Absolute measurement of (198)Au activity in gold foil using plastic scintillators and a well-type NaI(Tl) detector.

PubMed

Kim, Yun Ho; Kim, Jungho; Lee, Jong-Man; Park, Hyeonseo

2016-03-01

A beta-gamma coincidence system has been developed for measuring (198)Au activity in gold foils. The system was validated by Monte Carlo simulations and by measuring the activity of a (60)Co point-source. To study effects such as self-shielding of beta particles in gold foils, (198)Au activity measurements and simulations were performed for various scintillators and foil sizes. The measured (198)Au activities were ~1% above the reference activity, which might be due to self-shielding of beta particles. The measured and simulated (198)Au activities agreed, suggesting feasibility of precise activity measurement. Copyright © 2015 Elsevier Ltd. All rights reserved.

Gold-plasmon enhanced photocatalytic performance of anatase titania nanotubes under visible-light irradiation

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

Yang, Bingyang; He, Dawei, E-mail: dwhe@bjtu.edu.cn; Wang, Wenshuo

2016-02-15

Highlights: • APTMS/(TNTs-Au) was synthesized using a deposition-precipitation process. • APTMS/(TNTs-Au) showed superior visible light activity for the degradation of methylene blue. • The electromagnetic field distribution at the interface between TNTs and Au NPs were estimated by the 3D finite-difference time domain simulation. • The working mechanism of the photocatalytic activity of APTMS/(TNTs-Au) was illustrated. - Abstract: [3-Aminopropyl]trimethoxysilane-modified titania nanotubes decorated with Au nanoparticles (APTMS/(TNTs-Au)) nanocomposites were synthesized using a deposition-precipitation process. The results showed that Au nanoparticles (NPs) in the metallic state were firmly adhered to the surface of the anatase TNTs. APTMS/(TNTs-Au) exhibited great photocatalytic activities whichmore » were evaluated from the degradation rate of methylene blue aqueous solution under visible light irradiation. 3D finite-difference time domain simulation was performed to estimate the electromagnetic field distribution at the interface between TNTs and Au NPs. The visible photocatalytic activity of APTMS/(TNTs-Au) was largely attributed to the surface plasmon absorption of metallic Au NPs, which generated and transferred hot electrons to the CB of TNTs. In addition, the hot electrons on the surface of TNTs also suppressed the radiative electron–hole recombination and consequently enhanced the photocatalytic activity.« less

A recyclable Au(I) catalyst for selective homocoupling of arylboronic acids: significant enhancement of nano-surface binding for stability and catalytic activity.

PubMed

Zhang, Xin; Zhao, Haitao; Wang, Jianhui

2010-08-01

Au nanoparticles stabilized by polystyrene-co-polymethacrylic acid microspheres (PS-co-PMAA) were prepared and characterized via X-ray diffraction (XRD), and transmission electron microscope (TEM). The Au nanoparticles supported on the microspheres showed highly selective catalytic activity for homo-coupling reactions of arylboronic acids in a system of aryl-halides and arylboronic acids. X-ray photoelectron spectroscopy (XPS) spectra of the catalyst shows large amounts of Au(I) complexes band to the surface of the Au nanoparticles, which contributes to the selective homocoupling of the arylboronic acids. More importantly, this supported Au complex is a highly recyclable catalyst. The supported Au catalyst can be recycled and reused at least 6 times for a phenylboronic acid reactant, whereas the parent complex shows very low catalytic activity for this compound. The high catalytic activity of this material is attributed to: (1) the high surface to volume ratio which leads to more active sites being exposed to reactants; (2) the strong surface binding of the Au nanoparticle to the Au(I) complexes, which enhances both the stability and the catalytic activity of these complexes.

AuRu/AC as an effective catalyst for hydrogenation reactions

DOE PAGES

Villa, Alberto; Chan-Thaw, Carine E.; Campisi, Sebastiano; ...

2015-03-23

AuRu bimetallic catalysts have been prepared by sequential deposition of Au on Ru or vice versa obtaining different nanostructures: when Ru has been deposited on Au, a Au core–Ru shell has been observed, whereas the deposition of Au on Ru leads to a bimetallic phase with Ru enrichment on the surface. In the latter case, the unexpected Ru enrichment could be attributed to the weak adhesion of Ru on the carbon support, thus allowing Ru particles to diffuse on Au particles. Both structures result very active in catalysing the liquid phase hydrogenolysis of glycerol and levulinic acid but the activity,more » the selectivity and the stability depend on the structure of the bimetallic nanoparticles. Ru@Au/AC core–shell structure mostly behaved as the monometallic Ru, whereas the presence of bimetallic AuRu phase in Au@Ru/AC provides a great beneficial effect on both activity and stability.« less

Layered double hydroxide supported gold nanoclusters by glutathione-capped Au nanoclusters precursor method for highly efficient aerobic oxidation of alcohols.

PubMed

Li, Lun; Dou, Liguang; Zhang, Hui

2014-04-07

M3Al-layered double hydroxide (LDH, M = Mg, Ni, Co) supported Au nanoclusters (AuNCs) catalysts have been prepared for the first time by using water-soluble glutathione-capped Au nanoclusters as precursor. Detailed characterizations show that the ultrafine Au nanoclusters (ca. 1.5 ± 0.6 nm) were well dispersed on the surface of LDH with a loading of Au below ∼0.23 wt% upon synergetic interaction between AuNCs and M3Al-LDH. AuNCs/Mg3Al-LDH-0.23 exhibits much higher catalytic performance for the oxidation of 1-phenylethanol in toluene than Au/Mg3Al-LDH(DP) by the conventional deposition precipitation method and can be applied for a wide range of alcohols without basic additives. This catalyst can also be reused without loss of activity or selectivity. The AuNCs/M(= Ni, Co)3Al-LDH catalysts present even higher alcohol oxidation activity than AuNCs/Mg3Al-LDH. Particularly, AuNCs/Ni3Al-LDH-0.22 exhibits the highest activity (46 500 h(-1)) for the aerobic oxidation of 1-phenylethanol under solvent-free conditions attributed to its strongest Au-support synergy. The excellent activity and stability of AuNCs/M3Al-LDH catalysts render these materials promising candidates for green base-free selective oxidation of alcohols by molecular oxygen.

Active control of methanol carbonylation selectivity over Au/carbon anode by electrochemical potential.

PubMed

Funakawa, Akiyasu; Yamanaka, Ichiro; Otsuka, Kiyoshi

2005-05-12

Electrochemical oxidative carbonylation of methanol was studied over Au supported carbon anode in CO. The major carbonylation products were dimethyl oxalate (DMO) and dimethyl carbonate (DMC). The minor oxidation products were dimethoxy methane (DMM) and methyl formate (MF) from methanol and CO(2). Influences of various reaction conditions were studied on carbonylation activities and selectivities. The selectivities to DMO and DMC can be controlled by the electrochemical potential. Electrocatalysis of Au/carbon anode was studied by cyclic voltammetry (CV), stoichiometric reactions among Au(3+), methanol, and CO, and UV-vis spectra. The Au/carbon anode was characterized by XRD, SEM, and BE images before and after the carbonylation. These experimental facts strongly suggest that transition of oxidation states of Au affects changing of the carbonylation selectivities to DMO and DMC. Au(0) is the active species for the selective DMO formation by direct electrochemical carbonylation at low potentials (<+1.2 V (Ag/AgCl)). On the other hand, Au(3+) is the active spices for the selective DMC formation by indirect electrochemical carbonylation through Au(3+)/Au(+) redox at high potentials (>+1.3 V).

Enhanced catalyst activity by decorating of Au on Ag@Cu2O nanoshell

NASA Astrophysics Data System (ADS)

Chen, Lei; Liu, Maomao; Zhao, Yue; Kou, Qiangwei; Wang, Yaxin; Liu, Yang; Zhang, Yongjun; Yang, Jinghai; Jung, Young Mee

2018-03-01

We successfully synthesized Au-decorated Ag@Cu2O heterostructures via a simple galvanic replacement method. As the Au precursor concentration increased, the density of the Au nanoparticles (NPs) on the Ag@Cu2O surface increased, which changed the catalytic activity of the Ag@Cu2O-Au structure. The combination of Au, Ag, and Cu2O exhibited excellent catalytic properties, which can further effect on the catalyst activity of the Ag@Cu2O-Au structure. In addition, the proposed Ag@Cu2O-Au nanocomposite was used to transform the organic, toxic pollutant, 4-nitrophenol (4-NP), into its nontoxic and medicinally important amino derivative via a catalytic reduction to optimize the material performance. The proposed Au-decorated Ag@Cu2O exhibited excellent catalytic activity, and the catalytic reduction time greatly decreased (5 min). Thus, three novel properties of Ag@Cu2O-Au, i.e., charge redistribution and transfer, adsorption, and catalytic reduction of organic pollutants, were ascertained for water remediation. The proposed catalytic properties have potential applications for photocatalysis and localized surface plasmon resonance (LSPR)- and peroxidase-like catalysis.

Facile preparation of SERS and catalytically active Au nanostructures using furfuryl derivatives

NASA Astrophysics Data System (ADS)

Kim, Ki-Jung; Kim, Hyun-Chul; Park, Minsun; Huh, Seong

2017-08-01

Six different types of Au nanostructures with rough surfaces were readily prepared through the redox reactions between Au precursor, AuCl4-, and furfuryl derivatives without extra metal surface capping ligands, in deionized water at room temperature. Furfuryl alcohol (FA) or furfurylamine (FFA) was used as a sole reducing agent for the reduction of Au precursor. Both FA and FFA effectively polymerized during the redox reactions to form polyfuran polymers. These polymers are thought to act as surface capping ligands during the formation of Au nanostructures. Experiments were conducted with three different concentrations of each furfuryl derivative. Interestingly, Au particles prepared from the reaction with varying concentration of FA or FFA showed large differences in size, and revealed that the higher the ratios of [FA]/[AuCl4-] or [FFA]/[AuCl4-], the smaller the size of Au particles. The size of Au particles was in the range of 1 μm to under 30 nm. Among these samples, two nanostructured Au particles, AuFA-4 and AuFFA-1, deposited on a Si wafer by a simple drop-casting method, were revealed as highly active surface-enhanced Raman scattering (SERS) substrates for the detection of methylene blue (MB) and crystal violet (CV). High SERS enhancement factors (EFs) of 106 ∼ 108 for MB and CV were observed. Small size Au nanoparticles (AuFFA-2 and AuFFA-4) were also found to be very active for the catalytic hydrogenation of 4-nitrophenol to 4-aminophenol in the presence of NaBH4 at room temperature. AuFFA-2 could be recycled eight times, without losing its activity.

Influence of Au and TiO2 structures on hydrogen dissociation over TiO2/Au(100)

NASA Astrophysics Data System (ADS)

Nakamura, I.; Mantoku, H.; Furukawa, T.; Takahashi, A.; Fujitani, T.

2012-11-01

We performed H2-D2 exchange reactions over TiOx/Au(100) and compared the observed reaction kinetics with those reported for TiOx/Au(111) in order to clarify the influence of the Au and TiO2 structures on dissociation of H2 molecules. Low energy electron diffraction observations showed that the TiO2 produced on Au(100) was disordered, in contrast to the comparatively ordered TiO2 structure formed on Au(111). The activation energies and the turnover frequencies for HD formation over TiO2/Au(100) agreed well with those for TiO2/Au(111), clearly indicating that the hydrogen dissociation sites created over TiO2/Au(100) were the perimeter interface between stoichiometric TiO2 and Au, as was previously concluded for TiO2/Au(111). We concluded that the creation of active sites for hydrogen dissociation was independent of the Au and TiO2 structures consisting perimeter interface, and that local bonds that formed between Au and O atoms of stoichiometric TiO2 were essential for the creation of active sites.

The effect of copper and silver on the properties of Au-ZnO catalyst and its activity in glycerol oxidation

NASA Astrophysics Data System (ADS)

Kaskow, Iveta; Decyk, Piotr; Sobczak, Izabela

2018-06-01

The goal of this work was to use ZnO as a support for gold and copper (Au-Cu system) or gold and silver (Au-Ag system) and comparison of the effect of copper and silver on the properties of gold and its activity in glycerol oxidation with oxygen in the liquid phase. The samples prepared were fully characterized by XRD, TEM techniques and UV-vis, XPS, ESR spectroscopic methods. It was found that the introduction of copper and silver changed the electronic state of gold loaded on ZnO by the electron transfer between metals. Three different metallic gold species were identified in calcined catalysts: (Au°)δ- (Au-ZnO), (Au°)η- (AuCu-ZnO) and (Au°)γ- (AuAg-ZnO), where δ-,η-,γ- indicate a different partial negative charge on metallic gold and γ > δ > η. The results showed that (Au°)η- centers (metallic gold with the lowest negative charge) formed on AuCu-ZnO were the most active in glycerol oxidation. The increase in the negative charge on metallic gold loaded on AuAg-ZnO reduced the gold activity in silver containing sample. The glyceric acid adsorption and desorption rate influenced the selectivity of the catalysts.

Gallic acid conjugated with gold nanoparticles: antibacterial activity and mechanism of action on foodborne pathogens

PubMed Central

Rattanata, Narintorn; Klaynongsruang, Sompong; Leelayuwat, Chanvit; Limpaiboon, Temduang; Lulitanond, Aroonlug; Boonsiri, Patcharee; Chio-Srichan, Sirinart; Soontaranon, Siriwat; Rugmai, Supagorn; Daduang, Jureerut

2016-01-01

Foodborne pathogens, including Plesiomonas shigelloides and Shigella flexneri B, are the major cause of diarrheal endemics worldwide. Antibiotic drug resistance is increasing. Therefore, bioactive compounds with antibacterial activity, such as gallic acid (GA), are needed. Gold nanoparticles (AuNPs) are used as drug delivery agents. This study aimed to conjugate and characterize AuNP–GA and to evaluate the antibacterial activity. AuNP was conjugated with GA, and the core–shell structures were characterized by small-angle X-ray scattering and transmission electron microscopy. Antibacterial activity of AuNP–GA against P. shigelloides and S. flexneri B was evaluated by well diffusion method. AuNP–GA bactericidal mechanism was elucidated by Fourier transform infrared microspectroscopic analysis. The results of small-angle X-ray scattering showed that AuNP–GA conjugation was successful. Antibacterial activity of GA against both bacteria was improved by conjugation with AuNP because the minimum inhibitory concentration value of AuNP–GA was significantly decreased (P<0.0001) compared to that of GA. Fourier transform infrared analysis revealed that AuNP–GA resulted in alterations of lipids, proteins, and nucleic acids at the bacterial cell membrane. Our findings show that AuNP–GA has potential for further application in biomedical sciences. PMID:27555764

Gallic acid conjugated with gold nanoparticles: antibacterial activity and mechanism of action on foodborne pathogens.

PubMed

Rattanata, Narintorn; Klaynongsruang, Sompong; Leelayuwat, Chanvit; Limpaiboon, Temduang; Lulitanond, Aroonlug; Boonsiri, Patcharee; Chio-Srichan, Sirinart; Soontaranon, Siriwat; Rugmai, Supagorn; Daduang, Jureerut

2016-01-01

Foodborne pathogens, including Plesiomonas shigelloides and Shigella flexneri B, are the major cause of diarrheal endemics worldwide. Antibiotic drug resistance is increasing. Therefore, bioactive compounds with antibacterial activity, such as gallic acid (GA), are needed. Gold nanoparticles (AuNPs) are used as drug delivery agents. This study aimed to conjugate and characterize AuNP-GA and to evaluate the antibacterial activity. AuNP was conjugated with GA, and the core-shell structures were characterized by small-angle X-ray scattering and transmission electron microscopy. Antibacterial activity of AuNP-GA against P. shigelloides and S. flexneri B was evaluated by well diffusion method. AuNP-GA bactericidal mechanism was elucidated by Fourier transform infrared microspectroscopic analysis. The results of small-angle X-ray scattering showed that AuNP-GA conjugation was successful. Antibacterial activity of GA against both bacteria was improved by conjugation with AuNP because the minimum inhibitory concentration value of AuNP-GA was significantly decreased (P<0.0001) compared to that of GA. Fourier transform infrared analysis revealed that AuNP-GA resulted in alterations of lipids, proteins, and nucleic acids at the bacterial cell membrane. Our findings show that AuNP-GA has potential for further application in biomedical sciences.

One step electrochemical synthesis of bimetallic PdAu supported on nafion–graphene ribbon film for ethanol electrooxidation

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

Shendage, Suresh S., E-mail: sureshsshendage@gmail.com; Singh, Abilash S.; Nagarkar, Jayashree M., E-mail: jm.nagarkar@ictmumbai.edu.in

2015-10-15

Highlights: • Electrochemical deposition of bimetallic PdAu NPs. • Highly loaded PdAu NPs are obtained. • Nafion–graphene supported PdAu NPs shows good activity for ethanol electrooxidation. - Abstract: A nafion–graphene ribbon (Nf–GR) supported bimetallic PdAu nanoparticles (PdAu/Nf–GR) catalyst was prepared by electrochemical codeposition of Pd and Au at constant potential. The prepared catalyst was characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), transmission electron microscopy (TEM) and X-ray diffraction analysis (XRD). The average particle size of PdAu nanoparticles (NPs) determined from XRD was 3.5 nm. The electrocatalytic activity of the PdAu/Nf–GR catalyst was examined by cyclic voltametry.more » It was observed that the as prepared catalyst showed efficient activity and good stability for ethanol electrooxidation in alkaline medium.« less

Enhanced activity of Au-Fe/C anodic electrocatalyst for direct borohydride-hydrogen peroxide fuel cell

NASA Astrophysics Data System (ADS)

Yi, Lanhua; Wei, Wei; Zhao, Caixian; Tian, Li; Liu, Jing; Wang, Xianyou

2015-07-01

Carbon supported Au-Fe bimetallic nanocatalysts (Au-Fe/C) are facilely prepared via a modified NaBH4 reduction method in aqueous solution at room temperature, and used as the anode electrocatalyst of direct borohydride-hydrogen peroxide fuel cell (DBHFC). The physical and electrochemical properties of the Au-Fe/C electrocatalysts are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), cyclic voltammetry (CV), rotating disc electrode (RDE) voltammetry, chronoamperometry (CA), chronopotentiometry (CP), and fuel cell test. The results show that Au-Fe/C catalysts display higher catalytic activity for the direct electrooxidation of BH4- than carbon supported pure Au nanocatalyst (Au/C), especially Au50Fe50/C catalyst presents the highest catalytic activity among all as-prepared catalysts. Besides, the single DBHFC with Au50Fe50/C anode and Au/C cathode obtains the maximum power density as high as 34.9 mW cm-2 at 25 °C.

Catalytic activity of various pepsin reduced Au nanostructures towards reduction of nitroarenes and resazurin

NASA Astrophysics Data System (ADS)

Sharma, Bhagwati; Mandani, Sonam; Sarma, Tridib K.

2015-01-01

Pepsin, a digestive protease enzyme, could function as a reducing as well as stabilizing agent for the synthesis of Au nanostructures of various size and shape under different reaction conditions. The simple tuning of the pH of the reaction medium led to the formation of spherical Au nanoparticles, anisotropic Au nanostructures such as triangles, hexagons, etc., as well as ultra small fluorescent Au nanoclusters. The activity of the enzyme was significantly inhibited after its participation in the formation of Au nanoparticles due to conformational changes in the native structure of the enzyme which was studied by fluorescence, circular dichroism (CD), and infra red spectroscopy. However, the Au nanoparticle-enzyme composites served as excellent catalyst for the reduction of p-nitrophenol and resazurin, with the catalytic activity varying with size and shape of the nanoparticles. The presence of pepsin as the surface stabilizer played a crucial role in the activity of the Au nanoparticles as reduction catalysts, as the approach of the reacting molecules to the nanoparticle surface was actively controlled by the stabilizing enzyme.

Experimental and Computational Evidence of Highly Active Fe Impurity Sites on the Surface of Oxidized Au for the Electrocatalytic Oxidation of Water in Basic Media

DOE PAGES

Klaus, Shannon; Trotochaud, Lena; Cheng, Mu-Jeng; ...

2015-10-22

Addition of Fe to Ni- and Co-based (oxy)hydroxides has been shown to enhance the activity of these materials for electrochemical oxygen evolution. Here we show that Fe cations bound to the surface of oxidized Au exhibit enhanced oxygen evolution reaction (OER) activity. We find that the OER activity increases with increasing surface concentration of Fe. Density functional theory analysis of the OER energetics reveals that oxygen evolution over Fe cations bound to a hydroxyl-terminated oxidized Au (Fe-Au 2O 3) occurs at an overpotential ~0.3V lower than over hydroxylated Au 2O 3 (0.82V). This finding agrees well with experimental observations andmore » is a consequence of the more optimal binding energetics of OER reaction intermediates at Fe cations bound to the surface of Au 2O 3. These findings suggest that the enhanced OER activity reported recently upon low-potential cycling of Au may be due to surface Fe impurities rather than to "superactive" Au(III) surfaquo species.« less

Design and Preparation of Supported Au Catalyst with Enhanced Catalytic Activities by Rationally Positioning Au Nanoparticles on Anatase.

PubMed

Wang, Liang; Wang, Hong; Rice, Andrew E; Zhang, Wei; Li, Xiaokun; Chen, Mingshu; Meng, Xiangju; Lewis, James P; Xiao, Feng-Shou

2015-06-18

A synergistic effect between individual components is crucial for increasing the activity of metal/metal oxide catalysts. The greatest challenge is how to control the synergistic effect to obtain enhanced catalytic performance. Through density functional theory calculations of model Au/TiO2 catalysts, it is suggested that there is strong interaction between Au nanoparticles and Ti species at the edge/corner sites of anatase, which is favorable for the formation of stable oxygen vacancies. Motivated by this theoretical analysis, we have rationally prepared Au nanoparticles attached to edge/corner sites of anatase support (Au/TiO2-EC), confirmed by their HR-TEM images. As expected, this strong interaction is well characterized by Raman, UV-visible, and XPS techniques. Very interestingly, compared with conventional Au catalysts, Au/TiO2-EC exhibits superior catalytic activity in the oxidations using O2. Our approach to controlling Au nanoparticle positioning on anatase to obtain enhanced catalytic activity offers an efficient strategy for developing more novel supported metal catalysts.

Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters

NASA Astrophysics Data System (ADS)

Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

2016-08-01

Understanding of the “structure-activity” relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au3+ ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size.

Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters

PubMed Central

Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

2016-01-01

Understanding of the “structure-activity” relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au3+ ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size. PMID:27476577

Evolution of catalytic activity of Au-Ag bimetallic nanoparticles on mesoporous support for CO oxidation.

PubMed

Wang, Ai-Qin; Chang, Chun-Ming; Mou, Chung-Yuan

2005-10-13

We report a novel Au-Ag alloy catalyst supported on mesoporous aluminosilicate Au-Ag@MCM prepared by a one-pot synthesis procedure, which is very active for low-temperature CO oxidation. The activity was highly dependent on the hydrogen pretreatment conditions. Reduction at 550-650 degrees C led to high activity at room temperature, whereas as-synthesized or calcined samples did not show any activity at the same temperature. Using various characterization techniques, such as XRD, UV-vis, XPS, and EXAFS, we elucidated the structure and surface composition change during calcination and the reduction process. The XRD patterns show that particle size increased only during the calcination process on those Ag-containing samples. XPS and EXAFS data demonstrate that calcination led to complete phase segregation of the Au-Ag alloy and the catalyst surface is greatly enriched with AgBr after the calcination process. However, subsequent reduction treatment removed Br- completely and the Au-Ag alloy was formed again. The surface composition of the reduced Au-Ag@MCM (nominal Au/Ag = 3/1) was more enriched with Ag, with the surface Au/Ag ratio being 0.75. ESR spectra show that superoxides are formed on the surface of the catalyst and its intensity change correlates well with the trend of catalytic activity. A DFT calculation shows that CO and O2 coadsorption on neighboring sites on the Au-Ag alloy was stronger than that on either Au or Ag. The strong synergism in the coadsorption of CO and O2 on the Au-Ag nanoparticle can thus explain the observed synergetic effect in catalysis.

