; Cui, Jiaxi; Ikeda, Taichi

2015-01-01

Graphical abstract: - Highlights: • Electrochemically-active self-assembled monolayers with phenyl-capped bithiophene were prepared. • Post-functionalization method based on click chemistry solved the solubility issue of phenyl-capped thiophene alkanethiol. • The capture and release of the counter anions during the redox reaction were detectable by E-QCM. - Abstract: We immobilized tetra(ethylene glycol)-substituted phenyl-capped bithiophene with alkyne terminals (Ph2TPh-alkyne) on azide-terminated self-assembled monolayers (N 3 -SAMs) by Cu-catalyzed azide-alkyne cycloaddition reaction. Ph2TPh-functionalized SAMs on a gold substrate showed reversible electrochemical response. The surface densities of the azide groups in N 3 -SAMs and Ph2TPh units in Ph2TPh-functionalized SAMs were estimated to be 7.3 ± 0.3 × 10 −10 mol cm −2 and 4.6 ± 0.3 × 10 −10 mol cm −2 , respectively, by quartz crystal microbalance (QCM). Most of Ph2TPh-alkynes are considered to be anchored on N 3 -SAMs via both terminal groups. Ph2TPh-functionalized SAMs exhibited reversible redox peaks in cyclic voltammetry (CV). In redox reaction, reversible capture and release of the counter anion could be monitored by electrochemical QCM (E-QCM).

Click functionalization of phenyl-capped bithiophene on azide-terminated self-assembled monolayers

Energy Technology Data Exchange (ETDEWEB)

Zheng, Yijun; Cui, Jiaxi [Max Planck Institute for Polymer Research (MPIP), Ackermannweg 10, Mainz 55128 (Germany); Ikeda, Taichi, E-mail: IKEDA.Taichi@nims.go.jp [Max Planck Institute for Polymer Research (MPIP), Ackermannweg 10, Mainz 55128 (Germany); Polymer Materials Unit, National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba 305-0044 (Japan)

2015-11-15

Graphical abstract: - Highlights: • Electrochemically-active self-assembled monolayers with phenyl-capped bithiophene were prepared. • Post-functionalization method based on click chemistry solved the solubility issue of phenyl-capped thiophene alkanethiol. • The capture and release of the counter anions during the redox reaction were detectable by E-QCM. - Abstract: We immobilized tetra(ethylene glycol)-substituted phenyl-capped bithiophene with alkyne terminals (Ph2TPh-alkyne) on azide-terminated self-assembled monolayers (N{sub 3}-SAMs) by Cu-catalyzed azide-alkyne cycloaddition reaction. Ph2TPh-functionalized SAMs on a gold substrate showed reversible electrochemical response. The surface densities of the azide groups in N{sub 3}-SAMs and Ph2TPh units in Ph2TPh-functionalized SAMs were estimated to be 7.3 ± 0.3 × 10{sup −10} mol cm{sup −2} and 4.6 ± 0.3 × 10{sup −10} mol cm{sup −2}, respectively, by quartz crystal microbalance (QCM). Most of Ph2TPh-alkynes are considered to be anchored on N{sub 3}-SAMs via both terminal groups. Ph2TPh-functionalized SAMs exhibited reversible redox peaks in cyclic voltammetry (CV). In redox reaction, reversible capture and release of the counter anion could be monitored by electrochemical QCM (E-QCM).

Self-Assembly of Protein Monolayers Engineered for Improved Monoclonal Immunoglobulin G Binding

Directory of Open Access Journals (Sweden)

Jeremy H. Lakey

2011-08-01

Full Text Available Bacterial outer membrane proteins, along with a filling lipid molecule can be modified to form stable self-assembled monolayers on gold. The transmembrane domain of Escherichia coli outer membrane protein A has been engineered to create a scaffold protein to which functional motifs can be fused. In earlier work we described the assembly and structure of an antibody-binding array where the Z domain of Staphylococcus aureus protein A was fused to the scaffold protein. Whilst the binding of rabbit polyclonal immunoglobulin G (IgG to the array is very strong, mouse monoclonal IgG dissociates from the array easily. This is a problem since many immunodiagnostic tests rely upon the use of mouse monoclonal antibodies. Here we describe a strategy to develop an antibody-binding array that will bind mouse monoclonal IgG with lowered dissociation from the array. A novel protein consisting of the scaffold protein fused to two pairs of Z domains separated by a long flexible linker was manufactured. Using surface plasmon resonance the self-assembly of the new protein on gold and the improved binding of mouse monoclonal IgG were demonstrated.

In Situ Scanning Tunneling Microscopy Topography Changes of Gold (111) in Aqueous Sulfuric Acid Produced by Electrochemical Surface Oxidation and Reduction and Relaxation Phenomena

Science.gov (United States)

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.

Janus Monolayer Transition-Metal Dichalcogenides.

Science.gov (United States)

Zhang, Jing; Jia, Shuai; Kholmanov, Iskandar; Dong, Liang; Er, Dequan; Chen, Weibing; Guo, Hua; Jin, Zehua; Shenoy, Vivek B; Shi, Li; Lou, Jun

2017-08-22

The crystal configuration of sandwiched S-Mo-Se structure (Janus SMoSe) at the monolayer limit has been synthesized and carefully characterized in this work. By controlled sulfurization of monolayer MoSe 2 , the top layer of selenium atoms is substituted by sulfur atoms, while the bottom selenium layer remains intact. The structure of this material is systematically investigated by Raman, photoluminescence, transmission electron microscopy, and X-ray photoelectron spectroscopy and confirmed by time-of-flight secondary ion mass spectrometry. Density functional theory (DFT) calculations are performed to better understand the Raman vibration modes and electronic structures of the Janus SMoSe monolayer, which are found to correlate well with corresponding experimental results. Finally, high basal plane hydrogen evolution reaction activity is discovered for the Janus monolayer, and DFT calculation implies that the activity originates from the synergistic effect of the intrinsic defects and structural strain inherent in the Janus structure.

Magnetic memory of a single-molecule quantum magnet wired to a gold surface.

Science.gov (United States)

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.

Ultrafast photocurrents in monolayer MoS2

Science.gov (United States)

Parzinger, Eric; Wurstbauer, Ursula; Holleitner, Alexander W.

Two-dimensional transition metal dichalcogenides such as MoS2 have emerged as interesting materials for optoelectronic devices. In particular, the ultrafast dynamics and lifetimes of photoexcited charge carriers have attracted great interest during the last years. We investigate the photocurrent response of monolayer MoS2 on a picosecond time scale utilizing a recently developed pump-probe spectroscopy technique based on coplanar striplines. We discuss the ultrafast dynamics within MoS2 including photo-thermoelectric currents and the impact of built-in fields due to Schottky barriers as well as the Fermi level pinning at the contact region. We acknowledge support by the ERC via Project 'NanoREAL', the DFG via excellence cluster 'Nanosystems Initiative Munich' (NIM), and through the TUM International Graduate School of Science and Engineering (IGSSE) and BaCaTeC.

Selective electronalysis of peracetic acid in the presence of a large excess of H2O2 at Au(1 1 1)-like gold electrode

International Nuclear Information System (INIS)

Awad, M.I.

2012-01-01

Highlights: ► Analysis of peracetic acid in the presence of a large excess of H 2 O 2 is introduced. ► Au(1 1 1)-like gold electrode serves as an ideal for this purpose. ► The analysis is characterized by high selectivity and sensitivity. - Abstract: Peracetic acid (PAA) has been selectively electroanalyzed in the presence of a large excess of hydrogen peroxide (H 2 O 2 ), about 500 fold that of PAA, using Au (1 1 1)-like gold electrode in acetate buffer solutions of pH 5.4. Au(1 1 1)-like gold electrode was prepared by a controlled reductive desorption of a previously assembled thiol, typically cysteine, monolayer onto the polycrystalline gold (poly-Au) electrode. Cysteine molecules were selectively removed from the Au(1 1 1) facets of the poly-Au electrode, keeping the other two facets (i.e., Au(1 1 0) and Au(1 0 0)) under the protection of the adsorbed cysteine. It has been found that Au(1 1 1)-like gold electrode positively shifts the reduction peak of PAA, while, fortunately, shifts the reduction peak of H 2 O 2 negatively, achieving a large potential separation (around 750 mV) between the two reduction peaks as compared with that (around 450 mV) obtained at the poly-Au electrode. This large potential separation between the two reduction peaks enabled the analysis of PAA in the presence of a large excess of H 2 O 2 . In addition, the positive shift of the reduction peak of PAA gives the present method a high immunity against the interference of the dissolved oxygen.