Diphosphine-Protected Au 22 Nanoclusters on Oxide Supports Are Active for Gas-Phase Catalysis without Ligand Removal

DOE PAGES

Wu, Zili; Hu, Guoxiang; Jiang, De-en; ...

2016-09-29

Investigation of monodispersed and atomically-precise Au nanoclusters provides a route to understand the roles of coordination, size, and ligand effects in Au catalysis. We have explored the catalytic behavior of a newly-synthesized Au 22(L 8) 6 nanocluster (L = 1,8-bis(diphenylphosphino) octane) with in situ uncoordinated Au sites supported on TiO 2, CeO 2 and Al 2O 3. Stability of the supported Au 22 nanoclusters was probed structurally by EXAFS and HAADF-STEM, and their adsorption and reactivity for CO oxidation were investigated by IR absorption spectroscopy and temperature programed flow reaction. Low temperature CO oxidation activity was observed for the supportedmore » pristine Au 22(L 8) 6 nanoclusters without ligand removal. Isotopically labeled O 2 was used to demonstrate that the reaction pathway occurs through a redox mechanism, consistent with the observed support-dependent activity trend: CeO 2 > TiO 2 > Al 2O 3. Substantiated by density functional theory (DFT) calculations, we conclude that the uncoordinated Au sites in the intact Au 22(L 8) 6 nanoclusters are capable of adsorbing CO, activating O2 and promoting CO oxidation reaction. Thanks to the presence of the in situ coordination unsaturated Au atoms, this work is the first clear demonstration of a ligand-protected Au nanocluster that are active for gas phase catalysis without the need of ligand removal.« less

Improvement of mimetic peroxidase activity of gold nanoclusters on the luminol chemiluminescence reaction by surface modification with ethanediamine.

PubMed

Han, Lu; Li, Ying; Fan, Aiping

2018-06-01

Peroxidase is a commonly used catalyst in luminol-H 2 O 2 chemiluminescence (CL) reactions. Natural peroxidase has a sophisticated separation process, short shelf life and unstable activity, therefore it is important to develop peroxidases that have both high catalytic activity and good stability as alternatives to the natural enzyme. Gold nanoclusters (Au NCs) are an alternative peroxidase with catalytic activity in the luminol-H 2 O 2 CL reaction. In the present study, ethanediamine was modified on the surface of Au NCs forming cationic Au NCs. The zeta potential of the cationic Au NCs maintained its positive charge when the pH of the solution was between 4 and 9. The cationic Au NCs showed higher catalytic activity in the luminol-H 2 O 2 CL reaction than did unmodified Au NCs. A mechanism study showed that the better performance of cationic Au NCs may be attributed to the generation of 1 O 2 on the surface of cationic Au NCs and a positive surface charge, for better affinity to luminol. Cationic Au NC, acting as a peroxidase mimic, has much better stability than horseradish peroxidase over a wide range of temperatures. We believe that cationic Au NCs may be useful as an artificial peroxidase for a wide range of potential applications in CL and bioanalysis. Copyright © 2018 John Wiley & Sons, Ltd.

Preparation and catalytic activities for H{sub 2}O{sub 2} decomposition of Rh/Au bimetallic nanoparticles

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

Zhang, Haijun, E-mail: zhanghaijun@wust.edu.cn; The State Key Laboratory of Refractory and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081; Deng, Xiangong

2016-07-15

Graphical abstract: PVP-protected Rh/Au bimetallic nanoparticles (BNPs) were prepared by using hydrogen sacrificial reduction method, the activity of Rh80Au20 BNPs were about 3.6 times higher than that of Rh NPs. - Highlights: • Rh/Au bimetallic nanoparticles (BNPs) of 3∼5 nm in diameter were prepared. • Activity for H{sub 2}O{sub 2} decomposition of BNPs is 3.6 times higher than that of Rh NPs. • The high activity of BNPs was caused by the existence of charged Rh atoms. • The apparent activation energy for H{sub 2}O{sub 2} decomposition over the BNPs was calculated. - Abstract: PVP-protected Rh/Au bimetallic nanoparticles (BNPs) weremore » prepared by using hydrogen sacrificial reduction method and characterized by UV–vis, XRD, FT-IR, XPS, TEM, HR-TEM and DF-STEM, the effects of composition on their particle sizes and catalytic activities for H{sub 2}O{sub 2} decomposition were also studied. The as-prepared Rh/Au BNPs possessed a high catalytic activity for the H{sub 2}O{sub 2} decomposition, and the activity of the Rh{sub 80}Au{sub 20} BNPs with average size of 2.7 nm were about 3.6 times higher than that of Rh monometallic nanoparticles (MNPs) even the Rh MNPs possess a smaller particle size of 1.7 nm. In contrast, Au MNPs with size of 2.7 nm show no any activity. Density functional theory (DFT) calculation as well as XPS results showed that charged Rh and Au atoms formed via electronic charge transfer effects could be responsible for the high catalytic activity of the BNPs.« less

Photocatalytic properties of Au-deposited mesoporous SiO{sub 2}–TiO{sub 2} photocatalyst under simultaneous irradiation of UV and visible light

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

Okuno, T., E-mail: t093507@edu.imc.tut.ac.jp; Kawamura, G., E-mail: gokawamura@ee.tut.ac.jp; Muto, H., E-mail: muto@ee.tut.ac.jp

Mesoporous SiO{sub 2} templates deposited TiO{sub 2} nanocrystals are synthesized via a sol–gel route, and Au nanoparticles (NPs) are deposited in the tubular mesopores of the templates by a photodeposition method (Au/SiO{sub 2}–TiO{sub 2}). The photocatalytic characteristics of Au/SiO{sub 2}–TiO{sub 2} are discussed with the action spectra of photoreactions of 2-propanol and methylene blue. Photocatalytic activities of SiO{sub 2}–TiO{sub 2} under individual ultraviolet (UV) and visible (Vis) light illumination are enhanced by deposition of Au NPs. Furthermore, Au/SiO{sub 2}–TiO{sub 2} shows higher photocatalytic activities under simultaneous irradiation of UV and Vis light compared to the activity under individual UV andmore » Vis light irradiation. Since the photocatalytic activity under simultaneous irradiation is almost the same as the total activities under individual UV and Vis light irradiation, it is concluded that the electrons and the holes generated by lights of different wavelengths are efficiently used for photocatalysis without carrier recombination. - Graphical abstract: This graphic shows the possible charge behavior in Au/SiO{sub 2}–TiO{sub 2} under independent light irradiation of ultraviolet and visible light irradiation. Both reactions under independent UV and Vis light irradiation occurred in parallel when Au/SiO{sub 2}–TiO{sub 2} photocatalyst was illuminated UV and Vis light simultaneously, and then photocatalytic activity is improved by simultaneous irradiation. - Highlights: • Au nanoparticles were deposited in mesoporous SiO{sub 2}–TiO{sub 2} by a photodeposition method. • Photocatalytic activity under UV and Vis light was enhanced by deposition of Au. • Photocatalytic activity of Au/SiO{sub 2}–TiO{sub 2} was improved by simultaneous irradiation.« less

Au-CeO2 Janus-like nanoparticles fabricated by block copolymer templates and their catalytic activity in the degradation of methyl orange

NASA Astrophysics Data System (ADS)

Yu, Huan; Jiao, Yapei; Li, Na; Pang, Juanjuan; Li, Wenting; Zhang, Xiaokai; Li, Xue; Li, Chunsheng

2018-01-01

A simple approach towards the fabrication of Au-CeO2 Janus-like nanoparticles is presented. Composite micelles of polystyrene-block-poly (ethylene oxide) (PS-b-PEO)/Ce(NO3)3/HAuCl4 with HAuCl4 and Ce(NO3)3 precursors incorporated in the PEO domains are prepared first. By manipulating the pH value of the composite micelles solution, a redox reaction between Au(III) with Ce(III) in the PEO domains occurs and Au-CeO2 Janus-like nanoparticles composed of a porous CeO2 and an Au nanoparticle are generated. X-ray diffraction (XRD), UV-vis spectrum (UV), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) measurements are employed to characterize the Janus-like nanoparticles. The catalytic degradation of methyl orange dye (MO) under ultrasonic irradiation is chosen as the test reaction to examine the catalytic activity of the Au-CeO2 Janus-like nanoparticles. It is found that Au-CeO2 Janus-like nanoparticles show higher activity than that of CeO2 nanoparticles or Au-CeO2 composite nanoparticles. The increased catalytic activity of Au-CeO2 Janus-like nanoparticles is attributed to the exposed Au core on one side of the Janus nanoparticles and the Au-CeO2 heterointerfaces.

Plasmonic enhancement of visible-light water splitting with Au-TiO2 composite aerogels

NASA Astrophysics Data System (ADS)

Desario, Paul A.; Pietron, Jeremy J.; Devantier, Devyn E.; Brintlinger, Todd H.; Stroud, Rhonda M.; Rolison, Debra R.

2013-08-01

We demonstrate plasmonic enhancement of visible-light-driven splitting of water at three-dimensionally (3D) networked gold-titania (Au-TiO2) aerogels. The sol-gel-derived ultraporous composite nanoarchitecture, which contains 1 to 8.5 wt% Au nanoparticles and titania in the anatase form, retains the high surface area and mesoporosity of unmodified TiO2 aerogels and maintains stable dispersion of the ~5 nm Au guests. A broad surface plasmon resonance (SPR) feature centered at ~550 nm is present for the Au-TiO2 aerogels, but not Au-free TiO2 aerogels, and spans a wide range of the visible spectrum. Gold-derived SPR in Au-TiO2 aerogels cast as films on transparent electrodes drives photoelectrochemical oxidation of aqueous hydroxide and extends the photocatalytic activity of TiO2 from the ultraviolet region to visible wavelengths exceeding 700 nm. Films of Au-TiO2 aerogels in which Au nanoparticles are deposited on pre-formed TiO2 aerogels by a deposition-precipitation method (DP Au/TiO2) also photoelectrochemically oxidize aqueous hydroxide, but less efficiently than 3D Au-TiO2, despite having an essentially identical Au nanoparticle weight fraction and size distribution. For example, 3D Au-TiO2 containing 1 wt% Au is as active as DP Au/TiO2 with 4 wt% Au. The higher photocatalytic activity of 3D Au-TiO2 derives only in part from its ability to retain the surface area and porosity of unmodified TiO2 aerogel. The magnitude of improvement indicates that in the 3D arrangement either a more accessible photoelectrochemical reaction interphase (three-phase boundary) exists or more efficient conversion of excited surface plasmons into charge carriers occurs, thereby amplifying reactivity over DP Au/TiO2. The difference in photocatalytic efficiency between the two forms of Au-TiO2 demonstrates the importance of defining the structure of Au||TiO2 interfaces within catalytic Au-TiO2 nanoarchitectures.We demonstrate plasmonic enhancement of visible-light-driven splitting of water at three-dimensionally (3D) networked gold-titania (Au-TiO2) aerogels. The sol-gel-derived ultraporous composite nanoarchitecture, which contains 1 to 8.5 wt% Au nanoparticles and titania in the anatase form, retains the high surface area and mesoporosity of unmodified TiO2 aerogels and maintains stable dispersion of the ~5 nm Au guests. A broad surface plasmon resonance (SPR) feature centered at ~550 nm is present for the Au-TiO2 aerogels, but not Au-free TiO2 aerogels, and spans a wide range of the visible spectrum. Gold-derived SPR in Au-TiO2 aerogels cast as films on transparent electrodes drives photoelectrochemical oxidation of aqueous hydroxide and extends the photocatalytic activity of TiO2 from the ultraviolet region to visible wavelengths exceeding 700 nm. Films of Au-TiO2 aerogels in which Au nanoparticles are deposited on pre-formed TiO2 aerogels by a deposition-precipitation method (DP Au/TiO2) also photoelectrochemically oxidize aqueous hydroxide, but less efficiently than 3D Au-TiO2, despite having an essentially identical Au nanoparticle weight fraction and size distribution. For example, 3D Au-TiO2 containing 1 wt% Au is as active as DP Au/TiO2 with 4 wt% Au. The higher photocatalytic activity of 3D Au-TiO2 derives only in part from its ability to retain the surface area and porosity of unmodified TiO2 aerogel. The magnitude of improvement indicates that in the 3D arrangement either a more accessible photoelectrochemical reaction interphase (three-phase boundary) exists or more efficient conversion of excited surface plasmons into charge carriers occurs, thereby amplifying reactivity over DP Au/TiO2. The difference in photocatalytic efficiency between the two forms of Au-TiO2 demonstrates the importance of defining the structure of Au||TiO2 interfaces within catalytic Au-TiO2 nanoarchitectures. Electronic supplementary information (ESI) available: Nitrogen physisorption isotherms; Au4f X-ray photoelectron spectra; TEM-derived distributions of Au size and aspect ratio; relative IPCE enhancement ratio. See DOI: 10.1039/c3nr01429k

Oxygen reduction reaction activity and structural stability of Pt-Au nanoparticles prepared by arc-plasma deposition.

PubMed

Takahashi, Shuntaro; Chiba, Hiroshi; Kato, Takashi; Endo, Shota; Hayashi, Takehiro; Todoroki, Naoto; Wadayama, Toshimasa

2015-07-28

The oxygen reduction reaction (ORR) activity and durability of various Au(x)/Pt100 nanoparticles (where x is the atomic ratio of Au against Pt) are evaluated herein. The samples were fabricated on a highly-oriented pyrolytic graphite substrate at 773 K through sequential arc-plasma depositions of Pt and Au. The electrochemical hydrogen adsorption charges (electrochemical surface area), particularly the characteristic currents caused by the corner and edge sites of the Pt nanoparticles, decrease with increasing Au atomic ratio (x). In contrast, the specific ORR activities of the Au(x)/Pt100 samples were dependent on the atomic ratios of Pt and Au: the Au28/Pt100 sample showed the highest specific activity among all the investigated samples (x = 0-42). As for ORR durability evaluated by applying potential cycles between 0.6 and 1.0 V in oxygen-saturated 0.1 M HClO4, Au28/Pt100 was the most durable sample against the electrochemical potential cycles. The results clearly showed that the Au atoms located at coordinatively-unsaturated sites, e.g. at the corners or edges of the Pt nanoparticles, can improve the ORR durability by suppressing unsaturated-site-induced degradation of the Pt nanoparticles.

AGARD/SMP Review Damage Tolerance for Engine Structures. 4. Reliability and Quality Assurance (Revue AGARD/SMP Tolerance Aux Dommages pour les Composants de Moteurs. 4 Fiabilite et Assurance Qualite)

DTIC Science & Technology

1991-12-01

lequel e110 as fonde n’est en pratique gubre virifi6 par 1’exp~rtence industriolle. Augmenter Is variabilit6 d’un procd diminue rarement lea cofits do...analyses pour sanctionnor los non- -conformitdo. augmentation des retouches et rebuts, Is tout gdndrant une digradation Importante des cycles ot...is a priori dangerous since the principle which It is based on Is scarcely verified in the industrial reality . The increase of the variability of a

Ethanol electrooxidation in alkaline medium on electrochemically synthesized Co(OH)2/Au composite

NASA Astrophysics Data System (ADS)

Babu, Sreejith P.; Elumalai, Perumal

2017-01-01

Gold (Au), cobalt hydroxide (Co(OH)2) and different Co(OH)2/Au compositions were electro-deposited onto stainless steel by a potentiodynamic method from the respective metal-ion solutions. The deposits were characterized by x-ray diffraction (XRD), scanning electron microscope (SEM) and Fourier transformed infra-red spectroscopy (FT-IR). The XRD and IR data confirmed that the deposits were Au, α-Co(OH)2 or Co(OH)2/Au composites. The SEM observations confirmed that the morphology of the Au was spherical, while the α-Co(OH)2 was flakey with pores. The morphology of the Co(OH)2/Au composites consisted of highly agglomerated Au grains distributed on the Co(OH)2 matrix. The electrocatalytic activity of each of the Au, Co(OH)2 and Co(OH)2/Au-composite electrodes towards ethanol electrooxidation in an alkaline medium was investigated by cyclic voltammetry and chronoamperometry. It turned out that the Co(OH)2/Au-composite electrodes exhibited superior catalytic activity for ethanol electrooxidation compared with the pristine Au or Co(OH)2 electrodes. A peak current density as high as 25 mA cm-2 was exhibited by the Co(OH)2/ Au composite while the Au and Co(OH)2 showed only 0.9 and 13 mA cm-2, respectively. The enhanced conductivity of the Co(OH)2/Au matrix due to the presence of Au, as well as the combined catalytic activity, seemed to be responsible for the superior performance of the Co(OH)2/Au-composite electrodes.

Oxygen reduction kinetics on Pt monolayer shell highly affected by the structure of bimetallic AuNi cores

DOE PAGES

Chen, Guangyu; Kuttiyiel, Kurian A.; Su, Dong; ...

2016-07-12

Here, we describe pronounced effects of structural changes of the AuNi cores on the oxygen reduction reaction (ORR) activity of a Pt monolayer shell. The study of alloyed AuNi nanoparticles compared with AuNi core–shell structured nanoparticles revealed configurations having different electronic and electrochemical properties. Controlled alloying of Au with Ni was essential to tune the electronic properties of Au interacting with the Pt monolayer shell to achieve suitable adsorption of O 2 on Pt for expediting the ORR. The alloyed AuNi nanoparticles made the Pt shell more catalytically active for the ORR than the core–shell structured AuNi nanoparticles. The Ptmore » monolayer supported on the alloyed AuNi nanoparticles showed the Pt mass and specific activities as high as 1.52 A mg –1 and 1.18 mA cm –2, respectively, with almost no loss over 5 000 cycles of stability test. This high ORR activity is ascribed to the role of nonspecific steric configuration of Ni atoms changing the electronic properties of the alloy that affect the oxygen and water interaction with the Pt shell and facilitate increased ORR kinetics.« less

Enzyme activity of α-chymotrypsin: Deactivation by gold nano-cluster and reactivation by glutathione.

PubMed

Ghosh, Catherine; Mondal, Tridib; Bhattacharyya, Kankan

2017-05-15

Effect of gold nanoclusters (Au-NCs) on the circular dichroism (CD) spectra and enzymatic activity of α-chymotrypsin (ChT) (towards hydrolysis of a substrate, N-succinyl-l-phenylalanine p-nitroanilide) are studied. The CD spectra indicate that on binding to Au-NC, ChT is completely unfolded, resulting in nearly zero ellipticity. α-chymotrypsin (ChT) coated gold nano-clusters exhibit almost no enzymatic activity. Addition of glutathione (GSH) or oxidized glutathione (GSSG) restore the enzyme activity of α-chymotrypsin by 30-45%. ChT coated Au-NC exhibits two emission maxima-one at 480nm (corresponding to Au 10 ) and one at 640nm (Au 25 ). On addition of glutathione (GSH) or oxidized glutathione (GSSG) the emission peak at 640nm vanishes and only one peak at 480nm (Au 10 ) remains. MALDI mass spectrometry studies suggest addition of glutathione (GSH) to α-chymotrypsin capped Au-NCs results in the formation of glutathione-capped Au-NCs and α-chymotrypsin is released from Au-NCs. CD spectroscopy indicates that the conformation of the released α-chymotrypsin is different from that of the native α-chymotrypsin. Copyright © 2017 Elsevier Inc. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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 presence of an interferent, ascorbic acid. Electronic supplementary information (ESI) available: TEM image of GS-Au25, SWV of GS-Au25 in solution, effect of scan rate on the CV of GS-Au25ME, CVs of DA and AA at the bare GCE and CVs of GS-Au25ME at different pHs. See DOI: 10.1039/c2nr30481c

Controlled deposition of palladium nanodendrites on the tips of gold nanorods and their enhanced catalytic activity.

PubMed

Su, Gaoxing; Jiang, Huaqiao; Zhu, Hongyan; Lv, Jing-Jing; Yang, Guohai; Yan, Bing; Zhu, Jun-Jie

2017-08-31

Plasmonic Au-Pd nanostructures have drawn significant attention for use in heterogeneous catalysis. In this study, palladium nanodendrite-tipped gold nanorods (PdND-T-AuNRs) were subjected to a facile fabrication under mild reaction conditions. The palladium amounts on the two tips were tunable. In the preparation of PdND-T-AuNRs, dense capped AuNRs, a low reaction temperature, and suitable stabilizing agents were identified as critical reaction parameters for controlling palladium nanodendrites deposited on both ends of AuNRs. After overgrowth with palladium nanodendrites, the longitudinal surface plasmonic resonance peaks of PdND-T-AuNRs were red-shifted from 810 nm to 980 nm. The electrocatalytic activity of PdND-T-AuNRs for ethanol oxidation was examined, which was a bit weaker than that of cuboid core-shell Au-Pd nanodendrites; however, PdND-T-AuNRs were more stable in ethanol electrooxidation. Moreover, the photocatalytic activity of PdND-T-AuNRs for Suzuki cross-coupling reactions was investigated. At room temperature, nearly 100% yield was obtained under laser irradiation. The results can further enhance our capability of fine-tuning the optical, electronic, and catalytic properties of the bimetallic Au-Pd nanostructures.

Ultraviolet light and laser irradiation enhances the antibacterial activity of glucosamine-functionalized gold nanoparticles

PubMed Central

Govindaraju, Saravanan; Ramasamy, Mohankandhasamy; Baskaran, Rengarajan; Ahn, Sang Jung; Yun, Kyusik

2015-01-01

Here we report a novel method for the synthesis of glucosamine-functionalized gold nanoparticles (GlcN-AuNPs) using biocompatible and biodegradable glucosamine for antibacterial activity. GlcN-AuNPs were prepared using different concentrations of glucosamine. The synthesized AuNPs were characterized for surface plasmon resonance, surface morphology, fluorescence spectroscopy, and antibacterial activity. The minimum inhibitory concentrations (MICs) of the AuNPs, GlcN-AuNPs, and GlcN-AuNPs when irradiated by ultraviolet light and laser were investigated and compared with the MIC of standard kanamycin using Escherichia coli by the microdilution method. Laser-irradiated GlcN-AuNPs exhibited significant bactericidal activity against E. coli. Flow cytometry and fluorescence microscopic analysis supported the cell death mechanism in the presence of GlcN-AuNP-treated bacteria. Further, morphological changes in E. coli after laser treatment were investigated using atomic force microscopy and transmission electron microscopy. The overall results of this study suggest that the prepared nanoparticles have potential as a potent antibacterial agent for the treatment of a wide range of disease-causing bacteria. PMID:26345521

UV and visible light photocatalytic activity of Au/TiO2 nanoforests with Anatase/Rutile phase junctions and controlled Au locations.

PubMed

Yu, Yang; Wen, Wei; Qian, Xin-Yue; Liu, Jia-Bin; Wu, Jin-Ming

2017-01-24

To magnify anatase/rutile phase junction effects through appropriate Au decorations, a facile solution-based approach was developed to synthesize Au/TiO 2 nanoforests with controlled Au locations. The nanoforests cons®isted of anatase nanowires surrounded by radially grown rutile branches, on which Au nanoparticles were deposited with preferred locations controlled by simply altering the order of the fabrication step. The Au-decoration increased the photocatalytic activity under the illumination of either UV or visible light, because of the beneficial effects of either electron trapping or localized surface plasmon resonance (LSPR). Gold nanoparticles located preferably at the interface of anatase/rutile led to a further enhanced photocatalytic activity. The appropriate distributions of Au nanoparticles magnify the beneficial effects arising from the anatase/rutile phase junctions when illuminated by UV light. Under the visible light illumination, the LSPR effect followed by the consecutive electron transfer explains the enhanced photocatalysis. This study provides a facile route to control locations of gold nanoparticles in one-dimensional nanostructured arrays of multiple-phases semiconductors for achieving a further increased photocatalytic activity.

Alternative catalysts for low-temperature CO-oxidation

NASA Technical Reports Server (NTRS)

Gardner, Steven D.; Hoflund, Gar B.; Schryer, David R.; Schryer, Jacqueline; Upchurch, Billy T.; Brown, David R.

1990-01-01

MnO sub x, Ag/MnO sub x, Cu/MnO sub x, Pt/MnO sub x, Ru/MnO sub x, Au/CeO sub x, and Au/Fe2O3 were synthesized and tested for CO oxidation activity in low concentrations of stoichiometric CO and O2 at 30 to 75 C. Catalytic activity was measured for periods as long as 18000 minutes. At 75 deg Au/MnO sub x is most active sustaining nearly 100 percent CO conversion for 10000 minutes. It also retains high activity at 50 and 30 C with negligible decay in activity. A direct comparison between an unpretreated 10 percent Au/MnO sub x catalyst and an optimized 19.5 percent Pt/SnO sub 2 (pretreated) catalyst shows that the Au/MnO sub x catalyst exhibits much higher catalytic activity and far superior decay characteristics. Other catalysts including Au/CeO sub x and Au/Fe2O3 also perform well. The Cu/MnO sub x exhibits a high initial activity which decays rapidly. After the decay period the activity remains very stable making Cu/MnO sub x a potential candidate for long-term applications such as CO2 lasers in space.

The surface plasmon-induced hot carrier effect on the catalytic activity of CO oxidation on a Cu2O/hexoctahedral Au inverse catalyst.

PubMed

Lee, Si Woo; Hong, Jong Wook; Lee, Hyunhwa; Wi, Dae Han; Kim, Sun Mi; Han, Sang Woo; Park, Jeong Young

2018-06-14

The intrinsic correlation between an enhancement of catalytic activity and the flow of hot electrons generated at metal-oxide interfaces suggests an intriguing way to control catalytic reactions and is a significant subject in heterogeneous catalysis. Here, we show surface plasmon-induced catalytic enhancement by the peculiar nanocatalyst design of hexoctahedral (HOH) Au nanocrystals (NCs) with Cu2O clusters. We found that this inverse catalyst comprising a reactive oxide for the catalytic portion and a metal as the source of electrons by localized surface plasmon resonance (localized SPR) exhibits a change in catalytic activity by direct hot electron transfer or plasmon-induced resonance energy transfer (PIRET) when exposed to light. We prepared two types of inverse catalysts, Cu2O at the vertex sites of HOH Au NCs (Cu2O/Au vertex site) and a HOH Au NC-Cu2O core-shell structure (HOH Au@Cu2O), to test the structural effect on surface plasmons. Under broadband light illumination, the Cu2O/Au vertex site catalyst showed 30-90% higher catalytic activity and the HOH Au@Cu2O catalyst showed 10-30% higher catalytic activity than when in the dark. Embedding thin SiO2 layers between the HOH Au NCs and the Cu2O verified that the dominant mechanism for the catalytic enhancement is direct hot electron transfer from the HOH Au to the Cu2O. Finite-difference time domain calculations show that a much stronger electric field was formed on the vertex sites after growing the Cu2O on the HOH Au NCs. These results imply that the catalytic activity is enhanced when hot electrons, created from photon absorption on the HOH Au metal and amplified by the presence of surface plasmons, are transferred to the reactive Cu2O.

Non-specific adsorption of complement proteins affects complement activation pathways of gold nanomaterials.

PubMed

Quach, Quang Huy; Kah, James Chen Yong

2017-04-01

The complement system is a key humoral component of innate immunity, serving as the first line of defense against intruders, including foreign synthetic nanomaterials. Although gold nanomaterials (AuNMs) are widely used in nanomedicine, their immunological response is not well understood. Using AuNMs of three shapes commonly used in biomedical applications: spherical gold nanoparticles, gold nanostars and gold nanorods, we demonstrated that AuNMs activated whole complement system, leading to the formation of SC5b-9 complex. All three complement pathways were simultaneously activated by all the AuNMs. Recognition molecules of the complement system interacted with all AuNMs in vitro, except for l-ficolin, but the correlation between these interactions and corresponding complement pathway activation was only observed in the classical and alternative pathways. We also observed the mediating role of complement activation in cellular uptake of all AuNMs by human U937 promonocytic cells, which expresses complement receptors. Taken together, our results highlighted the potential immunological challenges for clinical applications of AuNMs that were often overlooked.

N-Heterocyclic molecule-capped gold nanoparticles as effective antibiotics against multi-drug resistant bacteria

NASA Astrophysics Data System (ADS)

Feng, Yan; Chen, Wenwen; Jia, Yuexiao; Tian, Yue; Zhao, Yuyun; Long, Fei; Rui, Yukui; Jiang, Xingyu

2016-07-01

We demonstrate that N-heterocyclic molecule-capped gold nanoparticles (Au NPs) have broad-spectrum antibacterial activity. Optimized antibacterial activity can be achieved by using different initial molar ratios (1 : 1 and 10 : 1) of N-heterocyclic prodrugs and the precursor of Au NPs (HAuCl4). This work opens up new avenues for antibiotics based on Au NPs.We demonstrate that N-heterocyclic molecule-capped gold nanoparticles (Au NPs) have broad-spectrum antibacterial activity. Optimized antibacterial activity can be achieved by using different initial molar ratios (1 : 1 and 10 : 1) of N-heterocyclic prodrugs and the precursor of Au NPs (HAuCl4). This work opens up new avenues for antibiotics based on Au NPs. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr03317b

Toward hybrid Au nanorods @ M (Au, Ag, Pd and Pt) core-shell heterostructures for ultrasensitive SERS probes

NASA Astrophysics Data System (ADS)

Xie, Xiaobin; Gao, Guanhui; Kang, Shendong; Lei, Yanhua; Pan, Zhengyin; Shibayama, Tamaki; Cai, Lintao

2017-06-01

Being able to precisely control the morphologies of noble metallic nanostructures is of essential significance for promoting the surface-enhanced Raman scattering (SERS) effect. Herein, we demonstrate an overgrowth strategy for synthesizing Au @ M (M = Au, Ag, Pd, Pt) core-shell heterogeneous nanocrystals with an orientated structural evolution and highly improved properties by using Au nanorods as seeds. With the same reaction condition system applied, we obtain four well-designed heterostructures with diverse shapes, including Au concave nanocuboids (Au CNs), Au @ Ag crystalizing face central cube nanopeanuts, Au @ Pd porous nanocuboids and Au @ Pt nanotrepangs. Subsequently, the exact overgrowth mechanism of the above heterostructural building blocks is further analysed via the systematic optimiziation of a series of fabrications. Remarkably, the well-defined Au CNs and Au @ Ag nanopeanuts both exhibit highly promoted SERS activity. We expect to be able to supply a facile strategy for the fabrication of multimetallic heterogeneous nanostructures, exploring the high SERS effect and catalytic activities.

Cytotoxicity of Ultrasmall Gold Nanoparticles on Planktonic and Biofilm Encapsulated Gram-Positive Staphylococci.

PubMed

Boda, Sunil Kumar; Broda, Janine; Schiefer, Frank; Weber-Heynemann, Josefine; Hoss, Mareike; Simon, Ulrich; Basu, Bikramjit; Jahnen-Dechent, Willi

2015-07-01

The emergence of multidrug resistant bacteria, especially biofilm-associated Staphylococci, urgently requires novel antimicrobial agents. The antibacterial activity of ultrasmall gold nanoparticles (AuNPs) is tested against two gram positive: S. aureus and S. epidermidis and two gram negative: Escherichia coli and Pseudomonas aeruginosa strains. Ultrasmall AuNPs with core diameters of 0.8 and 1.4 nm and a triphenylphosphine-monosulfonate shell (Au0.8MS and Au1.4MS) both have minimum inhibitory concentration (MIC) and minimum bactericidal concentration of 25 × 10(-6) m [Au]. Disc agar diffusion test demonstrates greater bactericidal activity of the Au0.8MS nanoparticles over Au1.4MS. In contrast, thiol-stabilized AuNPs with a diameter of 1.9 nm (AuroVist) cause no significant toxicity in any of the bacterial strains. Ultrasmall AuNPs cause a near 5 log bacterial growth reduction in the first 5 h of exposure, and incomplete recovery after 21 h. Bacteria show marked membrane blebbing and lysis in biofilm-associated bacteria treated with ultrasmall AuNP. Importantly, a twofold MIC dosage of Au0.8MS and Au1.4MS each cause around 80%-90% reduction in the viability of Staphylococci enveloped in biofilms. Altogether, this study demonstrates potential therapeutic activity of ultrasmall AuNPs as an effective treatment option against staphylococcal infections. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen.

PubMed

Baker, Thomas A; Liu, Xiaoying; Friend, Cynthia M

2011-01-07

Recently, gold has been intensely studied as a catalyst for key synthetic reactions. Gold is an attractive catalyst because, surprisingly, it is highly active and very selective for partial oxidation processes suggesting promise for energy-efficient "green" chemistry. The underlying origin of the high activity of Au is a controversial subject since metallic gold is commonly thought to be inert. Herein, we establish that one origin of the high activity for gold catalysis is the extremely reactive nature of atomic oxygen bound in 3-fold coordination sites on metallic gold. This is the predominant form of O at low concentrations on the surface, which is a strong indication that it is most relevant to catalytic conditions. Atomic oxygen bound to metallic Au in 3-fold sites has high activity for CO oxidation, oxidation of olefins, and oxidative transformations of alcohols and amines. Among the factors identified as important in Au-O interaction are the morphology of the surface, the local binding site of oxygen, and the degree of order of the oxygen overlayer. In this Perspective, we present an overview of both theory and experiments that identify the reactive forms of O and their associated charge density distributions and bond strengths. We also analyze and model the release of Au atoms induced by O binding to the surface. This rough surface also has the potential for O(2) dissociation, which is a critical step if Au is to be activated catalytically. We further show the strong parallels between product distributions and reactivity for O-covered Au at low pressure (ultrahigh vacuum) and for nanoporous Au catalysts operating at atmospheric pressure as evidence that atomic O is the active species under working catalytic conditions when metallic Au is present. We briefly discuss the possible contributions of oxidants that may contain intact O-O bonds and of the Au-metal oxide support interface in Au catalysis. Finally, the challenges and future directions for fully understanding the activity of gold are considered.

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

Wu, Zili; Hu, Guoxiang; Jiang, De-en

Investigation of monodispersed and atomically-precise Au nanoclusters provides a route to understand the roles of coordination, size, and ligand effects in Au catalysis. We have explored the catalytic behavior of a newly-synthesized Au 22(L 8) 6 nanocluster (L = 1,8-bis(diphenylphosphino) octane) with in situ uncoordinated Au sites supported on TiO 2, CeO 2 and Al 2O 3. Stability of the supported Au 22 nanoclusters was probed structurally by EXAFS and HAADF-STEM, and their adsorption and reactivity for CO oxidation were investigated by IR absorption spectroscopy and temperature programed flow reaction. Low temperature CO oxidation activity was observed for the supportedmore » pristine Au 22(L 8) 6 nanoclusters without ligand removal. Isotopically labeled O 2 was used to demonstrate that the reaction pathway occurs through a redox mechanism, consistent with the observed support-dependent activity trend: CeO 2 > TiO 2 > Al 2O 3. Substantiated by density functional theory (DFT) calculations, we conclude that the uncoordinated Au sites in the intact Au 22(L 8) 6 nanoclusters are capable of adsorbing CO, activating O2 and promoting CO oxidation reaction. Thanks to the presence of the in situ coordination unsaturated Au atoms, this work is the first clear demonstration of a ligand-protected Au nanocluster that are active for gas phase catalysis without the need of ligand removal.« less

The Xanthomonas euvesicatoria type III effector XopAU is an active protein kinase that manipulates plant MAP kinase signaling.

PubMed

Teper, Doron; Girija, Anil Madhusoodana; Bosis, Eran; Popov, Georgy; Savidor, Alon; Sessa, Guido

2018-01-01

The Gram-negative bacterium Xanthomonas euvesicatoria (Xe) is the causal agent of bacterial spot disease of pepper and tomato. Xe delivers effector proteins into host cells through the type III secretion system to promote disease. Here, we show that the Xe effector XopAU, which is conserved in numerous Xanthomonas species, is a catalytically active protein kinase and contributes to the development of disease symptoms in pepper plants. Agrobacterium-mediated expression of XopAU in host and non-host plants activated typical defense responses, including MAP kinase phosphorylation, accumulation of pathogenesis-related (PR) proteins and elicitation of cell death, that were dependent on the kinase activity of the effector. XopAU-mediated cell death was not dependent on early signaling components of effector-triggered immunity and was also observed when the effector was delivered into pepper leaves by Xanthomonas campestris pv. campestris, but not by Xe. Protein-protein interaction studies in yeast and in planta revealed that XopAU physically interacts with components of plant immunity-associated MAP kinase cascades. Remarkably, XopAU directly phosphorylated MKK2 in vitro and enhanced its phosphorylation at multiple sites in planta. Consistent with the notion that MKK2 is a target of XopAU, silencing of the MKK2 homolog or overexpression of the catalytically inactive mutant MKK2K99R in N. benthamiana plants reduced XopAU-mediated cell death and MAPK phosphorylation. Furthermore, yeast co-expressing XopAU and MKK2 displayed reduced growth and this phenotype was dependent on the kinase activity of both proteins. Together, our results support the conclusion that XopAU contributes to Xe disease symptoms in pepper plants and manipulates host MAPK signaling through phosphorylation and activation of MKK2.

Rationalization of Au concentration and distribution in AuNi@Pt core-shell nanoparticles for oxygen reduction reaction

DOE PAGES

An, Wei; Liu, Ping

2015-09-18

Improving the activity and stability of Pt-based core–shell nanocatalysts for proton exchange membrane fuel cells while lowering Pt loading has been one of the big challenges in electrocatalysis. Here, using density functional theory, we report the effect of adding Au as the third element to enhance the durability and activity of Ni@Pt core–shell nanoparticles (NPs) during the oxygen reduction reaction (ORR). Our results show that the durability and activity of a Ni@Pt NP can be finely tuned by controlling Au concentration and distribution. For a NiAu@Pt NP, the durability can be greatly promoted by thermodynamically favorable segregation of Au tomore » replace the Pt atoms at vertex, edge, and (100) facets on the shell, while still keeping the ORR activity on the active Pt(111) shell as high as that of Ni@Pt nanoparticles. Such behavior strongly depends on a direct interaction with the Ni interlayer. The results not only highlight the importance of interplay between surface strain on the shell and the interlayer–shell interaction in determining the durability and activity but also provide guidance on how to maximize the usage of Au to optimize the performance of core–shell (Pt) nanoparticles. As a result, such understanding has allowed us to discover a novel NiAu@Pt nanocatalyst for the ORR.« less

Comparative study of spasmolytic properties, antioxidant activity and phenolic content of Arbutus unedo from Montenegro and Greece.

PubMed

Pavlović, Dragana R; Branković, Suzana; Kovačević, Nada; Kitić, Dušanka; Veljković, Slavimir

2011-05-01

Arbutus unedo leaf is used traditionally for gastrointestinal complaints. Ethanol extracts from Arbutus unedo collected in both Montenegro (AuM) and Greece (AuG) were found to decrease the ileal basal tonus, with AuG producing a significantly higher (p < 0.05) reduction in contractile response to acetylcholine. AuM and AuG relaxed 80 mM K(+) induced contractions and shifted the Ca(++) concentration-response curves to the right, similar to that caused by verapamil, suggesting that the spasmolytic effect was induced through calcium channel inhibition. The antioxidant activity of AuM and AuG and the phenolic content of the extracts and dry plant material were studied, and both extracts were found to possess considerable antioxidant properties. AuG showed a stronger in vitro antioxidative activity in the DPPH assay and in the TBA test. Polyphenol, tannin and flavonoid levels were higher in AuG, supporting the more potent spasmolytic and antioxidative effects, whereas the arbutin content was higher in dry plant material collected in Montenegro. Copyright © 2011 John Wiley & Sons, Ltd.

Fluorescence and room temperature activity of Y₂O₃:(Eu³⁺,Au³⁺)/palygorskite nanocomposite.

PubMed

He, Xi; Yang, Huaming

2015-01-28

The fluorescence and room temperature activity of a palygorskite supported Y2O3:(Eu(3+),Au(3+)) nanocomposite were investigated to design a fluorescence-indicated catalyst. The effects of Au(3+) doping on the structure and surface properties of the host material were systematically characterized. The fluorescence intensity of Y2O3:Eu(3+) was affected by Au(3+) doping, which was related to the crystallinity of Y2O3. Excess Au(3+) ions were segregated to the host surface and reduced to metallic Au. The local symmetry of Eu(3+) was reduced by Au(3+) doping, which benefited the energy transfer between Eu(3+) and Au(3+). Energy absorbed by Eu(3+) was transferred from Au(3+) to metallic Au, where electrons were produced. These electrons were absorbed by O2 to change into O2(-), which acted as the oxidant for ortho-dichlorobenzene (o-DCB). The variation of fluorescence intensity during the catalytic reaction was observed. The room temperature catalytic activity of the nanocomposite under UV irradiation was revealed. The as-synthesized nanocomposite might have potential applications in environmental fields.

Controllable synthesis of Au@SnO2 core-shell nanohybrids with enhanced photocatalytic activities

NASA Astrophysics Data System (ADS)

Zhang, Shaofeng; Hao, Jinggang; Ren, Feng; Wu, Wei; Xiao, Xiangheng

2017-05-01

Combination of semiconductors with plasmonic nanostructures is an effective route to promote the solar light harvesting as well as the efficiency of photocatalysis. In the present work, the Au@SnO2 hybrid nanostructures with Au nanorods as the cores and highly crystallized SnO2 nanoparticles as the shells were fabricated by a facile hydrothermal method. A critical factor, which influences the coating state of the SnO2 shells over Au NRs, was found to be the concentration of CTAB agent in the system and the corresponding mechanism was also proposed. The photocatalytic activities of the Au@SnO2 nanohybrids were examined by degradation of rhodamine B (RhB) dyes at room temperature. The Au@SnO2 nanohybrids exhibited much higher catalytic activities than that of the commercial SnO2 NPs, which could be attributed to the localized electric field enhancement effect of Au nanorods plasmon and charges transfer between the Au nanorods and SnO2.

Photoinduced Glycerol Oxidation over Plasmonic Au and AuM (M = Pt, Pd and Bi) Nanoparticle-Decorated TiO2 Photocatalysts

PubMed Central

Jedsukontorn, Trin; Saito, Nagahiro; Hunsom, Mali

2018-01-01

In this study, sol-immobilization was used to prepare gold nanoparticle (Au NP)-decorated titanium dioxide (TiO2) photocatalysts at different Au weight % (wt. %) loading (Aux/TiO2, where x is the Au wt. %) and Au–M NP-decorated TiO2 photocatalysts (Au3M3/TiO2), where M is bismuth (Bi), platinum (Pt) or palladium (Pd) at 3 wt. %. The Aux/TiO2 photocatalysts exhibited a stronger visible light absorption than the parent TiO2 due to the localized surface plasmon resonance effect. Increasing the Au content from 1 wt. % to 7 wt. % led to increased visible light absorption due to the increasing presence of defective structures that were capable of enhancing the photocatalytic activity of the as-prepared catalyst. The addition of Pt and Pd coupled with the Au3/TiO2 to form Au3M3/TiO2 improved the photocatalytic activity of the Au3/TiO2 photocatalyst by maximizing their light-absorption property. The Au3/TiO2, Au3Pt3/TiO2 and Au3Pd3/TiO2 photocatalysts promoted the formation of glyceraldehyde from glycerol as the principle product, while Au3Bi3/TiO2 facilitated glycolaldehyde formation as the major product. Among all the prepared photocatalysts, Au3Pd3/TiO2 exhibited the highest photocatalytic activity with a 98.75% glycerol conversion at 24 h of reaction time. PMID:29690645

Tailor-made Au@Ag core-shell nanoparticle 2D arrays on protein-coated graphene oxide with assembly enhanced antibacterial activity

NASA Astrophysics Data System (ADS)

Wang, Huiqiao; Liu, Jinbin; Wu, Xuan; Tong, Zhonghua; Deng, Zhaoxiang

2013-05-01

Water-dispersible two-dimensional (2D) assemblies of Au@Ag core-shell nanoparticles are obtained through a highly selective electroless silver deposition on pre-assembled gold nanoparticles on bovine serum albumin (BSA)-coated graphene oxide (BSA-GO). While neither BSA-GO nor AuNP-decorated BSA-GO shows any antibacterial ability, the silver-coated GO@Au nanosheets (namely GO@Au@Ag) exhibit an enhanced antibacterial activity against Gram-negative Escherichia coli (E. coli) bacteria, superior to unassembled Au@Ag nanoparticles and even ionic Ag. Such an improvement may be attributed to the increased local concentration of silver nanoparticles around a bacterium and a polyvalent interaction with the bacterial surface. In addition, the colloidal stability of this novel nano-antimicrobial against the formation of random nanoparticle aggregates guarantees a minimized activity loss of the Au@Ag nanoparticles. The antibacterial efficacy of GO@Au@Ag is less sensitive to the existence of Cl-, in comparison with silver ions, providing another advantage for wound dressing applications. Our research unambiguously reveals a strong and very specific interaction between the GO@Au@Ag nanoassembly and E. coli, which could be an important clue toward a rational design, synthesis and assembly of innovative and highly active antibacterial nanomaterials.

Synthesis of Au@Pt bimetallic nanoparticles with concave Au nanocuboids as seeds and their enhanced electrocatalytic properties in the ethanol oxidation reaction

NASA Astrophysics Data System (ADS)

Tan, Lingyu; Li, Lidong; Peng, Yi; Guo, Lin

2015-12-01

Herein, a new type of uniform and well-structured Au@Pt bimetallic nanoparticles (BNPs) with highly active concave Au nanocuboids (NCs) as seeds was successfully synthesized by using the classic seed-mediated method. Electrochemical measurements were conducted to demonstrate their greatly enhanced catalytic performance in the ethanol oxidation reaction (EOR). It was found that the electrochemical performance for Au@Pt BNPs with the concave Au NCs as seeds, which were enclosed by {611} high-index facets, could be seven times higher than that of the Au@Pt bimetallic nanoparticles with regular spherical Au NPs as seeds. Furthermore, our findings show that the morphology and electrocatalytic activity of the Au@Pt BNPs can be tuned simply by changing the compositional ratios of the growth solution. The lower the amount of H2PtCl6 used in the growth solution, the thinner the Pt shell grew, and the more high-index facets of concave Au NCs seeds were exposed in Au@Pt BNPs, leading to higher electrochemical activity. These as-prepared concave Au@Pt BNPs will open up new strategies for improving catalytic efficiency and reducing the use of the expensive and scarce resource of platinum in the ethanol oxidation reaction, and are potentially applicable as electrochemical catalysts for direct ethanol fuel cells.