Unraveling the atomic structure of ultrafine iron clusters

KAUST Repository

Wang, Hongtao

2012-12-18

Unraveling the atomic structures of ultrafine iron clusters is critical to understanding their size-dependent catalytic effects and electronic properties. Here, we describe the stable close-packed structure of ultrafine Fe clusters for the first time, thanks to the superior properties of graphene, including the monolayer thickness, chemical inertness, mechanical strength, electrical and thermal conductivity. These clusters prefer to take regular planar shapes with morphology changes by local atomic shuffling, as suggested by the early hypothesis of solid-solid transformation. Our observations differ from observations from earlier experimental study and theoretical model, such as icosahedron, decahedron or cuboctahedron. No interaction was observed between Fe atoms or clusters and pristine graphene. However, preferential carving, as observed by other research groups, can be realized only when Fe clusters are embedded in graphene. The techniques introduced here will be of use in investigations of other clusters or even single atoms or molecules.

Preparation and Photoluminescence of Tungsten Disulfide Monolayer

Directory of Open Access Journals (Sweden)

Yanfei Lv

2018-05-01

Full Text Available Tungsten disulfide (WS2 monolayer is a direct band gap semiconductor. The growth of WS2 monolayer hinders the progress of its investigation. In this paper, we prepared the WS2 monolayer through chemical vapor transport deposition. This method makes it easier for the growth of WS2 monolayer through the heterogeneous nucleation-and-growth process. The crystal defects introduced by the heterogeneous nucleation could promote the photoluminescence (PL emission. We observed the strong photoluminescence emission in the WS2 monolayer, as well as thermal quenching, and the PL energy redshift as the temperature increases. We attribute the thermal quenching to the energy or charge transfer of the excitons. The redshift is related to the dipole moment of WS2.

Grafting of Oligo(ethylene glycol) Functionalized Calix[4]arene-tetra-diazonium Salts for Antifouling Germanium and Gold Surfaces.

Science.gov (United States)

Blond, Pascale; Mattiuzzi, Alice; Valkenier, Hennie; Troian-Gautier, Ludovic; Bergamini, Jean-François; Doneux, Thomas; Goormaghtigh, Erik; Raussens, Vincent; Jabin, Ivan

2018-05-03

Biosensors that can determine protein concentration and structure are highly desired for biomedical applications. For the development of such biosensors, the use of Fourier transformed infra-red (FTIR) spectroscopy with the attenuated internal total reflection (ATR) configuration is particularly attractive but it requires appropriate surface functionalization of the ATR optical element. Indeed, the surface has to specifically interact with a target protein in close contact with the optical element and must display antifouling properties to prevent nonspecific adsorption of other proteins. We here report robust monolayers of calix[4]arenes bearing oEGs chains, which were grafted on germanium and gold surfaces via their tetra-diazonium salts. The formation of monolayers of oEGylated calix[4]arenes was confirmed by AFM, IR and contact angle measurements. The antifouling properties of these modified surfaces were studied by ATR-FTIR spectroscopy and fluorescence microscopy and the non-specific absorption of BSA was found to be reduced by 85% compared to non-modified germanium. In other words, the organic coating by oEGylated calix[4]arenes provides remarkable antifouling properties, opening the way to the design of germanium- and gold-based biosensors.

Gd-functionalised Au nanoparticles as targeted contrast agents in MRI: relaxivity enhancement by polyelectrolyte coating.

Science.gov (United States)

Warsi, Muhammad Farooq; Adams, Ralph W; Duckett, Simon B; Chechik, Victor

2010-01-21

Monolayer-protected, Gd(3+)-functionalised gold nanoparticles with enhanced spin-lattice relaxivity (r(1)) were prepared; adsorption of polyelectrolytes on these materials further increased r(1) and ligand exchange with a biotin-derivatised disulfide led to a prototype avidin-targeted contrast agent.