Synthesis of Au@Pt bimetallic nanoparticles with concave Au nanocuboids as seeds and their enhanced electrocatalytic properties in the ethanol oxidation reaction.

PubMed

Tan, Lingyu; Li, Lidong; Peng, Yi; Guo, Lin

2015-12-18

Herein, a new type of uniform and well-structured Au@Pt bimetallic nanoparticles (BNPs) with highly active concave Au nanocuboids (NCs) as seeds was successfully synthesized by using the classic seed-mediated method. Electrochemical measurements were conducted to demonstrate their greatly enhanced catalytic performance in the ethanol oxidation reaction (EOR). It was found that the electrochemical performance for Au@Pt BNPs with the concave Au NCs as seeds, which were enclosed by {611} high-index facets, could be seven times higher than that of the Au@Pt bimetallic nanoparticles with regular spherical Au NPs as seeds. Furthermore, our findings show that the morphology and electrocatalytic activity of the Au@Pt BNPs can be tuned simply by changing the compositional ratios of the growth solution. The lower the amount of H2PtCl6 used in the growth solution, the thinner the Pt shell grew, and the more high-index facets of concave Au NCs seeds were exposed in Au@Pt BNPs, leading to higher electrochemical activity. These as-prepared concave Au@Pt BNPs will open up new strategies for improving catalytic efficiency and reducing the use of the expensive and scarce resource of platinum in the ethanol oxidation reaction, and are potentially applicable as electrochemical catalysts for direct ethanol fuel cells.

Comparative study of proteasome inhibitory, synergistic antibacterial, synergistic anticandidal, and antioxidant activities of gold nanoparticles biosynthesized using fruit waste materials.

PubMed

Patra, Jayanta Kumar; Baek, Kwang-Hyun

The aim of this study was to compare the biological synthesis of gold nanoparticles (AuNPs) generated using the aqueous extracts of outer oriental melon peel (OMP) and peach. The synthesized OMP-AuNPs and peach extract (PE)-AuNPs were characterized by ultraviolet-visible spectroscopy, field emission scanning electron microscopy, energy dispersive X-ray analysis, X-ray powder diffraction, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The surface plasmon resonance spectra were obtained at 545 nm and 540 nm for OMP-AuNPs and PE-AuNPs, respectively. The estimated absolute crystallite size of the synthesized AuNPs was calculated to be 78.11 nm for OMP-AuNPs and 39.90 nm for PE-AuNPs based on the Scherer equation of the X-ray powder diffraction peaks. Fourier transform infrared spectroscopy results revealed the involvement of bioactive compounds present in OMP and peach extracts in the synthesis and stabilization of synthesized AuNPs. Both the OMP-AuNPs and PE-AuNPs showed a strong antibacterial synergistic activity when combined with kanamycin (9.38-20.45 mm inhibition zones) and rifampicin (9.52-25.23 mm inhibition zones), and they also exerted a strong synergistic anticandidal activity (10.09-15.47 mm inhibition zones) when combined with amphotericin B against five pathogenic Candida species. Both the OMP-AuNPs and PE-AuNPs exhibited a strong antioxidant potential in terms of 1,1-diphenyl-2-picrylhydraxyl radical scavenging, nitric oxide scavenging, 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) radical scavenging, and a reducing power, along with a strong proteasome inhibitory potential that could be useful in cancer drug delivery and cancer treatments. The PE-AuNPs showed comparatively higher activity than OMP-AuNPs, which could be attributed to the presence of rich bioactive compounds in the PE that acted as reducing and capping agents in the synthesis of PE-AuNPs. Overall, the results of the current investigation highlighted a novel green technology for the synthesis of AuNPs using food waste materials and their potential applications in the biomedical, pharmaceutical, and cosmetic industries.

{331}-Faceted trisoctahedral gold nanocrystals: synthesis, superior electrocatalytic performance and highly efficient SERS activity

NASA Astrophysics Data System (ADS)

Song, Yahui; Miao, Tingting; Zhang, Peina; Bi, Cuixia; Xia, Haibing; Wang, Dayang; Tao, Xutang

2015-04-01

We investigate the effect of gold (Au) seeds prepared in cetyltrimethylammonium chloride solution (CTAC-Au seeds) on the index facets of trisoctahedral gold nanocrystals (TOH Au NCs). We demonstrate that monodisperse {331}-faceted TOH Au NCs with controllable sizes (from 60 to 255 nm) can be successfully prepared in high yield by using 3.0 nm CTAC-Au seeds or as-prepared 70 nm TOH Au NCs as seeds. We find that the electrocatalytic performance on methanol oxidation and surface enhancement Raman spectroscopy (SERS) activity of {331}-faceted TOH Au NCs is size-dependent. In comparison with well-known nanoporous gold (0.088 mA cm-2), {331}-faceted TOH Au NCs with sizes of 110 nm exhibit fairly high catalytic activity (0.178 mA cm-2) on methanol oxidation (1.0 M) in alkaline media due to the presence of increasing density of atomic steps, ledges, and kinks on the NC surfaces. Their current density is reduced by less than 7% after 500 cycling tests. {331}-Faceted TOH Au NCs with sizes of 175 nm exhibit the highest SERS activity for 4-aminothiophenol (4-ATP) molecules. The enhancement factors of a1 modes of 4-ATP molecules can reach the order of 109 when the 4-ATP concentration is 3 × 10-6 M. Moreover, Raman signals (ag modes) of 4,4'-dimercaptoazobenzene (DMAB) molecules on TOH Au NCs are stronger than those on spherical Au NCs of comparable size due to the enhanced laser-induced transformation of 4-ATP molecules by high-index {331}-facets during SERS measurement. Furthermore, the SERS intensities of 4-methylbenzenethiol (4-MTP) molecules on TOH Au NCs are also higher than those on spherical Au NCs of comparable size due to sharp extremities.We investigate the effect of gold (Au) seeds prepared in cetyltrimethylammonium chloride solution (CTAC-Au seeds) on the index facets of trisoctahedral gold nanocrystals (TOH Au NCs). We demonstrate that monodisperse {331}-faceted TOH Au NCs with controllable sizes (from 60 to 255 nm) can be successfully prepared in high yield by using 3.0 nm CTAC-Au seeds or as-prepared 70 nm TOH Au NCs as seeds. We find that the electrocatalytic performance on methanol oxidation and surface enhancement Raman spectroscopy (SERS) activity of {331}-faceted TOH Au NCs is size-dependent. In comparison with well-known nanoporous gold (0.088 mA cm-2), {331}-faceted TOH Au NCs with sizes of 110 nm exhibit fairly high catalytic activity (0.178 mA cm-2) on methanol oxidation (1.0 M) in alkaline media due to the presence of increasing density of atomic steps, ledges, and kinks on the NC surfaces. Their current density is reduced by less than 7% after 500 cycling tests. {331}-Faceted TOH Au NCs with sizes of 175 nm exhibit the highest SERS activity for 4-aminothiophenol (4-ATP) molecules. The enhancement factors of a1 modes of 4-ATP molecules can reach the order of 109 when the 4-ATP concentration is 3 × 10-6 M. Moreover, Raman signals (ag modes) of 4,4'-dimercaptoazobenzene (DMAB) molecules on TOH Au NCs are stronger than those on spherical Au NCs of comparable size due to the enhanced laser-induced transformation of 4-ATP molecules by high-index {331}-facets during SERS measurement. Furthermore, the SERS intensities of 4-methylbenzenethiol (4-MTP) molecules on TOH Au NCs are also higher than those on spherical Au NCs of comparable size due to sharp extremities. Electronic supplementary information (ESI) available: Extra TEM images and extinction spectra of the corresponding TOH Au NCs obtained with CTAB-Au seeds and CTAC-Au seeds, cyclic voltammograms of the corresponding TOH Au NCs with {221} facets and {331} facets in 0.50 M H2SO4 medium, cyclic voltammograms of TOH Au NCs with different sizes in 0.50 M H2SO4 medium and in 0.50 M KOH medium, the variation of oxidation peak current density of the GCEs modified by the 110 nm TOH Au NCs at different scanning cycle numbers, experimental extinction spectra of TOH Au NCs of different sizes, SERS spectra of 4-ATP molecules on the aggregates of 175 nm TOH Au NCs and 170 nm spherical Au NCs, the normal Raman spectrum of the neat film of the 4-ATP molecule, and summarized data of the Raman intensity and SERS enhancement factors of the TOH Au NCs with different sizes in specific Raman bands. See DOI: 10.1039/c5nr01049g

Enhanced Activity of Au/NiO Nanohybrids for the Reductive Amination of Benzyl Alcohol

PubMed Central

Chinchilla, Lidia E.; Sanchez Trujillo, Felipe Juan; Dimitratos, Nikolaos; Botton, Gianluigi A.

2017-01-01

Gold nanoparticles were prepared by sol immobilization (AuSI) or deposition precipitation (AuDP), then deposited on NiO and commercial TiO2 (P25). The Au/NiO catalysts showed higher activity and yield to the secondary amine, compared to Au/TiO2 catalysts, when tested for the reductive amination of benzyl alcohol with isopropylamine. We attribute this result to a synergistic effect between Au and NiO. Moreover, as a result of the protective effect of the polyvinyl alcohol used in the sol immobilization synthesis, the gold nanoparticles on NiO demonstrate an increased resistance to structural changes during the reaction. This effect results in enhanced catalytic efficiency in terms of activity, and better stability against deactivation. PMID:29258170

Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: structure-activity relationship

NASA Astrophysics Data System (ADS)

Guo, Yu; Gu, Dong; Jin, Zhao; Du, Pei-Pei; Si, Rui; Tao, Jing; Xu, Wen-Qian; Huang, Yu-Ying; Senanayake, Sanjaya; Song, Qi-Sheng; Jia, Chun-Jiang; Schüth, Ferdi

2015-03-01

Uniform Au nanoparticles (~2 nm) with narrow size-distribution (standard deviation: 0.5-0.6 nm) supported on both hydroxylated (Fe_OH) and dehydrated iron oxide (Fe_O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. Transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) showed high homogeneity in the supported Au nanoparticles. The ex situ and in situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reduction by hydrogen (H2-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe_OH < Au/Fe_O) and CD (Au/Fe_OH > Au/Fe_O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe_OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeOx catalysts with very similar structural characteristics in CO oxidation.

The bright side of plasmonic gold nanoparticles; activation of Nrf2, the cellular protective pathway

NASA Astrophysics Data System (ADS)

Goldstein, Alona; Soroka, Yoram; Frušić-Zlotkin, Marina; Lewis, Aaron; Kohen, Ron

2016-06-01

Plasmonic gold nanoparticles (AuNPs) are widely investigated for cancer therapy, due to their ability to strongly absorb light and convert it to heat and thus selectively destroy tumor cells. In this study we shed light on a new aspect of AuNPs and their plasmonic excitation, wherein they can provide anti-oxidant and anti-inflammatory protection by stimulating the cellular protective Nrf2 pathway. Our study was carried out on cells of the immune system, macrophages, and on skin cells, keratinocytes. A different response to AuNPs was noted in the two types of cells, explained by their distinct uptake profiles. In keratinocytes, the exposure to AuNPs, even at low concentrations, was sufficient to activate the Nrf2 pathway, without any irradiation, due to the presence of free AuNPs inside the cytosol. In contrast, in macrophages, the plasmonic excitation of the AuNPs by a low, non-lethal irradiation dose was required for their release from the constraining vesicles. The mechanism by which AuNPs activate the Nrf2 pathway was studied. Direct and indirect activation were suggested, based on the inherent ability of the AuNPs to react with thiol groups and to generate reactive oxygen species, in particular, under plasmonic excitation. The ability of AuNPs to directly activate the Nrf2 pathway renders them good candidates for treatment of disorders in which the up-regulation of Nrf2 is beneficial, specifically for topical treatment of inflammatory skin diseases.

Uniform 2 nm gold nanoparticles supported on iron oxides as active catalysts for CO oxidation reaction: Structure-activity relationship

DOE PAGES

Guo, Yu; Senanayake, Sanjaya; Gu, Dong; ...

2015-01-12

Uniform Au nanoparticles (~2 nm) with narrow size-distribution (standard deviation: 0.5–0.6 nm) supported on both hydroxylated (Fe_OH) and dehydrated iron oxide (Fe_O) have been prepared by either deposition-precipitation (DP) or colloidal-deposition (CD) methods. Different structural and textural characterizations were applied to the dried, calcined and used gold-iron oxide samples. The transmission electron microscopy (TEM) and high-resolution TEM (HRTEM) described the high homogeneity in the supported Au nanoparticles. The ex-situ and in-situ X-ray absorption fine structure (XAFS) characterization monitored the electronic and short-range local structure of active gold species. The synchrotron-based in-situ X-ray diffraction (XRD), together with the corresponding temperature-programmed reductionmore » by hydrogen (H₂-TPR), indicated a structural evolution of the iron-oxide supports, correlating to their reducibility. An inverse order of catalytic activity between DP (Au/Fe_OH < Au/Fe_O) and CD (Au/Fe_OH > Au/Fe_O) was observed. Effective gold-support interaction results in a high activity for gold nanoparticles, locally generated by the sintering of dispersed Au atoms on the oxide support in the DP synthesis, while a hydroxylated surface favors the reactivity of externally introduced Au nanoparticles on Fe_OH support for the CD approach. This work reveals why differences in the synthetic protocol translate to differences in the catalytic performance of Au/FeO x catalysts with very similar structural characteristics in CO oxidation.« less

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

Yoon, Yeung-Pil; Kim, Jae-Hong; Ahn, Kwang-Soon, E-mail: kstheory@ynu.ac.kr

Au was electrodeposited potentiostatically at 0.3 V for 5 min on nanoporous Pt nanoparticle-coated F-doped SnO{sub 2} (FTO/Pt) substrates. For comparison, Au-electrodeposited FTO (FTO/Au) and Au-uncoated FTO/Pt were prepared. FTO/Au showed large-sized Au clusters dispersed sparsely over FTO, which resulted in lower electrocatalytic activity than FTO/Pt. In contrast, FTO/Pt exhibited poor stability unlike FTO/Au due to poisoning by the adsorption of sulfur species. The Au-electrodeposited FTO/Pt (FTO/Pt/Au) consisted of small Au clusters deposited over the entire area of Pt due to the effective Au nucleation provided by nanoporous metallic Pt. FTO/Pt/Au exhibited enhanced electrocatalytic activity and excellent stability because the small Aumore » particles well-dispersed over the nanoporous metallic Pt network provided numerous electrochemical reaction sites, and the Pt surface was not exposed to the electrolyte. When FTO/Pt/Au was used as the counter electrode (CE) of a quantum dot-sensitized solar cell, the significantly enhanced electrocatalytic activity of the FTO/Pt/Au CE facilitated the reduction reaction of S{sub n}{sup 2− }+ 2e{sup −} (CE) → S{sub n−1}{sup 2−} + S{sup 2−} at the CE/electrolyte interface, resulting in a significantly hindered recombination reaction, S{sub n}{sup 2− }+ 2e{sup −} (TiO{sub 2} in the photoanode) → S{sub n-1}{sup 2−} + S{sup 2−}, and significantly improved overall energy conversion efficiency.« less

Glutathione regulation-based dual-functional upconversion sensing-platform for acetylcholinesterase activity and cadmium ions.

PubMed

Fang, Aijin; Chen, Hongyu; Li, Haitao; Liu, Meiling; Zhang, Youyu; Yao, Shouzhuo

2017-01-15

A dual-functional platform for the sensing of acetylcholinesterase (AChE) activity and cadmium ions (Cd 2+ ) was developed based on the fluorescence resonance energy transfer (FRET) between NaYF 4 :Yb,Er upconversion nanoparticles (UCNPs) and gold nanoparticles (AuNPs) via glutathione regulation. The detection mechanism is based on the fact that AuNPs can quench the fluorescence of UCNPs. AChE catalyzes the hydrolysis of acetylthiocholine (ATC) into thiocholine which reacts with AuNPs by S-Au conjunction and results the aggregation of AuNPs and change in fluorescence of UCNPs. Therefore, the AChE activity can be detected through the changes of the color of solution and fluorescence recovery of UCNPs. However, the presence of glutathione (GSH) can protect AuNPs from aggregation and enlarge the inter-particle distance between AuNPs and UCNPs. When Cd 2+ is added into the stable mixture of AuNPs, GSH and AChE/ATC, Cd 2+ could interact with GSH to form a spherical shaped (GSH) 4 Cd complex, which decreases the free GSH on the surface of AuNPs to weaken the stability of AuNPs and lead to the easily aggregation of them in the system. The aggregated-AuNPs are released from the surface of UCNPs, which results in the fluorescence of UCNPs gradually recovered. Under the optimized conditions, the detection limits of AChE activity and Cd 2+ are estimated to be 0.015mU/mL and 0.2µM, respectively. The small molecules regulated dual-functional platform based on UCNPs/AuNPs is a simple, label-free method and can be applied for the turn-on fluorescence detection of AChE activity in human serum and Cd 2+ in real water samples. The present work demonstrates a general strategy for the design of small molecules regulated multifunctional platform and will be expanded for different areas in the future. Copyright © 2016 Elsevier B.V. All rights reserved.

Surface-enhanced Raman spectroscopy with Au-nanoparticle substrate fabricated by using femtosecond pulse

NASA Astrophysics Data System (ADS)

Zhang, Wending; Li, Cheng; Gao, Kun; Lu, Fanfan; Liu, Min; Li, Xin; Zhang, Lu; Mao, Dong; Gao, Feng; Huang, Ligang; Mei, Ting; Zhao, Jianlin

2018-05-01

Au-nanoparticle (Au-NP) substrates for surface-enhanced Raman spectroscopy (SERS) were fabricated by grid-like scanning a Au-film using a femtosecond pulse. The Au-NPs were directly deposited on the Au-film surface due to the scanning process. The experimentally obtained Au-NPs presented local surface plasmon resonance effect in the visible spectral range, as verified by finite difference time domain simulations and measured reflection spectrum. The SERS experiment using the Au-NP substrates exhibited high activity and excellent substrate reproducibility and stability, and a clearly present Raman spectra of target analytes, e.g. Rhodamine-6G, Rhodamine-B and Malachite green, with concentrations down to 10‑9 M. This work presents an effective approach to producing Au-NP SERS substrates with advantages in activity, reproducibility and stability, which could be used in a wide variety of practical applications for trace amount detection.

Surface-enhanced Raman spectroscopy with Au-nanoparticle substrate fabricated by using femtosecond pulse.

PubMed

Zhang, Wending; Li, Cheng; Gao, Kun; Lu, Fanfan; Liu, Min; Li, Xin; Zhang, Lu; Mao, Dong; Gao, Feng; Huang, Ligang; Mei, Ting; Zhao, Jianlin

2018-05-18

Au-nanoparticle (Au-NP) substrates for surface-enhanced Raman spectroscopy (SERS) were fabricated by grid-like scanning a Au-film using a femtosecond pulse. The Au-NPs were directly deposited on the Au-film surface due to the scanning process. The experimentally obtained Au-NPs presented local surface plasmon resonance effect in the visible spectral range, as verified by finite difference time domain simulations and measured reflection spectrum. The SERS experiment using the Au-NP substrates exhibited high activity and excellent substrate reproducibility and stability, and a clearly present Raman spectra of target analytes, e.g. Rhodamine-6G, Rhodamine-B and Malachite green, with concentrations down to 10 -9 M. This work presents an effective approach to producing Au-NP SERS substrates with advantages in activity, reproducibility and stability, which could be used in a wide variety of practical applications for trace amount detection.

Synergistic effect in an Au-Ag alloy nanocatalyst: CO oxidation.

PubMed

Liu, Jun-Hong; Wang, Ai-Qin; Chi, Yu-Shan; Lin, Hong-Ping; Mou, Chung-Yuan

2005-01-13

Au-Ag alloy nanoparticles supported on mesoporous aluminosilicate have been prepared by one-pot synthesis using hexadecyltrimethylammonium bromide (CTAB) both as a stabilizing agent for nanoparticles and as a template for the formation of mesoporous structure. The formation of Au-Ag alloy nanoparticles was confirmed by X-ray diffraction (XRD), ultraviolet-visible (UV-vis) spectroscopy, and transmission electron microscopy (TEM). Although the Au-Ag alloy nanoparticles have a larger particle size than the monometallic gold particles, they exhibited exceptionally high activity in catalysis for low-temperature CO oxidation. Even at a low temperature of 250 K, the reaction rate can reach 8.7 x 10(-6) mol.g(cat.)(-1).s(-1) at an Au/Ag molar ratio of 3/1. While neither monometallic Au@MCM-41 nor Ag@MCM-41 shows activity at this temperature, the Au-Ag alloy system shows a strongly synergistic effect in high catalytic activity. In this alloy system, the size effect is no longer a critical factor, whereas Ag is believed to play a key role in the activation of oxygen.

Inverse Catalysts for CO Oxidation: Enhanced Oxide–Metal Interactions in MgO/Au(111), CeO 2/Au(111), and TiO 2/Au(111)

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

Palomino, Robert M.; Gutiérrez, Ramón A.; Liu, Zongyuan

Au(111) does not bind CO and O 2 well. The deposition of small nanoparticles of MgO, CeO 2, and TiO 2 on Au(111) produces excellent catalysts for CO oxidation at room temperature. In an inverse oxide/metal configuration there is a strong enhancement of the oxide–metal interactions, and the inverse catalysts are more active than conventional Au/MgO(001), Au/CeO 2(111), and Au/TiO 2(110) catalysts. An identical trend was seen after comparing the CO oxidation activity of TiO2/Au and Au/TiO 2 powder catalysts. In the model systems, the activity increased following the sequence: MgO/Au(111) < CeO 2/Au(111) < TiO 2/Au(111). Ambient pressure X-raymore » photoelectron spectroscopy (AP-XPS) was used to elucidate the role of the titania–gold interface in inverse TiO 2/Au(111) model catalysts during CO oxidation. Stable surface intermediates such as CO(ads), CO 3 2–(ads), and OH(ads) were identified under reaction conditions. CO 3 2–(ads) and OH(ads) behaved as spectators. The concentration of CO(ad) initially increased and then decreased with increasing TiO 2 coverage, demonstrating a clear role of the Ti–Au interface and the size of the TiO 2 nanostructures in the catalytic process. Overall, our results show an enhancement in the strength of the oxide–metal interactions when working with inverse oxide/metal configurations, a phenomenon that can be utilized for the design of efficient catalysts useful for green and sustainable chemistry.« less

Inverse Catalysts for CO Oxidation: Enhanced Oxide–Metal Interactions in MgO/Au(111), CeO 2/Au(111), and TiO 2/Au(111)

DOE PAGES

Palomino, Robert M.; Gutiérrez, Ramón A.; Liu, Zongyuan; ...

2017-09-26

Au(111) does not bind CO and O 2 well. The deposition of small nanoparticles of MgO, CeO 2, and TiO 2 on Au(111) produces excellent catalysts for CO oxidation at room temperature. In an inverse oxide/metal configuration there is a strong enhancement of the oxide–metal interactions, and the inverse catalysts are more active than conventional Au/MgO(001), Au/CeO 2(111), and Au/TiO 2(110) catalysts. An identical trend was seen after comparing the CO oxidation activity of TiO2/Au and Au/TiO 2 powder catalysts. In the model systems, the activity increased following the sequence: MgO/Au(111) < CeO 2/Au(111) < TiO 2/Au(111). Ambient pressure X-raymore » photoelectron spectroscopy (AP-XPS) was used to elucidate the role of the titania–gold interface in inverse TiO 2/Au(111) model catalysts during CO oxidation. Stable surface intermediates such as CO(ads), CO 3 2–(ads), and OH(ads) were identified under reaction conditions. CO 3 2–(ads) and OH(ads) behaved as spectators. The concentration of CO(ad) initially increased and then decreased with increasing TiO 2 coverage, demonstrating a clear role of the Ti–Au interface and the size of the TiO 2 nanostructures in the catalytic process. Overall, our results show an enhancement in the strength of the oxide–metal interactions when working with inverse oxide/metal configurations, a phenomenon that can be utilized for the design of efficient catalysts useful for green and sustainable chemistry.« less

Highly Efficient Selective Hydrogenation of Cinnamaldehyde to Cinnamyl Alcohol over Gold Supported on Zinc Oxide Materials

DOE PAGES

Chen, Hangning; Cullen, David A.; Larese, J. Z.