Simulation of depositions of a Lennard-Jones cluster on a crystalline surface

International Nuclear Information System (INIS)

Saitoh, Kuniyasu; Hayakawa, Hisao

2009-01-01

Depositions of amorphous Lennard-Jones clusters on a crystalline surface are numerically investigated. From the results of the molecular dynamics simulation, we found that the deposited clusters exhibit a transition from multilayered adsorption to monolayered adsorption at a critical incident speed. Employing the energy conservation law, we can explain the behavior of the ratio of the number of atoms adsorbed on the substrate to the cluster size. The boundary shape of the deposited cluster depends strongly on the incident speed, and some unstable modes grow during the spread of the deposited cluster on the substrate. We also discuss the wettability between different Lennard-Jones atoms. (author)

Optical Observation of Plasnionic Nonlocal Effects in a 2D Superlattice of Ultrasmall Gold Nanoparticles

DEFF Research Database (Denmark)

Shen, Hao; Chen, Li; Ferrari, Lorenzo

2017-01-01

in single ultrasmall silver nanopartides have been experimentally observed in single-particle spectroscopy enabled by the unprecedented high spatial resolution of electron energy loss spectroscopy (EELS). However, the unambig-optical observation of such new effects in gold nanopartides has yet not been...... reported, due to the extremely weak scattering and the obscuring fingerprint of strong interband transitions. Here we present a nanosystem, a superlattice monolayer formed by sub-10 nm gold nanopartides. Plasmon resonances are spectrally well-separated from interband transitions, while exhibiting clearly...... distinguishable blue-shifts compared to predictions by the classical local-response model. Our far-field spectroscopy was performed by a standard optical transmission and reflection setup, and the results agreed excellently with the hydrodynamic nonlocal model, opening a simple and Widely accessible way...

Structure and shear response of lipid monolayers

International Nuclear Information System (INIS)

Dutta, P.; Ketterson, J.B.

1990-02-01

Organic monolayers and multilayers are both scientifically fascinating and technologically promising; they are, however, both complex systems and relatively inaccessible to experimental probes. In this Progress Report, we describe our X-ray diffraction studies, which have given us substantial new information about the structures and phase transitions in monolayers on the surface of water; our use of these monolayers as a unique probe of the dynamics of wetting and spreading; and our studies of monolayer mechanical properties using a simple but effective technique available to anyone using the Wilhelmy method to measure surface tension

Adsorption kinetics of WS2 quantum dots onto a polycrystalline gold surface.

Science.gov (United States)

Ozhukil Valappil, Manila; Roopesh, Mekkat; Alwarappan, Subbiah; Pillai, Vijayamohanan K

2018-04-18

In this work, we report the adsorption kinetics of electrochemically synthesized WS2 quantum dots (ca. 3 nm) onto a polycrystalline gold electrode. Langmuir adsorption isotherm approach was employed to explore the temperature and adsorbate concentration dependence of experimentally calculated equilibrium constant of adsorption (Keq) and free energy for adsorption (ΔGads). Subsequently, we extract other thermodynamic parameters such as adsorption rate constant (Kads), desorption rate constant (Kd), the enthalpy of adsorption (ΔHads) and the entropy of adsorption (ΔSads). Our findings indicate that ΔGads is temperature dependent and ca. -1.74 kcal mol-1, ΔHads = -10.697 kcal mol-1 and ΔSads = -30 cal/(mol.K). These investigations on the contribution of the enthalpic and entropic forces to the total free energy of this system underscore the role of entropic forces on the stability of the WS2 QDs monolayer and provide new thermodynamic insights into other TMDQDs monolayers as well.

Monolayer Superconductivity in WS2

NARCIS (Netherlands)

Zheliuk, Oleksandr; Lu, Jianming; Yang, Jie; Ye, Jianting

Superconductivity in monolayer tungsten disulfide (2H-WS2) is achieved by strong electrostatic electron doping of an electric double-layer transistor (EDLT). Single crystals of WS2 are grown by a scalable method - chemical vapor deposition (CVD) on standard Si/SiO2 substrate. The monolayers are