2015-11-30

We used Au/ZnO catalysts for liquid-phase selective hydrogenation of cinnamaldehyde to cinnamyl alcohol and compared with Au/Fe 2O 3 catalysts. To investigate the influence of the support on the hydrogenation activity and selectivity, three different Au/ZnO catalysts were synthesized, including Au/rod-tetrapod ZnO, Au/porous ZnO, and Au/ZnO-CP prepared using a coprecipitation method. Moreover, the influence of calcination temperature was also systematically investigated in this study. The characterization of Au/ZnO catalysts was performed using ICP, N 2 adsorption/desorption isotherms, X-ray diffraction, scanning transmission electron microscopy, and X-ray photoelectron spectroscopy. Among all the supported Au catalysts prepared in this study, Au/ZnO-CP exhibits bothmore » the highest hydrogenation activity and selectivity. Using a 1.5% Au/ZnO-CP catalyst, 100% selectivity could be achieved with 94.9% conversion. Finally, we find that the Au particle (size and shape), the ZnO support (size and surface texture) and the interaction between Au and ZnO are three important parameters for achieving a highly efficient Au/ZnO catalyst.« less

Gold nanoparticles stabilized by poly(4-vinylpyridine) grafted cellulose nanocrystals as efficient and recyclable catalysts.

PubMed

Zhang, Zhen; Sèbe, Gilles; Wang, Xiaosong; Tam, Kam C

2018-02-15

pH-responsive poly(4-vinylpyridine) (P4VP) grafted cellulose nanocrystals (P4VP-g-CNC) were prepared by Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP) and subsequently used to stabilize gold nanoparticles (Au NPs) as efficient and recyclable nanocatalysts for the reduction of 4-nitrophenol (4NP). The presence of P4VP brushes on the CNC surface controlled the growth of Au NPs yielding smaller averaged diameter compared to Au NPs deposited directly on pristine CNC. The catalytic performances of pristine Au NPs, Au@CNC and Au@P4VP-g-CNC were compared by measuring the turnover frequency (TOF) for the catalytic reduction of 4NP. Compared to pristine Au NPs, the catalytic activity of Au@CNC and Au@P4VP-g-CNC were 10 and 24 times better. Moreover, the Au@P4VP-g-CNC material could be recovered via flocculation at pH>5, and the recycled nanocatalyst remained highly active. Copyright © 2017 Elsevier Ltd. All rights reserved.

Surface-Enhanced Raman Scattering Active Plasmonic Nanoparticles with Ultrasmall Interior Nanogap for Multiplex Quantitative Detection and Cancer Cell Imaging.

PubMed

Li, Jiuxing; Zhu, Zhi; Zhu, Bingqing; Ma, Yanli; Lin, Bingqian; Liu, Rudi; Song, Yanling; Lin, Hui; Tu, Song; Yang, Chaoyong

2016-08-02

Due to its large enhancement effect, nanostructure-based surface-enhanced Raman scattering (SERS) technology had been widely applied for bioanalysis and cell imaging. However, most SERS nanostructures suffer from poor signal reproducibility, which hinders the application of SERS nanostructures in quantitative detection. We report an etching-assisted approach to synthesize SERS-active plasmonic nanoparticles with 1 nm interior nanogap for multiplex quantitative detection and cancer cell imaging. Raman dyes and methoxy poly(ethylene glycol) thiol (mPEG-SH) were attached to gold nanoparticles (AuNPs) to prepare gold cores. Next, Ag atoms were deposited on gold cores in the presence of Pluronic F127 to form a Ag shell. HAuCl4 was used to etch the Ag shell and form an interior nanogap in Au@AgAuNPs, leading to increased Raman intensity of dyes. SERS intensity distribution of Au@AgAuNPs was found to be more uniform than that of aggregated AuNPs. Finally, Au@AgAuNPs were used for multiplex quantitative detection and cancer cell imaging. With the advantages of simple and rapid preparation of Au@AgAuNPs with highly uniform, stable, and reproducible Raman intensity, the method reported here will widen the applications of SERS-active nanoparticles in diagnostics and imaging.

Effect of Spin Multiplicity in O2 Adsorption and Dissociation on Small Bimetallic AuAg Clusters.

PubMed

García-Cruz, Raúl; Poulain, Enrique; Hernández-Pérez, Isaías; Reyes-Nava, Juan A; González-Torres, Julio C; Rubio-Ponce, A; Olvera-Neria, Oscar

2017-08-17

To dispose of atomic oxygen, it is necessary the O 2 activation; however, an energy barrier must be overcome to break the O-O bond. This work presents theoretical calculations of the O 2 adsorption and dissociation on small pure Au n and Ag m and bimetallic Au n Ag m (n + m ≤ 6) clusters using the density functional theory (DFT) and the zeroth-order regular approximation (ZORA) to explicitly include scalar relativistic effects. The most stable Au n Ag m clusters contain a higher concentration of Au with Ag atoms located in the center of the cluster. The O 2 adsorption energy on pure and bimetallic clusters and the ensuing geometries depend on the spin multiplicity of the system. For a doublet multiplicity, O 2 is adsorbed in a bridge configuration, whereas for a triplet only one O-metal bond is formed. The charge transfer from metal toward O 2 occupies the σ* O-O antibonding natural bond orbital, which weakens the oxygen bond. The Au 3 ( 2 A) cluster presents the lowest activation energy to dissociate O 2 , whereas the opposite applies to the AuAg ( 3 A) system. In the O 2 activation, bimetallic clusters are not as active as pure Au n clusters due to the charge donated by Ag atoms being shared between O 2 and Au atoms.

Core–Shell Au@Metal-Oxide Nanoparticle Electrocatalysts for Enhanced Oxygen Evolution

DOE PAGES

Strickler, Alaina L.; Escudero-Escribano, Marı́a; Jaramillo, Thomas F.

2017-09-25

Enhanced catalysis for electrochemical oxygen evolution is essential for the efficacy of many renewable energy technologies, including water electrolyzers and metal–air batteries. Recently, Au supports have been shown to enhance the activity of many 3d transition metal-oxide thin films for the oxygen evolution reaction (OER) in alkaline media. In this paper, we translate the beneficial impact of Au supports to high surface area, device-ready core–shell nanoparticles consisting of a Au-core and a metal-oxide shell (Au@M xO y where M = Ni, Co, Fe, and CoFe). Through a systematic evaluation, we establish trends in performance and illustrate the universal activity enhancementmore » when employing the Au-core in the 3d transition metal-oxide nanoparticles. Finally, the highest activity particles, Au@CoFeO x, demonstrate an overpotential of 328 ± 3 mV over a 2 h stability test at 10 mA cm –2, illustrating that strategically coupling Au support and mixed metal-oxide effects in a core–shell nanoparticle morphology is a promising avenue to achieve device-ready, high-performance OER catalysts.« less

Core–Shell Au@Metal-Oxide Nanoparticle Electrocatalysts for Enhanced Oxygen Evolution

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

Strickler, Alaina L.; Escudero-Escribano, Marı́a; Jaramillo, Thomas F.

Enhanced catalysis for electrochemical oxygen evolution is essential for the efficacy of many renewable energy technologies, including water electrolyzers and metal–air batteries. Recently, Au supports have been shown to enhance the activity of many 3d transition metal-oxide thin films for the oxygen evolution reaction (OER) in alkaline media. In this paper, we translate the beneficial impact of Au supports to high surface area, device-ready core–shell nanoparticles consisting of a Au-core and a metal-oxide shell (Au@M xO y where M = Ni, Co, Fe, and CoFe). Through a systematic evaluation, we establish trends in performance and illustrate the universal activity enhancementmore » when employing the Au-core in the 3d transition metal-oxide nanoparticles. Finally, the highest activity particles, Au@CoFeO x, demonstrate an overpotential of 328 ± 3 mV over a 2 h stability test at 10 mA cm –2, illustrating that strategically coupling Au support and mixed metal-oxide effects in a core–shell nanoparticle morphology is a promising avenue to achieve device-ready, high-performance OER catalysts.« less

CO2 hydrogenation to methanol on supported Au catalysts under moderate reaction conditions: support and particle size effects.

PubMed

Hartadi, Yeusy; Widmann, Daniel; Behm, R Jürgen

2015-02-01

The potential of metal oxide supported Au catalysts for the formation of methanol from CO2 and H2 under conditions favorable for decentralized and local conversion, which could be concepts for chemical energy storage, was investigated. Significant differences in the catalytic activity and selectivity of Au/Al2 O3 , Au/TiO2 , AuZnO, and Au/ZrO2 catalysts for methanol formation under moderate reaction conditions at a pressure of 5 bar and temperatures between 220 and 240 °C demonstrate pronounced support effects. A high selectivity (>50 %) for methanol formation was obtained only for Au/ZnO. Furthermore, measurements on Au/ZnO samples with different Au particle sizes reveal distinct Au particle size effects: although the activity increases strongly with the decreasing particle size, the selectivity decreases. The consequences of these findings for the reaction mechanism and for the potential of Au/ZnO catalysts for chemical energy storage and a "green" methanol technology are discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gold nanoparticle size and shape influence on osteogenesis of mesenchymal stem cells

NASA Astrophysics Data System (ADS)

Li, Jingchao; Li, Jia'en Jasmine; Zhang, Jing; Wang, Xinlong; Kawazoe, Naoki; Chen, Guoping

2016-04-01

Gold nanoparticles (AuNPs) have been extensively explored for biomedical applications due to their advantages of facile synthesis and surface functionalization. Previous studies have suggested that AuNPs can induce differentiation of stem cells into osteoblasts. However, how the size and shape of AuNPs affect the differentiation response of stem cells has not been elucidated. In this work, a series of bovine serum albumin (BSA)-coated Au nanospheres, Au nanostars and Au nanorods with different diameters of 40, 70 and 110 nm were synthesized and their effects on osteogenic differentiation of human mesenchymal stem cells (hMSCs) were investigated. All the AuNPs showed good cytocompatibility and did not influence proliferation of hMSCs at the studied concentrations. Osteogenic differentiation of hMSCs was dependent on the size and shape of AuNPs. Sphere-40, sphere-70 and rod-70 significantly increased the alkaline phosphatase (ALP) activity and calcium deposition of cells while rod-40 reduced the ALP activity and calcium deposition. Gene profiling revealed that the expression of osteogenic marker genes was down-regulated after incubation with rod-40. However, up-regulation of these genes was found in the sphere-40, sphere-70 and rod-70 treatment. Moreover, it was found that the size and shape of AuNPs affected the osteogenic differentiation of hMSCs through regulating the activation of Yes-associated protein (YAP). These results indicate that the size and shape of AuNPs had an influence on the osteogenic differentiation of hMSCs, which should provide useful guidance for the preparation of AuNPs with defined size and shape for their biomedical applications.Gold nanoparticles (AuNPs) have been extensively explored for biomedical applications due to their advantages of facile synthesis and surface functionalization. Previous studies have suggested that AuNPs can induce differentiation of stem cells into osteoblasts. However, how the size and shape of AuNPs affect the differentiation response of stem cells has not been elucidated. In this work, a series of bovine serum albumin (BSA)-coated Au nanospheres, Au nanostars and Au nanorods with different diameters of 40, 70 and 110 nm were synthesized and their effects on osteogenic differentiation of human mesenchymal stem cells (hMSCs) were investigated. All the AuNPs showed good cytocompatibility and did not influence proliferation of hMSCs at the studied concentrations. Osteogenic differentiation of hMSCs was dependent on the size and shape of AuNPs. Sphere-40, sphere-70 and rod-70 significantly increased the alkaline phosphatase (ALP) activity and calcium deposition of cells while rod-40 reduced the ALP activity and calcium deposition. Gene profiling revealed that the expression of osteogenic marker genes was down-regulated after incubation with rod-40. However, up-regulation of these genes was found in the sphere-40, sphere-70 and rod-70 treatment. Moreover, it was found that the size and shape of AuNPs affected the osteogenic differentiation of hMSCs through regulating the activation of Yes-associated protein (YAP). These results indicate that the size and shape of AuNPs had an influence on the osteogenic differentiation of hMSCs, which should provide useful guidance for the preparation of AuNPs with defined size and shape for their biomedical applications. Electronic supplementary information (ESI) available: Additional experimental results. See DOI: 10.1039/c5nr08808a

Grain-boundary-dependent CO2 electroreduction activity.

PubMed

Feng, Xiaofeng; Jiang, Kaili; Fan, Shoushan; Kanan, Matthew W

2015-04-15

Uncovering new structure-activity relationships for metal nanoparticle (NP) electrocatalysts is crucial for advancing many energy conversion technologies. Grain boundaries (GBs) could be used to stabilize unique active surfaces, but a quantitative correlation between GBs and catalytic activity has not been established. Here we use vapor deposition to prepare Au NPs on carbon nanotubes (Au/CNT). As deposited, the Au NPs have a relatively high density of GBs that are readily imaged by transmission electron microscopy (TEM); thermal annealing lowers the density in a controlled manner. We show that the surface-area-normalized activity for CO2 reduction is linearly correlated with GB surface density on Au/CNT, demonstrating that GB engineering is a powerful approach to improving the catalytic activity of metal NPs.

Green synthesis and characterization of Au@Pt core-shell bimetallic nanoparticles using gallic acid

NASA Astrophysics Data System (ADS)

Zhang, Guojun; Zheng, Hongmei; Shen, Ming; Wang, Lei; Wang, Xiaosan

2015-06-01

In this study, we developed a facile and benign green synthesis approach for the successful fabrication of well-dispersed urchin-like Au@Pt core-shell nanoparticles (NPs) using gallic acid (GA) as both a reducing and protecting agent. The proposed one-step synthesis exploits the differences in the reduction potentials of AuCl4- and PtCl62-, where the AuCl4- ions are preferentially reduced to Au cores and the PtCl62- ions are then deposited continuously onto the Au core surface as a Pt shell. The as-prepared Au@Pt NPs were characterized by transmission electron microscope (TEM); high-resolution transmission electron microscope (HR-TEM); scanning electron microscope (SEM); UV-vis absorption spectra (UV-vis); X-ray diffraction (XRD); Fourier transmission infrared spectra (FT-IR). We systematically investigated the effects of some experimental parameters on the formation of the Au@Pt NPs, i.e., the reaction temperature, the molar ratios of HAuCl4/H2PtCl6, and the amount of GA. When polyvinylpyrrolidone K-30 (PVP) was used as a protecting agent, the Au@Pt core-shell NPs obtained using this green synthesis method were better dispersed and smaller in size. The as-prepared Au@Pt NPs exhibited better catalytic activity in the reaction where NaBH4 reduced p-nitrophenol to p-aminophenol. However, the results showed that the Au@Pt bimetallic NPs had a lower catalytic activity than the pure Au NPs obtained by the same method, which confirmed the formation of Au@Pt core-shell nanostructures because the active sites on the surfaces of the Au NPs were covered with a Pt shell.

Highly sensitive and robust peroxidase-like activity of Au-Pt core/shell nanorod-antigen conjugates for measles virus diagnosis.

PubMed

Long, Lin; Liu, Jianbo; Lu, Kaishun; Zhang, Tao; Xie, Yunqing; Ji, Yinglu; Wu, Xiaochun

2018-05-02

As a promising candidate for artificial enzymes, catalytically active nanomaterials show several advantages over natural enzymes, such as controlled synthesis at low cost, tunability of catalytic activities, and high stability under stringent conditions. Rod-shaped Au-Pt core/shell nanoparticles (Au@Pt NRs), prepared by Au nanorod-mediated growth, exhibit peroxidase-like activities and could serve as an inexpensive replacement for horseradish peroxidase, with potential applications in various bio-detections. The determination of measles virus is accomplished by a capture-enzyme-linked immunosorbent assay (ELISA) using Au@Pt NR-antigen conjugates. Based on the enhanced catalytic properties of this nanozyme probe, a linear response was observed up to 10 ng/mL measles IgM antibodies in human serum, which is 1000 times more sensitive than commercial ELISA. Hence, these findings provide positive proof of concept for the potential of Au@Pt NR-antigen conjugates in the development of colorimetric biosensors that are simple, robust, and cost-effective.

Metal-Metal Interactions in Heterobimetallic Complexes with Dinucleating Redox-Active Ligands.

PubMed

Broere, Daniël L J; Modder, Dieuwertje K; Blokker, Eva; Siegler, Maxime A; van der Vlugt, Jarl Ivar

2016-02-12

The tuning of metal-metal interactions in multinuclear assemblies is a challenge. Selective P coordination of a redox-active PNO ligand to Au(I) followed by homoleptic metalation of the NO pocket with Ni(II) affords a unique trinuclear Au-Ni-Au complex. This species features two antiferromagnetically coupled ligand-centered radicals and a double intramolecular d(8)-d(10) interaction, as supported by spectroscopic, single-crystal X-ray diffraction, and computational data. A corresponding cationic dinuclear Au-Ni analogue with a stronger d(8)-d(10) interaction is also reported. Although both heterobimetallic structures display rich electrochemistry, only the trinuclear Au-Ni-Au complex facilitates electrocatalytic C-X bond activation of alkyl halides in its doubly reduced state. Hence, the presence of a redox-active ligand framework, an available coordination site at gold, and the nature of the nickel-gold interaction appear to be essential for this reactivity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparative study of proteasome inhibitory, synergistic antibacterial, synergistic anticandidal, and antioxidant activities of gold nanoparticles biosynthesized using fruit waste materials

PubMed Central

Patra, Jayanta Kumar; Baek, Kwang-Hyun

2016-01-01

The aim of this study was to compare the biological synthesis of gold nanoparticles (AuNPs) generated using the aqueous extracts of outer oriental melon peel (OMP) and peach. The synthesized OMP-AuNPs and peach extract (PE)-AuNPs were characterized by ultraviolet–visible spectroscopy, field emission scanning electron microscopy, energy dispersive X-ray analysis, X-ray powder diffraction, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The surface plasmon resonance spectra were obtained at 545 nm and 540 nm for OMP-AuNPs and PE-AuNPs, respectively. The estimated absolute crystallite size of the synthesized AuNPs was calculated to be 78.11 nm for OMP-AuNPs and 39.90 nm for PE-AuNPs based on the Scherer equation of the X-ray powder diffraction peaks. Fourier transform infrared spectroscopy results revealed the involvement of bioactive compounds present in OMP and peach extracts in the synthesis and stabilization of synthesized AuNPs. Both the OMP-AuNPs and PE-AuNPs showed a strong antibacterial synergistic activity when combined with kanamycin (9.38–20.45 mm inhibition zones) and rifampicin (9.52–25.23 mm inhibition zones), and they also exerted a strong synergistic anticandidal activity (10.09–15.47 mm inhibition zones) when combined with amphotericin B against five pathogenic Candida species. Both the OMP-AuNPs and PE-AuNPs exhibited a strong antioxidant potential in terms of 1,1-diphenyl-2-picrylhydraxyl radical scavenging, nitric oxide scavenging, 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) radical scavenging, and a reducing power, along with a strong proteasome inhibitory potential that could be useful in cancer drug delivery and cancer treatments. The PE-AuNPs showed comparatively higher activity than OMP-AuNPs, which could be attributed to the presence of rich bioactive compounds in the PE that acted as reducing and capping agents in the synthesis of PE-AuNPs. Overall, the results of the current investigation highlighted a novel green technology for the synthesis of AuNPs using food waste materials and their potential applications in the biomedical, pharmaceutical, and cosmetic industries. PMID:27695326

Alternative complement pathway activation during invasive coronary procedures in acute myocardial infarction and stable angina pectoris.

PubMed

Horváth, Zsófia; Csuka, Dorottya; Vargova, Katarina; Kovács, Andrea; Leé, Sarolta; Varga, Lilian; Préda, István; Tóth Zsámboki, Emese; Prohászka, Zoltán; Kiss, Róbert Gábor

2016-12-01

The effect of invasive percutaneous coronary procedures on complement activation has not been elucidated. We enrolled stable angina patients with elective percutaneous coronary intervention (SA-PCI, n=24), diagnostic coronary angiography (CA, n=52) and 23 patients with ST segment elevation myocardial infarction and primary PCI (STEMI-PCI). Complement activation products (C1rC1sC1inh, C3bBbP and SC5b-9) were measured on admission, 6 and 24h after coronary procedures. The alternative pathway product, C3bBbP significantly and reversibly increased 6h after elective PCI (baseline: 7.81AU/ml, 6h: 16.09AU/ml, 24h: 4.27AU/ml, p<0.01, n=23) and diagnostic angiography (baseline: 6.13AU/ml, 6h: 12.08AU/ml, 24h: 5.4AU/ml, p<0.01, n=52). Six hour C3bBbP values correlated with post-procedural CK, creatinine level and the applied contrast material volume (r=0.41, r=0.4, r=0.3, p<0.05, respectively). In STEMI-PCI, baseline C3bBbP level was higher, compared to SA-PCI or CA patients (11.33AU/ml vs. 7.81AU/ml or 6.13AU/ml, p<0.001). Similarly, the terminal complex (SC5b-9) level was already elevated at baseline compared to SA-PCI group (3.49AU/ml vs. 1.87AU/ml, p=0.011). Complement pathway products did not increase further after primary PCI. Elective coronary procedures induced transient alternative complement pathway activation, influenced by the applied contrast volume. In STEMI, the alternative complement pathway is promptly activated during the atherothrombotic event and PCI itself had no further detectable effect. Copyright © 2016 Elsevier B.V. All rights reserved.

Insights into the dominant factors of porous gold for CO oxidation

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

Kameoka, Satoshi, E-mail: kameoka@tagen.tohoku.ac.jp; Miyamoto, Kanji; Tanabe, Toyokazu

2016-01-21

Three different porous Au catalysts that exhibit high catalytic activity for CO oxidation were prepared by the leaching of Al from an intermetallic compound, Al{sub 2}Au, with 10 wt. %-NaOH, HNO{sub 3}, or HCl aqueous solutions. The catalysts were investigated using Brunauer-Emmett-Teller measurements, synchrotron X-ray powder diffraction, hard X-ray photoelectron spectroscopy, field emission scanning electron microscopy, and transmission electron microscopy (TEM). Broad diffraction peaks generated during the leaching process correlated with high activity for all the porous Au catalysts. CO oxidation catalyzed by porous Au leached with NaOH and HNO{sub 3} is considered to be dominated by different mechanisms atmore » low (< 320 K) and high (> 370 K) temperatures. Activity in the low-temperature region is mainly attributed to the perimeter interface between residual Al species (AlO{sub x}) and porous Au, whereas activity in the high-temperature region results from a high density of lattice defects such as twins and dislocations, which were evident from diffraction peak broadening and were observed with high-resolution TEM in the porous Au leached with NaOH. It is proposed that atoms located at lattice defects on the surfaces of porous Au are the active sites for catalytic reactions.« less

Synthesis and antimicrobial activity of gold/silver-tellurium nanostructures.

PubMed

Chang, Hsiang-Yu; Cang, Jinshun; Roy, Prathik; Chang, Huan-Tsung; Huang, Yi-Cheng; Huang, Chih-Ching

2014-06-11

Gold-tellurium nanostructures (Au-Te NSs), silver-tellurium nanostructures (Ag-Te NSs), and gold/silver-tellurium nanostructures (Au/Ag-Te NSs) have been prepared through galvanic reactions of tellurium nanotubes (Te NTs) with Au(3+), Ag(+), and both ions, respectively. Unlike the use of less environmentally friendly hydrazine, fructose as a reducing agent has been used to prepare Te NTs from TeO2 powders under alkaline conditions. The Au/Ag-Te NSs have highly catlaytic activity to convert nonfluorescent Amplex Red to form fluorescent product, revealing their great strength of generating reactive oxygen species (ROS). Au/Ag-Te NSs relative to the other two NSs exhibit greater antimicrobial activity toward the growth of E. coli, S. enteritidis, and S. aureus; the minimal inhibitory concentration (MIC) values of Au/Ag-Te NSs were much lower (>10-fold) than that of Ag-Te NSs and Au-Te NSs. The antibacterial activity of Au/Ag-Te NSs is mainly due to the release of Ag(+) ions and Te-related ions and also may be due to the generated ROS which destroys the bacteria membrane. In vitro cytotoxicity and hemolysis analyses have revealed their low toxicity in selected human cell lines and insignificant hemolysis in red blood cells. In addition, inhibition zone measurements using a Au/Ag-Te NSs-loaded konjac jelly film have suggested that it has great potential in practial application such as wound dressing for reducing bacterial wound infection. Having great antibacterial activitiy and excellent biocompatibility, the low-cost Au/Ag-Te NSs hold great potential as effective antimicrobial drugs.

Volume-confined synthesis of ligand-free gold nanoparticles with tailored sizes for enhanced catalytic activity

NASA Astrophysics Data System (ADS)

Shaik, Firdoz; Zhang, Weiqing; Niu, Wenxin; Lu, Xianmao

2014-10-01

Ligand-free Au nanoparticles with controlled sizes are synthesized via a volume-confined method. In this synthesis, mesoporous hollow silica shells (mHSS) are used as nano-containers for the impregnation of HAuCl4 solution before they are separated from the bulk solution. With a simple heating process, the Au precursor confined within the cavity of the isolated hollow shells is converted into ligand-free Au nanoparticles. The size of the Au nanoparticles can be tuned precisely by loading HAuCl4 solution of different concentrations, or by using mHSS with different cavity volumes. The ligand-free Au nanoparticles demonstrate superior catalytic activity than sodium citrate-capped Au nanoparticles.

The Enhanced Catalytic Activities of Asymmetric Au-Ni Nanoparticle Decorated Halloysite-Based Nanocomposite for the Degradation of Organic Dyes

NASA Astrophysics Data System (ADS)

Jia, Lei; Zhou, Tao; Xu, Jun; Li, Xiaohui; Dong, Kun; Huang, Jiancui; Xu, Zhouqing

2016-02-01

Janus particles (JPs) are unique among the nano-/microobjects because they provide asymmetry and can thus impart drastically different chemical or physical properties. In this work, we have fabricated the magnetic halloysite nanotube (HNT)-based HNTs@Fe3O4 nanocomposite (NCs) and then anchored the Janus Au-Ni or isotropic Au nanoparticles (NPs) to the surface of external wall of sulfydryl modified magnetic nanotubes. The characterization by physical methods authenticates the successful fabrication of two different magnetic HNTs@Fe3O4@Au and HNTs@Fe3O4@Au-Ni NCs. The catalytic activity and recyclability of the two NCs have been evaluated considering the degradation of Congo red (CR) and 4-nitrophenol (4-NP) using sodium borohydride as a model reaction. The results reveal that the symmetric Au NPs participated NCs display low activity in the degradation of the above organic dyes. However, a detailed kinetic study demonstrates that the employ of bimetallic Janus Au-Ni NPs in the NCs indicates enhanced catalytic activity, owing to the structurally specific nature. Furthermore, the magnetic functional NCs reported here can be used as recyclable catalyst which can be recovered simply by magnet.

Simple size-controlled synthesis of Au nanoparticles and their size-dependent catalytic activity

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

Suchomel, Petr; Kvitek, Libor; Prucek, Robert

The controlled preparation of Au nanoparticles (NPs) in the size range of 6 to 22 nm is explored in this study. The Au NPs were prepared by the reduction of tetrachloroauric acid using maltose in the presence of nonionic surfactant Tween 80 at various concentrations to control the size of the resulting Au NPs. With increasing concentration of Tween 80 a decrease in the size of produced Au NPs was observed, along with a significant decrease in their size distribution. The size-dependent catalytic activity of the synthesized Au NPs was tested in the reduction of 4-nitrophenol with sodium borohydride, resultingmore » in increasing catalytic activity with decreasing size of the prepared nanoparticles. Eley-Rideal catalytic mechanism emerges as the more probable, in contrary to the Langmuir-Hinshelwood mechanism reported for other noble metal nanocatalysts.« less

Simple size-controlled synthesis of Au nanoparticles and their size-dependent catalytic activity

DOE PAGES

Suchomel, Petr; Kvitek, Libor; Prucek, Robert; ...

2018-03-15

The controlled preparation of Au nanoparticles (NPs) in the size range of 6 to 22 nm is explored in this study. The Au NPs were prepared by the reduction of tetrachloroauric acid using maltose in the presence of nonionic surfactant Tween 80 at various concentrations to control the size of the resulting Au NPs. With increasing concentration of Tween 80 a decrease in the size of produced Au NPs was observed, along with a significant decrease in their size distribution. The size-dependent catalytic activity of the synthesized Au NPs was tested in the reduction of 4-nitrophenol with sodium borohydride, resultingmore » in increasing catalytic activity with decreasing size of the prepared nanoparticles. Eley-Rideal catalytic mechanism emerges as the more probable, in contrary to the Langmuir-Hinshelwood mechanism reported for other noble metal nanocatalysts.« less

Colloidal Au and Au-alloy catalysts for direct borohydride fuel cells: Electrocatalysis and fuel cell performance

NASA Astrophysics Data System (ADS)

Atwan, Mohammed H.; Macdonald, Charles L. B.; Northwood, Derek O.; Gyenge, Elod L.

Supported colloidal Au and Au-alloys (Au-Pt and Au-Pd, 1:1 atomic ratio) on Vulcan XC-72 (with 20 wt% metal load) were prepared by the Bönneman method. The electrocatalytic activity of the colloidal metals with respect to borohydride electro-oxidation for fuel cell applications was investigated by voltammetry on static and rotating electrodes, chronoamperometry, chronopotentiometry and fuel cell experiments. The fundamental electrochemical techniques showed that alloying Au, a metal that leads to the maximum eight-electron oxidation of BH 4 -, with Pd or Pt, well-known catalysts of dehydrogenation reactions, improved the electrode kinetics of BH 4 - oxidation. Fuel cell experiments corroborated the kinetic studies. Using 5 mg cm -2 colloidal metal load on the anode, it was found that Au-Pt was the most active catalyst giving a cell voltage of 0.47 V at 100 mA cm -2 and 333 K, while under identical conditions the cell voltage using colloidal Au was 0.17 V.

AuRu/meso-Mn2O3: A Highly Active and Stable Catalyst for Methane Combustion

NASA Astrophysics Data System (ADS)

Han, Z.; Fang, J. Y.; Xie, S. H.; Deng, J. G.; Liu, Y. X.; Dai, H. X.

2018-05-01

Three-dimensionally ordered mesoporous Mn2O3 (meso-Mn2O3) and its supported Au, Ru, and AuRu alloy (0.49 wt% Au/meso-Mn2O3, 0.48 wt% Ru/meso-Mn2O3, and 0.97 wt% AuRu/meso-Mn2O3 (Au/Ru molar ratio = 0.98)) nanocatalysts were prepared using the KIT-6-templating and polyvinyl alcohol-protected reduction methods, respectively. Physicochemical properties of the samples were characterized by means of numerous techniques, and their catalytic activities were evaluated for the combustion of methane. It is found that among all of the samples, 0.48 wt% Ru/meso-Mn 2O3 and 0.97 wt% AuRu/meso-Mn2O3 performed the best (the reaction temperature (T90% ) at 90% methane conversion was 530-540°C), but the latter showed a better thermal stability than the former. The partial deactivation of 0.97 wt% AuRu/meso-Mn2O3 due to H2O or CO2 introduction was reversible. It is concluded that the good catalytic activity and thermal stability of 0.97 wt% AuRu/meso-Mn2O3 was associated with the high dispersion of AuRu alloy NPs (2-5 nm) on the surface of meso-Mn2O3 and good low-temperature reducibility.

Gold nanoparticles on titanium and interaction with prototype protein.

PubMed

Padmos, J Daniel; Duchesne, Paul; Dunbar, Michael; Zhang, Peng

2010-10-01

Modifying titanium (Ti) implant surfaces with functional proteins can strengthen the interface between prosthesis and bone. A prototype system was developed using gold nanoparticles (AuNPs) to immobilize proteins onto Ti. An electroless (galvanic displacement) deposition method was first used to form AuNPs of controlled size and coverage on commercial Ti foil (giving Ti-AuNPs). Parameters were then modified to create two groups of discs (n = 26) with different average AuNP diameters. Scanning electron microscopy and X-ray photoelectron spectroscopy were used to characterize the morphology and surface structure of Ti-AuNPs. To study the interaction of Ti-AuNPs with proteins, Ti discs (n = 8) modified with plain AuNPs and discs (n = 8) modified with thiol (HS--R--COOH)-functionalized AuNPs were treated with lysozyme solution. The amount and activity of the lysozyme on the discs were examined with Micro-BCA and enzymatic assays. Lysozyme was immobilized onto the discs, and the assays showed that the discs with thiol-functionalized AuNPs, discs with bare AuNPs, and Ti controls had average lysozyme adsorptions of 23 x 10(4), 2.3 x 10(4), and 5.7 x 10(4) microg/m2, respectively. The activity assays showed that 21.5, 18.4, and 12.5% of the adsorbed lysozyme was active on the discs with thiol-functionalized AuNPs, discs with bare AuNPs, and Ti controls, respectively. This technique holds promise for binding functional biomolecules to surgical implants, hence possibly creating implant surfaces that react to their local environment. Copyright 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part A, 2010.

Novel synthesis of core-shell Au-Pt dendritic nanoparticles supported on carbon black for enhanced methanol electro-oxidation

NASA Astrophysics Data System (ADS)

Cao, Ribing; Xia, Tiantian; Zhu, Ruizhi; Liu, Zhihua; Guo, Jinming; Chang, Gang; Zhang, Zaoli; Liu, Xiong; He, Yunbin

2018-03-01

Core-shell Au-Pt dendritic nanoparticles (Au-Pt NPs) has been synthesized via a facile seed-mediated growth method, in which dendritic Pt nanoparticles as shell grow on the surface of gold nanocores by using ascorbic acid (AA) as "green" reducing reagents. The morphologies and compositions of the as-prepared nanocomposites with core-shell structure are characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Electrochemical experiments, including cyclic voltammetry (CV) and chronoamperometry (CA) are performed to investigate the electrocatalytic properties of the Au-Pt NPs loaded carbon black composites (Au-Pt NPs/V) towards methanol oxidation in an alkaline solution. It is found that the reduction time of AA could regulate the thickness and amount of Pt on the Au nanocores, which significantly affect catalytic activity of the Au-Pt NPs/V toward methanol oxidation. Au-Pt NPs/V with optimum reduction time 4 h exhibit 2.3-times higher electrocatalytic activity than that of a commercial catalyst (Pt/carbon black) and an excellent CO tolerance toward methanol oxidation. This behavior is attributed to large active electrochemical area of the bimetallic nanocomposites and the change in the electronic structure of Pt when Au surface modified with fewer Pt nanoparticles.

Biocompatible gold nanorods: one-step surface functionalization, highly colloidal stability, and low cytotoxicity.

PubMed

Liu, Kang; Zheng, Yuanhui; Lu, Xun; Thai, Thibaut; Lee, Nanju Alice; Bach, Udo; Gooding, J Justin

2015-05-05

The conjugation of gold nanorods (AuNRs) with polyethylene glycol (PEG) is one of the most effective ways to reduce their cytotoxicity arising from the cetyltrimethylammonium bromide (CTAB) and silver ions used in their synthesis. However, typical PEGylation occurs only at the tips of the AuNRs, producing partially modified AuNRs. To address this issue, we have developed a novel, facile, one-step surface functionalization method that involves the use of Tween 20 to stabilize AuNRs, bis(p-sulfonatophenyl)phenylphosphine (BSPP) to activate the AuNR surface for the subsequent PEGylation, and NaCl to etch silver from the AuNRs. This method allows for the complete removal of the surface-bound CTAB and the most active surface silver from the AuNRs. The produced AuNRs showed far lower toxicity than other methods to PEGylate AuNRs, with no apparent toxicity when their concentration is lower than 5 μg/mL. Even at a high concentration of 80 μg/mL, their cell viability is still four times higher than that of the tip-modified AuNRs.

Enhanced photocatalytic activity for H2 evolution under irradiation of UV-vis light by Au-modified nitrogen-doped TiO2.

PubMed

Zhao, Weirong; Ai, Zhuyu; Dai, Jiusong; Zhang, Meng

2014-01-01

Photocatalytic water splitting for hydrogen evolution is a potential way to solve many energy and environmental issues. Developing visible-light-active photocatalysts to efficiently utilize sunlight and finding proper ways to improve photocatalytic activity for H2 evolution have always been hot topics for research. This study attempts to expand the use of sunlight and to enhance the photocatalytic activity of TiO2 by N doping and Au loading. Au/N-doped TiO2 photocatalysts were synthesized and successfully used for photocatalytic water splitting for H2 evolution under irradiation of UV and UV-vis light, respectively. The samples were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PL), and photoelectrochemical characterizations. DRS displayed an extension of light absorption into the visible region by doping of N and depositing with Au, respectively. PL analysis indicated electron-hole recombination due to N doping and an efficient inhibition of electron-hole recombination due to the loaded Au particles. Under the irradiation of UV light, the photocatalytic hydrogen production rate of the as-synthesized samples followed the order Au/TiO2 > Au/N-doped TiO2 > TiO2 > N-doped TiO2. While under irradiation of UV-vis light, the N-TiO2 and Au/N-TiO2 samples show higher H2 evolution than their corresponding nitrogen-free samples (TiO2 and Au/TiO2). This inconsistent result could be attributed to the doping of N and the surface plasmonic resonance (SPR) effect of Au particles extending the visible light absorption. The photoelectrochemical characterizations further indicated the enhancement of the visible light response of Au/N-doped TiO2. Comparative studies have shown that a combination of nitrogen doping and Au loading enhanced the visible light response of TiO2 and increased the utilization of solar energy, greatly boosting the photocatalytic activity for hydrogen production under UV-vis light.

Magnetic activity of surface plasmon resonance using dielectric magnetic materials fabricated on quartz glass substrate

NASA Astrophysics Data System (ADS)

Narushima, Kazuki; Ashizawa, Yoshito; Brachwitz, Kerstin; Hochmuth, Holger; Lorenz, Michael; Grundmann, Marius; Nakagawa, Katsuji

2016-07-01

The magnetic activity of surface plasmons in Au/MFe2O4 (M = Ni, Co, and Zn) polycrystalline bilayer films fabricated on a quartz glass substrate was studied for future magnetic sensor applications using surface plasmon resonance. The excitation of surface plasmons and their magnetic activity were observed in all investigated Au/MFe2O4 films. The magnetic activity of surface plasmons of the polycrystalline Au/NiFe2O4 film was larger than those of the other polycrystalline Au/MFe2O4 films, the epitaxial NiFe2O4 film, and metallic films. The large magnetic activity of surface plasmons of the polycrystalline film is controlled by manipulating surface plasmon excitation conditions and magnetic properties.

Guazuma ulmifolia bark-synthesized Ag, Au and Ag/Au alloy nanoparticles: Photocatalytic potential, DNA/protein interactions, anticancer activity and toxicity against 14 species of microbial pathogens.

PubMed

Karthika, Viswanathan; Arumugam, Ayyakannu; Gopinath, Kasi; Kaleeswarran, Periyannan; Govindarajan, Marimuthu; Alharbi, Naiyf S; Kadaikunnan, Shine; Khaled, Jamal M; Benelli, Giovanni

2017-02-01

In the present study, we focused on a quick and green method to fabricate Ag, Au and Ag/Au alloy nanoparticles (NPs) using the bark extract of Guazuma ulmifolia L. Green synthesized metal NPs were characterized using different techniques, including UV-Vis spectroscopy, FT-IR, XRD, AFM and HR-TEM analyses. The production of Ag, Au and Ag/Au alloy NPs was observed monitoring color change from colorless to brown, followed by pink and dark brown, as confirmed by UV-Vis spectroscopy characteristic peaks at 436, 522 and 510nm, respectively. TEM shed light on the spherical shapes of NPs with size ranges of 10-15, 20-25 and 10-20nm. Biosynthesized NPs showed good catalytic activity reducing two organic dyes, 4-nitrophenol (4-NP) and Congo red (CR). UV-vis spectroscopy, fluorescence, circular dichroism spectroscopy and viscosity analyses were used to investigate the NP binding with calf thymus DNA. The binding constant of NPs with DNA calculated in UV-Vis absorption studies were 1.18×10 4 , 1.83×10 4 and 2.91×10 4 M -1 , respectively, indicating that NPs were able to bind DNA with variable binding affinity: Ag/Au alloy NPs>Ag NPs>Au NPs. Ag/Au alloy NPs also showed binding activity to bovine serum albumin (BSA) over the other NPs. Ag and Ag/Au alloy NPs exhibited good antimicrobial activity on 14 species of microbial pathogens. In addition, the cytotoxic effects of Ag/Au alloy NPs were studied on human cervical cancer cells (HeLa) using MTT assay. Overall, our work showed the promising potential of bark-synthesized Ag and Ag/Au alloy NPs as cheap sources to develop novel and safer photocatalytic, antimicrobial and anticancer agents. Copyright © 2017. Published by Elsevier B.V.

Branch number matters: Promoting catalytic reduction of 4-nitrophenol over gold nanostars by raising the number of branches and coating with mesoporous SiO2.

PubMed

Ndokoye, Pancras; Zhao, Qidong; Li, Xinyong; Li, Tingting; Tade, Moses O; Wang, Shaobin

2016-09-01

In this study, we demonstrate for the first time that highly branched gold nanostars (AuNSs) and silica-coated AuNSs (AuNSs@mSiO2) could potentially serve as efficient hydrogenation catalysts. The catalytic activity could be promoted by raising the number of tipped-branches of AuNSs, which reveals that the tips play an important role as active sites. The fabricated sharply-pointed AuNSs benefit the electron transfer from BH4 anions to 4-nitrophenol. Coating AuNSs with mesoporous silica (AuNSs@mSiO2) further enhanced the reduction rate and recyclability, and also contributed to reducing the induction period. The AuNSs@mSiO2 (50-100nm in diameter) are large enough to be catalytically inactive, but they consist of sharply-pointed tips with the radius of 2.6-3.6nm, which are rich in coordinately unsaturated sites similar to those of nanoparticles and clusters. Such features in structure and activity would also extend their application range in heterogeneous catalysis. Copyright © 2016 Elsevier Inc. All rights reserved.

Rational Design of Au@Pt Multibranched Nanostructures as Bifunctional Nanozymes.

PubMed

Wu, Jiangjiexing; Qin, Kang; Yuan, Dan; Tan, Jun; Qin, Li; Zhang, Xuejin; Wei, Hui

2018-04-18

One of the current challenges in nanozyme-based nanotechnology is the utilization of multifunctionalities in one material. In this regard, Au@Pt nanoparticles (NPs) with excellent enzyme-mimicking activities due to the Pt shell and unique surface plasmon resonance features from the Au core have attracted enormous research interest. However, the unique surface plasmon resonance features from the Au core have not been widely utilized. The practical problem of the optical-damping nature of Pt hinders the research into the combination of Au@Pt NPs' enzyme-mimicking properties with their surface-enhanced Raman scattering (SERS) activities. Herein, we rationally tuned the Pt amount to achieve Au@Pt NPs with simultaneous plasmonic and enzyme-mimicking activities. The results showed that Au@Pt NPs with 2.5% Pt produced the highest Raman signal in 2 min, which benefited from the remarkably accelerated catalytic oxidation of 3,3',5,5'-tetramethylbenzidine with the decorated Pt and strong electric field retained from the Au core for SERS. This study not only demonstrates the great promise of combining bimetallic nanomaterials' multiple functionalities but also provides rational guidelines to design high-performance nanozymes for potential biomedical applications.

New pathway to prepare gold nanoparticles and their applications in catalysis and surface-enhanced Raman scattering.

PubMed

Chang, Chun-Chao; Yang, Kuang-Hsuan; Liu, Yu-Chuan; Hsu, Ting-Chu

2012-05-01

As shown in the literature, additional energies are necessary for the reduction of positively charged noble metal ions to prepare metal nanoparticles (NPs). In this work, we report a new green pathway to prepare Au NPs in neutral 0.1M NaCl aqueous solutions from bulk Au substrates without addition of any stabilizer and reductant just via aid of natural chitosan (Ch) at room temperature. Au- and Ch-containing complexes in aqueous solution were electrochemically prepared. The role of Ch is just an intermediate to perform electron transfer with Au NPs. The stability of these prepared Au NPs is well maintained by Au NPs themselves with slightly positively charged Au remained on the surface of Au NPs. The particle size of prepared spherical Au (111) NPs is ca. 15 nm in diameter. Moreover, increasing the pH of preparation solutions can be contributive to preparing concentrated Au NPs in solutions. The prepared Au NPs are surface-enhanced Raman scattering (SERS)-active for probe molecules of Rhodamine 6G. They also demonstrate significantly catalytic activity for decomposition of acetaldehyde in rice wine. Copyright © 2012 Elsevier B.V. All rights reserved.

On the activation of molecular hydrogen by gold: a theoretical approximation to the nature of potential active sites.

PubMed

Corma, Avelino; Boronat, Mercedes; González, Silvia; Illas, Francesc

2007-08-28

The study of adsorption and dissociation of molecular hydrogen on single crystal Au(111) and Au(001) surfaces, monoatomic rows in an extended line defect and different Au nanoparticles by means of DF calculations allows us to firmly conclude that the necessary and sufficient condition for H2 dissociation is the existence of low coordinated Au atoms, regardless if they are in nanoparticles or at extended line defects.

Dispersed-nanoparticle loading synthesis for monodisperse Au-titania composite particles and their crystallization for highly active UV and visible photocatalysts.

PubMed

Sakamoto, Takeshi; Nagao, Daisuke; Noba, Masahiro; Ishii, Haruyuki; Konno, Mikio

2014-06-24

Submicrometer-sized amorphous titania spheres incorporating Au nanoparticles (NPs) were prepared in a one-pot synthesis consisting of a sol-gel reaction of titanium(IV) isopropoxide in the presence of chloroauric acid and a successive reduction with sodium borohydride in a mixed solvent of ethanol/acetonitrile. The synthesis was allowed to prepare monodisperse titania spheres that homogeneously incorporated Au NPs with sizes of ca. 7 nm. The Au NP-loaded titania spheres underwent different crystallization processes, including 500 °C calcination in air, high-temperature hydrothermal treatment (HHT), and/or low-temperature hydrothermal treatment (LHT). Photocatalytic experiments were conducted with the Au NP-loaded crystalline titania spheres under irradiation of UV and visible light. A combined process of LHT at 80 °C followed by calcination at 500 °C could effectively crystallize titania spheres maintaining the dispersion state of Au NPs, which led to photocatalytic activity higher than that of commercial P25 under UV irradiation. Under visible light irradiation, the Au NP-titania spheres prepared with a crystallization process of LHT at 80 °C for 6 h showed photocatalytic activity much higher than a commercial product of visible light photocatalyst. Structure analysis of the visible light photocatalysts indicates the importance of prevention of the Au NPs aggregation in the crystallization processes for enhancement of photocatalytic activity.

Propylene epoxidation over biogenic Au/TS-1 catalysts by Cinnamomum camphora extract in the presence of H2 and O2

NASA Astrophysics Data System (ADS)

Du, Mingming; Huang, Jiale; Sun, Daohua; Li, Qingbiao

2016-03-01

The Au/TS-1 catalysts with different Au nanoparticles (NPs) sizes ranging from 3.1 to 8.4 nm but the same Au loading of 0.5 wt% were prepared by Cinnamomum camphora (CC) extract, and were used for propylene epoxidation. The results showed that the interaction between Au and TS-1 support surface is important for propylene epoxidation and much smaller Au NPs (<3 nm) are the dominant active sites. After reaction of 100 h, there is no decreasing in both the activity and the PO selectivity for the Au/TS-1 catalysts, and only 1.8 wt% of the carbonaceous deposits on the surface of the catalyst after reaction, suggesting that the desorption of the product from the modified catalysts surface by residual biomolecules is much easier.

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

Barroo, Cedric; Janvelyan, Nare; Zugic, Branko

To improve the understanding of catalytic processes, the surface structure and composition of the active materials need to be determined before and after reaction. Morphological changes may occur under reaction conditions and can dramatically influence the reactivity and/or selectivity of a catalyst. Goldbased catalysts with different architectures are currently being developed for selective oxidation reactions at low temperatures. Specifically, nanoporous Au (npAu) with a composition of Au 97-Ag 3 is obtained by dealloying a Ag 70-Au 30 bulk alloy. Recent studies highlight the efficiency of npAu catalysts for methanol oxidation using ozone to activate the catalysts before methanol oxidation. Inmore » this paper, we studied the morphological and compositional changes occurring at the surface of Au-based catalysts in certain conditions.« less

Gold nanoparticle-catalyzed environmentally benign deoxygenation of epoxides to alkenes.

PubMed

Noujima, Akifumi; Mitsudome, Takato; Mizugaki, Tomoo; Jitsukawa, Koichiro; Kaneda, Kiyotomi

2011-09-28

We have developed a highly efficient and green catalytic deoxygenation of epoxides to alkenes using gold nanoparticles (NPs) supported on hydrotalcite [HT: Mg(6)Al(2)CO(3)(OH)(16)] (Au/HT) with alcohols, CO/H(2)O or H(2) as the reducing reagent. Various epoxides were selectively converted to the corresponding alkenes. Among the novel metal NPs on HT, Au/HT was found to exhibit outstanding catalytic activity for the deoxygenation reaction. Moreover, Au/HT can be separated from the reaction mixture and reused with retention of its catalytic activity and selectivity. The high catalytic performance of Au/HT was attributed to the selective formation of Au-hydride species by the cooperative effect between Au NPs and HT.

A novel green one-step synthesis of gold nanoparticles using crocin and their anti-cancer activities.

PubMed

Hoshyar, Reyhane; Khayati, Gholam Reza; Poorgholami, Maliheh; Kaykhaii, Massoud

2016-06-01

Functionalized nanoparticles are specifically designed to deliver drugs at tumor cells and can potentially enhance anticancer activity of drugs such as crocin. In the present study, we have applied antioxidant crocin as a reducing agent for one pot green synthesis of controlled size gold nanoparticles (AuNPs). Spherical, stable and uniform AuNPs were synthesized using crocin. These AuNPs are characterized by UV-Vis, TEM and XRD techniques. The prepared AuNPs showed surface plasm on resonance centered at 520nm with the average particle size of about 4-10nm. The anti-cancer effect of AuNPs was determined using MTT and LDH tests. The cellular data showed that these AuNPs significantly decreased cancerous cells' growth after 24 and 48hours in a time- and dose-dependent manner (P<0.05). The results suggest that such AuNPs can be synthesized simply and quickly with invaluable clinical as well as pharmaceutical activities which can help to treat human breast cancer. Copyright © 2016 Elsevier B.V. All rights reserved.

Improving gold catalysis of nitroarene reduction with surface Pd

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

Pretzer, Lori A.; Heck, Kimberly N.; Kim, Sean S.

2016-04-01

Nitroarene reduction reactions are commercialized catalytic processes that play a key role in the synthesisof many products including medicines, rubbers, dyes, and herbicides. Whereas bimetallic compositionshave been studied, a better understanding of the bimetallic structure effects may lead to improved indus-trial catalysts. In this work, the influence of surface palladium atoms supported on 3-nm Au nanoparticles(Pd-on-Au NPs) on catalytic activity for 4-nitrophenol reduction is explored. Batch reactor studies indi-cate Pd-on-Au NPs exhibit maximum catalytic activity at a Pd surface coverage of 150 sc%, with aninitial turnover frequency of ~3.7 mol-nitrophenol/mol-metalsurface/s, which was ~5.5× and ~13× moreactive than pure Au NPsmore » and Pd NPs, respectively. Pd NPs, Au NPs, and Pd-on-Au NPs below 175 sc%show compensation behavior. Three-dimensional Pd surface ensembles (with ~4–5 atoms) previouslyidentified through X-ray adsorption spectroscopy provide the active sites responsible for the catalyticmaximum. These results demonstrate the ability to adjust systematically a structural feature (i.e., Pdsurface coverage) to yield a more active material.« less

Postprandial anti-hyperglycemic activity of marine Streptomyces coelicoflavus SRBVIT13 mediated gold nanoparticles in streptozotocin induced diabetic male albino Wister rats.

PubMed

Sathish Kumar, Sathyanarayanan Ravi; Bhaskara Rao, Kokati Venkata

2016-10-01

The present study focuses on the biosynthesis of gold nanoparticles (AuNPs) using Streptomyces coelicoflavus ( S. coelicoflavus ) SRBVIT13 isolated from marine salt pan soils collected from Ongole, Andhra Pradesh, India. The biosynthesised AuNPs are characterised by UV-visible spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, high-resolution transmission electron microscopy and energy-dispersive X-ray analysis. Transmission electron microscopy study suggests that the biosynthesised AuNPs are spherical in shape within a size range of 12-20 nm (mean diameter as 14 nm). The anti-type II diabetes activity of AuNPs is carried out by testing it in vitro α -glucosidase and α -amylase enzyme inhibition activity and in vivo postprandial anti-hyperglycemic activity in sucrose and glucose-loaded streptozotocin induced diabetic albino Wister rats. AuNPs has shown a significant inhibitory activity of 84.70 and 87.82% with IC 50 values of 67.65 and 65.59 μg/mL to α -glucosidase and α -amylase enzymes, while the diabetic rats have shown significant reduction in the post postprandial blood glucose level by 57.80 and 88.09%, respectively compared with control group after AuNPs treatment at the concentration of 300 and 600 mg/kg body weight. Hence, this biosynthesised AuNPs might be useful in combating type II diabetes mellitus for the betterment of human life.

Novel electrochemical redox-active species: one-step synthesis of polyaniline derivative-Au/Pd and its application for multiplexed immunoassay

NASA Astrophysics Data System (ADS)

Wang, Liyuan; Feng, Feng; Ma, Zhanfang

2015-11-01

Electrochemical redox-active species play crucial role in electrochemically multiplexed immunoassays. A one-pot method for synthesizing four kinds of new electrochemical redox-active species was reported using HAuCl4 and Na2PdCl4 as dual oxidating agents and aniline derivatives as monomers. The synthesized polyaniline derivative-Au/Pd composites, namely poly(N-methyl-o-benzenediamine)-Au/Pd, poly(N-phenyl-o-phenylenediamine)-Au/Pd, poly(N-phenyl-p-phenylenediamine)-Au/Pd and poly(3,3’,5,5’-tetramethylbenzidine)-Au/Pd, exhibited electrochemical redox activity at -0.65 V, -0.3 V, 0.12 V, and 0.5 V, respectively. Meanwhile, these composites showed high H2O2 electrocatalytic activity because of the presence of Au/Pd. The as-prepared composites were used as electrochemical immunoprobes in simultaneous detection of four tumor biomarkers (carcinoembryonic antigen (CEA), carbohydrate antigen 19-9 (CA199), carbohydrate antigen 72-4 (CA724), and alpha fetoprotein (AFP)). This immunoassay shed light on potential applications in simultaneous gastric cancer (related biomarkers: CEA, CA199, CA724) and liver cancer diagnosis (related biomarkers: CEA, CA199, AFP). The present strategy to the synthesize redox species could be easily extended to other polymers such as polypyrrole derivatives and polythiophene derivatives. This would be of great significance in the electrochemical detection of more analytes.

The neural coding of creative idea generation across adolescence and early adulthood

PubMed Central

Kleibeuker, Sietske W.; Koolschijn, P. Cédric M. P.; Jolles, Dietsje D.; De Dreu, Carsten K. W.; Crone, Eveline A.

2013-01-01

Creativity is considered key to human prosperity, yet the neurocognitive principles underlying creative performance, and their development, are still poorly understood. To fill this void, we examined the neural correlates of divergent thinking in adults (25–30 years) and adolescents (15–17 years). Participants generated alternative uses (AU) or ordinary characteristics (OC) for common objects while brain activity was assessed using fMRI. Adults outperformed adolescents on the number of solutions for AU and OC trials. Contrasting neural activity for AU with OC trials revealed increased recruitment of left angular gyrus, left supramarginal gyrus, and bilateral middle temporal gyrus in both adults and adolescents. When only trials with multiple AU were included in the analysis, participants showed additional left inferior frontal gyrus (IFG)/middle frontal gyrus (MFG) activation for AU compared to OC trials. Correspondingly, individual difference analyses showed a positive correlation between activations for AU relative to OC trials in left IFG/MFG and divergent thinking performance and activations were more pronounced in adults than in adolescents. Taken together, the results of this study demonstrated that creative idea generation involves recruitment of mainly left lateralized parietal and temporal brain regions. Generating multiple creative ideas, a hallmark of divergent thinking, shows additional lateral PFC activation that is not yet optimized in adolescence. PMID:24416008

Preparation of plasmonic porous Au@AgVO3 belt-like nanocomposites with enhanced visible light photocatalytic activity.

PubMed

Fu, Haitao; Yang, Xiaohong; Zhang, Zhikui; Wang, Wenwen; An, Xizhong; Dong, Yu; Li, Xue

2018-07-20

This study reports a visible light-driven plasmonic photocatalyst of Au deposited AgVO 3 nanocomposites prepared by a hydrothermal method, and further in situ modification of Au nanoparticles by a reducing agent of NaHSO 3 in an aqueous solution at room temperature. Various characterization techniques, such as SEM, TEM, XRD, EDS, XPS, and Brunauer-Emmett-Teller, were used to reveal the morphology, composition, and related properties. The results show that belt-like AgVO 3 nanoparticles with a width of ∼100 nm were successfully synthesized, and Au nanoparticles with controlled sizes (5-20 nm) were well distributed on the surface of the nanobelts. The UV-vis absorption spectra indicate that the decoration of Au nanoparticles can modulate the optical properties of the nanocomposites, namely, red shift occurs with the increase of Au content. The photocatalytic activities were measured by monitoring the degradation of Rhodamine B (RhB) with the presence of photocatalysts under visible light irradiation. The photodegradation results show that AgVO 3 nanobelts exhibit good visible light photocatalytic activities with a degradation efficiency of 98% in 50 min and a reaction rate constant of 0.025 min -1 towards 30 ppm RhB. With the modification of Au nanoparticles, photocatalytic activity basically increases with the molar ratio of Au to V. Among the Au@AgVO 3 nanocomposites, the 3% (molar ratio) Au decorated AgVO 3 nanobelts showed the highest photocatalytic activity, and the k (0.064 min -1 ) was almost two times higher than that of the pure AgVO 3 nanobelts. This can be attributed to several factors including specific surface areas, optical properties, and the energy band structure of the composites under visible light illumination. These findings may be useful for the practical use of visible light-driven photocatalysts with enhanced photocatalytic efficiencies for environmental remediation.

Preparation of plasmonic porous Au@AgVO3 belt-like nanocomposites with enhanced visible light photocatalytic activity

NASA Astrophysics Data System (ADS)

Fu, Haitao; Yang, Xiaohong; Zhang, Zhikui; Wang, Wenwen; An, Xizhong; Dong, Yu; Li, Xue

2018-07-01

This study reports a visible light-driven plasmonic photocatalyst of Au deposited AgVO3 nanocomposites prepared by a hydrothermal method, and further in situ modification of Au nanoparticles by a reducing agent of NaHSO3 in an aqueous solution at room temperature. Various characterization techniques, such as SEM, TEM, XRD, EDS, XPS, and Brunauer–Emmett–Teller, were used to reveal the morphology, composition, and related properties. The results show that belt-like AgVO3 nanoparticles with a width of ∼100 nm were successfully synthesized, and Au nanoparticles with controlled sizes (5–20 nm) were well distributed on the surface of the nanobelts. The UV–vis absorption spectra indicate that the decoration of Au nanoparticles can modulate the optical properties of the nanocomposites, namely, red shift occurs with the increase of Au content. The photocatalytic activities were measured by monitoring the degradation of Rhodamine B (RhB) with the presence of photocatalysts under visible light irradiation. The photodegradation results show that AgVO3 nanobelts exhibit good visible light photocatalytic activities with a degradation efficiency of 98% in 50 min and a reaction rate constant of 0.025 min‑1 towards 30 ppm RhB. With the modification of Au nanoparticles, photocatalytic activity basically increases with the molar ratio of Au to V. Among the Au@AgVO3 nanocomposites, the 3% (molar ratio) Au decorated AgVO3 nanobelts showed the highest photocatalytic activity, and the k (0.064 min‑1) was almost two times higher than that of the pure AgVO3 nanobelts. This can be attributed to several factors including specific surface areas, optical properties, and the energy band structure of the composites under visible light illumination. These findings may be useful for the practical use of visible light-driven photocatalysts with enhanced photocatalytic efficiencies for environmental remediation.

Structure-activity relationships in cytotoxic Au(I)/Au(III) complexes derived from 2-(2'-pyridyl)benzimidazole.

PubMed

Maiore, Laura; Aragoni, Maria Carla; Deiana, Carlo; Cinellu, Maria Agostina; Isaia, Francesco; Lippolis, Vito; Pintus, Anna; Serratrice, Maria; Arca, Massimiliano

2014-04-21

Gold(I) and gold(III) complexes derived from 2-(2'-pyridyl)benzimidazole (pbiH) were proven to be a promising class of in vitro antitumor agents against A2780 human ovarian cancer cells. In this paper, a comparative electrochemical, UV-vis absorption, and emission spectroscopic investigation is reported on pbiH, the two mononuclear Au(III) complexes [(pbi)AuX2] (X = Cl (1), AcO (2)), the four mononuclear Au(I) derivatives [(pbiH)AuCl] (3), [(pbiH)Au(PPh3)]PF6 ((4(+))(PF6(-))), [(pbi)Au(PPh3)] (5), and [(pbi)Au(TPA)] (6), the three mixed-valence Au(III)/Au(I) complexes [(μ-pbi)Au2Cl3] (7), [(Ph3P)Au(μ-pbi)AuX2]PF6 (X = Cl ((8(+))(PF6(-))), AcO ((9(+))(PF6(-)))), and the binuclear Au(I)-Au(I) compound [(μ-pbi)Au2(PPh3)2]PF6 ((10(+))(PF6(-))). All complexes feature irreversible reduction processes related to the Au(III)/Au(I) or Au(I)/Au(0) processes and peculiar luminescent emission at about 360-370 nm in CH2Cl2, with quantum yields that are remarkably lower ((0.7-14.5) × 10(-2)) in comparison to that determined for the free pbiH ligand (31.5 × 10(-2)) in the same solvent. The spectroscopic and electrochemical properties of all complexes were interpreted on the grounds of time-dependent PBE0/DFT calculations carried out both in the gas phase and in CH2Cl2 implicitly considered within the IEF-PCM SCRF approach. The electronic structure of the complexes, and in particular the energy and composition of the Kohn-Sham LUMOs, can be related to the antiproliferative properties against the A2780 ovarian carcinoma cell line, providing sound quantitative structure-activity relationships and shedding a light on the role played by the global charge and nature of ancillary ligands in the effectiveness of Au-based antitumor drugs.

Evaluation d'un ecosysteme pastoral sahelien: Apport de la geomatique (Oursi, Burkina Faso)

NASA Astrophysics Data System (ADS)

Kabore, Seraphine Sawadogo

L'objectif principal de cette recherche est la mise au point d'une architecture d'integration de donnees socio-bio-geographiques et de donnees satellitales dans un Systeme d'Information Geographique (SIG) en vue d'une aide a la prise de decisions dans un environnement semi-aride au nord du Burkina Faso. Elle repond a la question fondamentale de l'interpretation des effets des facteurs climatiques et socioeconomiques sur le milieu pastoral. La recherche s'est appuyee sur plusieurs hypotheses de travail: possibilite d'utilisation de modele de simulation, d'approche multicritere et de donnees de teledetection dans un cadre de systeme d'information geographique. L'evolution spatiotemporelle des parametres de productivite du milieu a ete evaluee par approche dynamique selon le modele de Wu et al. (1996) qui modelise les interactions entre le climat, le milieu physique, le vegetal et l'animal pour mieux quantifier la biomasse primaire. A ce modele, quatre parametres ont ete integres par approche floue et multicritere afin de prendre en compte la dimension socioeconomique de la productivite pastorale (apport majeur de la recherche): la sante, l'education, l'agriculture et l'eau. La teledetection (imagerie SPOT) a permis de definir la production primaire a partir de laquelle les simulations ont ete realisees sur 10 annees. Les resultats obtenus montrent une bonne correlation entre biomasse primaire in situ et celle calculee pour les deux modeles, avec toutefois une meilleure efficacite du modele modifie (4 fois plus) dans les zones de forte productivite ou l'on note un taux de surexploitation agricole eleve. A cause de la variabilite spatiale de la production primaire in situ, les erreurs des resultats de simulation (8 a 11%) sont acceptables et montrent la pertinence de l'approche grace a l'utilisation des SIG pour la spatialisation et l'integration des differents parametres des modeles. Les types de production secondaire preconises (production de lait pendant 7 mois ou de viande pendant 6 mois) sont bases sur les besoins de l'UBT et le disponible fourrager qui est de qualite mediocre en saison seche. Dans les deux cas de figure, un deficit fourrager est observe. Deux types de transhumance sont proposes afin d'assurer une production durable selon deux scenarios: exploitation rationnelle des unites pastorales selon un plan de rotation annuelle et mise en defens a moyen terme des zones degradees pour une regeneration. Les zones potentielles pour la transhumance ont ete determinees selon les limites acceptables des criteres d'exploitation durable des milieux saheliens definis par Kessler (1994) soit 0,2 UBT.ha-1.

Surface plasmon resonance-induced photocatalysis by Au nanoparticles decorated mesoporous g-C{sub 3}N{sub 4} nanosheets under direct sunlight irradiation

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

Tonda, Surendar; Kumar, Santosh; Shanker, Vishnu, E-mail: vishnu@nitw.ac.in

Highlights: • The Au/mp-g-C{sub 3}N{sub 4} was synthesized via a template-free and green in situ strategy. • Au/mp-g-C{sub 3}N{sub 4} nanosheets possesses high surface area and porous structure. • Au/mp-g-C{sub 3}N{sub 4} showed dramatic photocurrent response and photocatalytic activity. • The high performance is due to SPR of Au and mesoporous structure. • Au/mp-g-C{sub 3}N{sub 4} nanosheets exhibited high photostability. - Abstract: In recent years, surface plasmon-induced photocatalytic materials with tunable mesoporous framework have attracted considerable attention in energy conversion and environmental remediation. Herein we report a novel Au nanoparticles decorated mesoporous graphitic carbon nitride (Au/mp-g-C{sub 3}N{sub 4}) nanosheets viamore » a template-free and green in situ photo-reduction method. The synthesized Au/mp-g-C{sub 3}N{sub 4} nanosheets exhibit a strong absorption edge in visible and near-IR region owing to the surface plasmon resonance effect of Au nanoparticles. More attractively, Au/mp-g-C{sub 3}N{sub 4} exhibited much higher photocatalytic activity than that of pure mesoporous and bulk g-C{sub 3}N{sub 4} for the degradation of rhodamine B under sunlight irradiation. Furthermore, the photocurrent and photoluminescence studies demonstrated that the deposition of Au nanoparticles on the surface of mesoporous g-C{sub 3}N{sub 4} could effectively inhibit the recombination of photogenerated charge carriers leading to the enhanced photocatalytic activity. More importantly, the synthesized Au/mp-g-C{sub 3}N{sub 4} nanosheets possess high reusability. Hence, Au/mp-g-C{sub 3}N{sub 4} could be promising photoactive material for energy and environmental applications.« less

Oxygen reduction of several gold alloys in 1-molar potassium hydroxide

NASA Technical Reports Server (NTRS)

Miller, R. O.

1975-01-01

With rotated disk-and-ring equipment, polarograms and other electrochemical measurements were made of oxygen reduction in 1-molar potassium hydroxide on an equiatomic gold-copper (Au-Cu) alloy and a Au-Cu alloy doped with either indium (In) or cobalt (Co) and on Au doped with either nickel (Ni) or platinum (Pt). The results were compared with those for pure Au and pure Pt. The two-electron reaction dominated on all Au alloys as it did on Au. The polarographic results at lower polarization potentials were compared, assuming exclusively a two-step reduction. A qualified ranking of cathodic electrocatalytic activity on the freshly polished reduced disks was indicated: anodized Au Au-Cu-In Au-Cu Au-Cu-Co is equivalent or equal to Au-Pt Au-Ni. Aging in distilled water improved the electrocatalytic efficiency of Au-Cu-Co, Au-Cu, and (to a lesser extent) Au-Cu-In.

Self-catalytic growth of unmodified gold nanoparticles as conductive bridges mediated gap-electrical signal transduction for DNA hybridization detection.

PubMed

Zhang, Jing; Nie, Huagui; Wu, Zhan; Yang, Zhi; Zhang, Lijie; Xu, Xiangju; Huang, Shaoming

2014-01-21

A simple and sensitive gap-electrical biosensor based on self-catalytic growth of unmodified gold nanoparticles (AuNPs) as conductive bridges has been developed for amplifying DNA hybridization events. In this strategy, the signal amplification degree of such conductive bridges is closely related to the variation of the glucose oxidase (GOx)-like catalytic activity of AuNPs upon interaction with single- and double-stranded DNA (ssDNA and dsDNA), respectively. In the presence of target DNA, the obtained dsDNA product cannot adsorb onto the surface of AuNPs due to electrostatic interaction, which makes the unmodified AuNPs exhibit excellent GOx-like catalytic activity. Such catalytic activity can enlarge the diameters of AuNPs in the glucose and HAuCl4 solution and result in a connection between most of the AuNPs and a conductive gold film formation with a dramatically increased conductance. For the control sample, the catalytic activity sites of AuNPs are fully blocked by ssDNA due to the noncovalent interaction between nucleotide bases and AuNPs. Thus, the growth of the assembled AuNPs will not happen and the conductance between microelectrodes will be not changed. Under the optimal experimental conditions, the developed strategy exhibited a sensitive response to target DNA with a high signal-to-noise ratio. Moreover, this strategy was also demonstrated to provide excellent differentiation ability for single-nucleotide polymorphism. Such performances indicated the great potential of this label-free electrical strategy for clinical diagnostics and genetic analysis under real biological sample separation.

Novel photocatalyst gold nanoparticles with dumbbell-like structure and their superiorly photocatalytic performance for ammonia borane hydrolysis

NASA Astrophysics Data System (ADS)

Zhu, Mingyun; Dai, Yunqian; Fu, Wanlin; Wu, Yanan; Zou, Xixi; You, Tengye; Sun, Yueming

2018-04-01

Gold nanoparticles (Au NPs) have attracted remarkable research interest in heterogeneous catalysis due to their unique physical and chemical properties. However, only small-sized Au NPs (<7 nm) exhibit promising catalytic activity. In this work, dumbbell-like Au NPs (D-Au NPs) with an average size of 37 × 11 nm were prepared by a secondary seed-mediated growth method to serve as novel photocatalysts for ammonia borane (AB) hydrolysis in a solution with a specific pH value. Our results demonstrate that (i) the strengthened localized surface plasmon resonance (LSPR) compensation effect could effectively remedy the loss of catalytic activity resulting from the size enlarging of D-Au NPs, proved by the observation that the heating power of a single Au nanoparticle (Ps) and turnover frequency of AB molecules within 10 min of D-Au NPs are 52.5 and 3.89 times higher, respectively, than those of spherical Au NPs; (ii) the extinction coefficient and Ps of D-Au NPs are almost 2.72 and 2.42 times as high, respectively, as those of rod-like Au NPs, demonstrating the promoting structure-property relationship of the dumbbell-like structure; (iii) when the pH value of the AB solution was lower than 6.0, the hydrolysis rate was highly promoted, indicating that H+ ions play an active role in the hydrolysis process. This work greatly extends the application of noble metals and provides a new insight into AB hydrolysis.

Increasing Stability and Activity of Core-Shell Catalysts by Preferential Segregation of Oxide on Edges and Vertexes: Oxygen Reduction on Ti-Au@Pt/C

DOE PAGES

Hu, J.; Wu, L.; Kuttiyiel, K.; ...

2016-06-30

We describe a new class of core-shell nanoparticle catalysts having edges and vertexes covered by refractory metal oxide that preferentially segregates onto these catalyst sites. The monolayer shell is deposited on the oxidefree core atoms. The oxide on edges and vertexes induces high catalyst’s stability and activity. The catalyst and synthesis are exemplified by fabrication of Au nanoparticles doped by Ti atoms that segregate as oxide onto low–coordination sites of edges and vertexes. Pt monolayer shell deposited on Au sites has the mass and specific activities for the oxygen reduction reaction about 13 and 5 times higher than those ofmore » commercial Pt/C catalysts. The durability tests show no activity loss after 10000 potential cycles from 0.6 to 1.0V. The superior activity and durability of the Ti-Au@Pt catalyst originate from protective Ti oxide located at the most dissolution-prone edge and vertex sites, and Au-supported active and stable Pt shell.« less

Understanding Interactions between Manganese Oxide and Gold That Lead to Enhanced Activity for Electrocatalytic Water Oxidation

PubMed Central

2015-01-01

To develop active nonprecious metal-based electrocatalysts for the oxygen evolution reaction (OER), a limiting reaction in several emerging renewable energy technologies, a deeper understanding of the activity of the first row transition metal oxides is needed. Previous studies of these catalysts have reported conflicting results on the influence of noble metal supports on the OER activity of the transition metal oxides. Our study aims to clarify the interactions between a transition metal oxide catalyst and its metal support in turning over this reaction. To achieve this goal, we examine a catalytic system comprising nanoparticulate Au, a common electrocatalytic support, and nanoparticulate MnOx, a promising OER catalyst. We conclusively demonstrate that adding Au to MnOx significantly enhances OER activity relative to MnOx in the absence of Au, producing an order of magnitude higher turnover frequency (TOF) than the TOF of the best pure MnOx catalysts reported to date. We also provide evidence that it is a local rather than bulk interaction between Au and MnOx that leads to the observed enhancement in the OER activity. Engineering improvements in nonprecious metal-based catalysts by the addition of Au or other noble metals could still represent a scalable catalyst as even trace amounts of Au are shown to lead a significant enhancement in the OER activity of MnOx. PMID:24661269

New Surface-Enhanced Raman Sensing Chip Designed for On-Site Detection of Active Ricin in Complex Matrices Based on Specific Depurination.

PubMed

Tang, Ji-Jun; Sun, Jie-Fang; Lui, Rui; Zhang, Zong-Mian; Liu, Jing-Fu; Xie, Jian-Wei

2016-01-27

Quick and accurate on-site detection of active ricin has very important realistic significance in view of national security and defense. In this paper, optimized single-stranded oligodeoxynucleotides named poly(21dA), which function as a depurination substrate of active ricin, were screened and chemically attached on gold nanoparticles (AuNPs, ∼100 nm) via the Au-S bond [poly(21dA)-AuNPs]. Subsequently, poly(21dA)-AuNPs were assembled on a dihydrogen lipoic-acid-modified Si wafer (SH-Si), thus forming the specific surface-enhanced Raman spectroscopy (SERS) chip [poly(21dA)-AuNPs@SH-Si] for depurination of active ricin. Under optimized conditions, active ricin could specifically hydrolyze multiple adenines from poly(21dA) on the chip. This depurination-induced composition change could be conveniently monitored by measuring the distinct attenuation of the SERS signature corresponding to adenine. To improve sensitivity of this method, a silver nanoshell was deposited on post-reacted poly(21dA)-AuNPs, which lowered the limit of detection to 8.9 ng mL(-1). The utility of this well-controlled SERS chip was successfully demonstrated in food and biological matrices spiked with different concentrations of active ricin, thus showing to be very promising assay for reliable and rapid on-site detection of active ricin.

Understanding interactions between manganese oxide and gold that lead to enhanced activity for electrocatalytic water oxidation.

PubMed

Gorlin, Yelena; Chung, Chia-Jung; Benck, Jesse D; Nordlund, Dennis; Seitz, Linsey; Weng, Tsu-Chien; Sokaras, Dimosthenis; Clemens, Bruce M; Jaramillo, Thomas F

2014-04-02

To develop active nonprecious metal-based electrocatalysts for the oxygen evolution reaction (OER), a limiting reaction in several emerging renewable energy technologies, a deeper understanding of the activity of the first row transition metal oxides is needed. Previous studies of these catalysts have reported conflicting results on the influence of noble metal supports on the OER activity of the transition metal oxides. Our study aims to clarify the interactions between a transition metal oxide catalyst and its metal support in turning over this reaction. To achieve this goal, we examine a catalytic system comprising nanoparticulate Au, a common electrocatalytic support, and nanoparticulate MnO(x), a promising OER catalyst. We conclusively demonstrate that adding Au to MnO(x) significantly enhances OER activity relative to MnO(x) in the absence of Au, producing an order of magnitude higher turnover frequency (TOF) than the TOF of the best pure MnO(x) catalysts reported to date. We also provide evidence that it is a local rather than bulk interaction between Au and MnO(x) that leads to the observed enhancement in the OER activity. Engineering improvements in nonprecious metal-based catalysts by the addition of Au or other noble metals could still represent a scalable catalyst as even trace amounts of Au are shown to lead a significant enhancement in the OER activity of MnO(x).

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

DOE PAGES

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

2015-12-31

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

Measurement of activation cross sections of alpha particle induced reactions on iridium up to an energy of 50 MeV.

PubMed

Takács, S; Ditrói, F; Szűcs, Z; Aikawa, M; Haba, H; Komori, Y; Saito, M

2018-06-01

Cross sections of alpha particle induced nuclear reactions on iridium were investigated using a 51.2-MeV alpha particle beam. The standard stacked-foil target technique and the activation method were applied. The activity of the reaction products was assessed without chemical separation using high resolution gamma-ray spectrometry. Excitation functions for production of gold, platinum and iridium isotopes ( 196m2 Au, 196m,g Au, 195m,g Au, 194 Au, 193 m,g Au, 192 Au, 191m,g Au, 191 Pt, 195m Pt, 194g Ir, 194m Ir, 192g Ir, 190g Ir and 189 Ir) were determined and compared with available earlier measured experimental data and results of theoretical calculations using TALYS code system. Cross section data were reported for the first time for the nat Ir(α,x) 196m2 Au, nat Ir(α,x) 196m,g Au, nat Ir(α,x) 191 Pt, nat Ir(α,x) 195m Pt, nat Ir(α,x) 194g Ir, nat Ir(α,x) 194m Ir, nat Ir(α,x) 190g Ir and nat Ir(α,x) 189 Ir processes. A possible production route for 195m Pt, the potentially important radionuclide in nuclear medicine, is discussed. Copyright © 2018 Elsevier Ltd. All rights reserved.

Bioinspired Au/TiO2 photocatalyst derived from butterfly wing (Papilio Paris).

PubMed

Chen, Jianjun; Su, Huilan; Song, Fang; Moon, Won-Jin; Kim, Yang-Soo; Zhang, Di

2012-03-15

The reticular hierarchical structure of butterfly wings (Papilio Paris) is introduced as template for Au/TiO(2) photocatalyst by depositing the Au nanoparticles on TiO(2) matrix, which is carried out by a water-ethanol sol-gel procedure combined with subsequent calcination. The obtained Au/TiO(2) nanocomposites present the reticular hierarchical structure of butterfly wings, and Au nanoparticles with an average size of 7 nm are homogeneously dispersed in TiO(2) substrate. Benefiting from such unique reticular hierarchical structure and composition, the biomorphic Au/TiO(2) exhibits high-harvesting capability and presents superior photocatalytic activity. Especially, the biomorphic Au/TiO(2) at the nominal content of gold to titanium of 8 wt% shows the highest photocatalytic activity and can completely decompose methyl orange within 80 min, which is obviously higher than that of commercial Degussa P25 powders. Copyright © 2011 Elsevier Inc. All rights reserved.

In Situ Synthesis of Gold Nanoparticles on Wool Powder and Their Catalytic Application.

PubMed

Tang, Bin; Zhou, Xu; Zeng, Tian; Lin, Xia; Zhou, Ji; Ye, Yong; Wang, Xungai

2017-03-15

Gold nanoparticles (AuNPs) were synthesized in situ on wool powder (WP) under heating conditions. Wool powder not only reduced Au ions to AuNPs, but also provided a support for as-synthesized AuNPs. WPs were treated under different concentrations of Au ions, and corresponding optical features and morphologies of the treated WPs were investigated by UV-VIS diffuse reflectance absorption spectroscopy and scanning electron microscopy (SEM). X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscope (TEM) were also employed to characterize the WP treated with AuNPs. The results demonstrate that AuNPs were produced in the presence of WP and distributed over the wool particles. The porous structure led to the synthesis of AuNPs in the internal parts of WP. Acid conditions and high temperature facilitated the synthesis of AuNPs by WP in aqueous solution. The reducibility of wool was improved after being converted to powder from fibers, due to exposure of more active groups. Moreover, the obtained AuNP-WP complexes showed significant catalytic activity to accelerate the reduction reaction of 4-nitrophenol (4-NP) by sodium borohydride (NaBH₄).

Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen

DOE PAGES

Qian, Linping; Wang, Zhen; Beletskiy, Evgeny V.; ...

2017-03-28

Here, the ability of Au catalysts to effect the challenging task of utilizing molecular oxygen for the selective epoxidation of cyclooctene is fascinating. Although supported nanometre-size Au particles are poorly active, here we show that solubilized atomic Au clusters, present in ng ml –1 concentrations and stabilized by ligands derived from the oxidized hydrocarbon products, are active. They can be formed from various Au sources. They generate initiators and propagators to trigger the onset of the auto-oxidation reaction with an apparent turnover frequency of 440 s –1, and continue to generate additional initiators throughout the auto-oxidation cycle without direct participationmore » in the cycle. Spectroscopic characterization suggests that 7–8 atom clusters are effective catalytically. Extension of work based on these understandings leads to the demonstration that these Au clusters are also effective in selective oxidation of cyclohexene, and that solubilized Pt clusters are also capable of generating initiators for cyclooctene epoxidation.« less

Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen

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

Qian, Linping; Wang, Zhen; Beletskiy, Evgeny V.

Here, the ability of Au catalysts to effect the challenging task of utilizing molecular oxygen for the selective epoxidation of cyclooctene is fascinating. Although supported nanometre-size Au particles are poorly active, here we show that solubilized atomic Au clusters, present in ng ml –1 concentrations and stabilized by ligands derived from the oxidized hydrocarbon products, are active. They can be formed from various Au sources. They generate initiators and propagators to trigger the onset of the auto-oxidation reaction with an apparent turnover frequency of 440 s –1, and continue to generate additional initiators throughout the auto-oxidation cycle without direct participationmore » in the cycle. Spectroscopic characterization suggests that 7–8 atom clusters are effective catalytically. Extension of work based on these understandings leads to the demonstration that these Au clusters are also effective in selective oxidation of cyclohexene, and that solubilized Pt clusters are also capable of generating initiators for cyclooctene epoxidation.« less

Direct synthesis of hydrogen peroxide and benzyl alcohol oxidation using Au-Pd catalysts prepared by sol immobilization.

PubMed

Pritchard, James; Kesavan, Lokesh; Piccinini, Marco; He, Qian; Tiruvalam, Ramchandra; Dimitratos, Nikolaos; Lopez-Sanchez, Jose A; Carley, Albert F; Edwards, Jennifer K; Kiely, Christopher J; Hutchings, Graham J

2010-11-02

We report the preparation of Au-Pd nanocrystalline catalysts supported on activated carbon prepared via a sol-immobilization technique and explore their use for the direct synthesis of hydrogen peroxide and the oxidation of benzyl alcohol. In particular, we examine the synthesis of a systematic set of Au-Pd colloidal nanoparticles having a range of Au/Pd ratios. The catalysts have been structurally characterized using a combination of UV-visible spectroscopy, transmission electron microscopy, STEM HAADF/XEDS, and X-ray photoelectron spectroscopy. The Au-Pd nanoparticles are found in the majority of cases to be homogeneous alloys, although some variation is observed in the AuPd composition at high Pd/Au ratios. The optimum performance for the synthesis of hydrogen peroxide is observed for a catalyst having a Au/Pd 1:2 molar ratio. However, the competing hydrogenation reaction of hydrogen peroxide increases with increasing Pd content, although Pd alone is less effective than when Au is also present. Investigation of the oxidation of benzyl alcohol using these materials also shows that the optimum selective oxidation to the aldehyde occurs for the Au/Pd 1:2 molar ratio catalyst. These measured activity trends are discussed in terms of the structure and composition of the supported Au-Pd nanoparticles.

The effect of defects on the catalytic activity of single Au atom supported carbon nanotubes and reaction mechanism for CO oxidation.

PubMed

Ali, Sajjad; Fu Liu, Tian; Lian, Zan; Li, Bo; Sheng Su, Dang

2017-08-23

The mechanism of CO oxidation by O 2 on a single Au atom supported on pristine, mono atom vacancy (m), di atom vacancy (di) and the Stone Wales defect (SW) on single walled carbon nanotube (SWCNT) surface is systematically investigated theoretically using density functional theory. We determine that single Au atoms can be trapped effectively by the defects on SWCNTs. The defects on SWCNTs can enhance both the binding strength and catalytic activity of the supported single Au atom. Fundamental aspects such as adsorption energy and charge transfer are elucidated to analyze the adsorption properties of CO and O 2 and co-adsorption of CO and O 2 molecules. It is found that CO binds stronger than O 2 on Au supported SWCNT. We clearly demonstrate that the defected SWCNT surface promotes electron transfer from the supported single Au atom to O 2 molecules. On the other hand, this effect is weaker for pristine SWCNTs. It is observed that the high density of spin-polarized states are localized in the region of the Fermi level due to the strong interactions between Au (5d orbital) and the adjacent carbon (2p orbital) atoms, which influence the catalytic performance. In addition, we elucidate both the Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms of CO oxidation by O 2 . For the LH pathway, the barriers of the rate-limiting step are calculated to be 0.02 eV and 0.05 eV for Au/m-SWCNT and Au/di-SWCNT, respectively. To regenerate the active sites, an ER-like reaction occurs to form a second CO 2 molecule. The ER pathway is observed on Au/m-SWCNT, Au/SW-SWCNT and Au/SWCNT in which the Au/m-SWCNT has a smaller barrier. The comparison with a previous study (Lu et al., J. Phys. Chem. C, 2009, 113, 20156-20160.) indicates that the curvature effect of SWCNTs is important for the catalytic property of the supported single Au. Overall, Au/m-SWCNT is identified as the most active catalyst for CO oxidation compared to pristine SWCNT, SW-SWCNT and di-SWCNT. Our findings give a clear description on the relationship between the defects in the support and the catalytic properties of Au and open a new avenue to develop carbon nanomaterial-based single atom catalysts for application in environmental and energy related fields.

Gold nano-particle formation from crystalline AuCN: Comparison of thermal, plasma- and ion-beam activated decomposition

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

Beck, Mihály T.; Bertóti, Imre, E-mail: bertoti.imre@ttk.mta.hu; Mohai, Miklós

In this work, in addition to the conventional thermal process, two non-conventional ways, the plasma and ion beam activations are described for preparing gold nanoparticles from microcrystalline AuCN precursor. The phase formation at plasma and ion beam treatments was compared with that at thermal treatments and the products and transformations were characterized by thermogravimetry-mass-spectrometry (TG-MS), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). TG-MS measurements in Ar atmosphere revealed that AuCN decomposition starts at 400 °C and completes at ≈700 °C with evolution of gaseous (CN){sub 2}. XPS and TEM show that in heat treatment at 450 °C formore » 1 h in Ar, loss of nitrogen and carbon occurs and small, 5–30 nm gold particles forms. Heating at 450 °C for 10 h in sealed ampoule, much larger, 60–200 nm size and well faceted Au particles develop together with a fibrous (CN){sub n} polymer phase, and the Au crystallites are covered by a 3–5 nm thick polymer shell. Low pressure Ar plasma treatment at 300 eV energy results in 4–20 nm size Au particles and removes most of the nitrogen and part of carbon. During Ar{sup +} ion bombardment with 2500 eV energy, 5–30 nm size Au crystallites form already in 10 min, with preferential loss of nitrogen and with increased amount of carbon residue. The results suggest that plasma and ion beam activation, acting similarly to thermal treatment, may be used to prepare Au nanoparticles from AuCN on selected surface areas either by depositing AuCN precursors on selected regions or by focusing the applied ionized radiation. Thus they may offer alternative ways for preparing tailor-made catalysts, electronic devices and sensors for different applications. - Graphical abstract: Proposed scheme of the decomposition mechanism of AuCN samples: heat treatment in Ar flow (a) and in sealed ampoule (b); Ar{sup +} ion treatment at 300 eV (c) and at 2500 eV (d). Cross section sketches illustrate the Au phase formation and the corresponding TEM micrographs are shown as top views. The dotted lines represent the original boundaries of the AuCN crystals. - Highlights: • AuCN decomposes between 400 and 700 °C with evolution of gaseous (CN){sub 2}. • Epitaxial relationship is established between Au and parent AuCN crystals. • Ar plasma treatment results in similar phase transition than the thermal treatment. • Plasma and ion-beam activation offer alternative way for preparing Au nanocrystals. • Reaction mechanisms of Au particle formation at the three treatments are proposed.« less

Correlating structural dynamics and catalytic activity of AgAu nanoparticles with ultrafast spectroscopy and all-atom molecular dynamics simulations.

PubMed

Ferbonink, G F; Rodrigues, T S; Dos Santos, D P; Camargo, P H C; Albuquerque, R Q; Nome, R A

2018-05-29

In this study, we investigated hollow AgAu nanoparticles with the goal of improving our understanding of the composition-dependent catalytic activity of these nanoparticles. AgAu nanoparticles were synthesized via the galvanic replacement method with controlled size and nanoparticle compositions. We studied extinction spectra with UV-Vis spectroscopy and simulations based on Mie theory and the boundary element method, and ultrafast spectroscopy measurements to characterize decay constants and the overall energy transfer dynamics as a function of AgAu composition. Electron-phonon coupling times for each composition were obtained from pump-power dependent pump-probe transients. These spectroscopic studies showed how nanoscale surface segregation, hollow interiors and porosity affect the surface plasmon resonance wavelength and fundamental electron-phonon coupling times. Analysis of the spectroscopic data was used to correlate electron-phonon coupling times to AgAu composition, and thus to surface segregation and catalytic activity. We have performed all-atom molecular dynamics simulations of model hollow AgAu core-shell nanoparticles to characterize nanoparticle stability and equilibrium structures, besides providing atomic level views of nanoparticle surface segregation. Overall, the basic atomistic and electron-lattice dynamics of core-shell AgAu nanoparticles characterized here thus aid the mechanistic understanding and performance optimization of AgAu nanoparticle catalysts.

Thiol-Capped Gold Nanoparticles Swell-Encapsulated into Polyurethane as Powerful Antibacterial Surfaces Under Dark and Light Conditions

PubMed Central

Macdonald, Thomas J.; Wu, Ke; Sehmi, Sandeep K.; Noimark, Sacha; Peveler, William J.; du Toit, Hendrik; Voelcker, Nicolas H.; Allan, Elaine; MacRobert, Alexander J.; Gavriilidis, Asterios; Parkin, Ivan P.

2016-01-01

A simple procedure to develop antibacterial surfaces using thiol-capped gold nanoparticles (AuNPs) is shown, which effectively kill bacteria under dark and light conditions. The effect of AuNP size and concentration on photo-activated antibacterial surfaces is reported and we show significant size effects, as well as bactericidal activity with crystal violet (CV) coated polyurethane. These materials have been proven to be powerful antibacterial surfaces against both Gram-positive and Gram-negative bacteria. AuNPs of 2, 3 or 5 nm diameter were swell-encapsulated into PU before a coating of CV was applied (known as PU-AuNPs-CV). The antibacterial activity of PU-AuNPs-CV samples was tested against Staphylococcus aureus and Escherichia coli as representative Gram-positive and Gram-negative bacteria under dark and light conditions. All light conditions in this study simulated a typical white-light hospital environment. This work demonstrates that the antibacterial activity of PU-AuNPs-CV samples and the synergistic enhancement of photoactivity of triarylmethane type dyes is highly dependent on nanoparticle size and concentration. The most powerful PU-AuNPs-CV antibacterial surfaces were achieved using 1.0 mg mL−1 swell encapsulation concentrations of 2 nm AuNPs. After two hours, Gram-positive and Gram-negative bacteria were reduced to below the detection limit (>4 log) under dark and light conditions. PMID:27982122

Tailoring Enzyme-Like Activities of Gold Nanoclusters by Polymeric Tertiary Amines for Protecting Neurons Against Oxidative Stress.

PubMed

Liu, Ching-Ping; Wu, Te-Haw; Lin, Yu-Lung; Liu, Chia-Yeh; Wang, Sabrina; Lin, Shu-Yi

2016-08-01

The cytotoxicity of nanozymes has drawn much attention recently because their peroxidase-like activity can decompose hydrogen peroxide (H2 O2 ) to produce highly toxic hydroxyl radicals (•OH) under acidic conditions. Although catalytic activities of nanozymes are highly associated with their surface properties, little is known about the mechanism underlying the surface coating-mediated enzyme-like activities. Herein, it is reported for the first time that amine-terminated PAMAM dendrimer-entrapped gold nanoclusters (AuNCs-NH2 ) unexpectedly lose their peroxidase-like activity while still retaining their catalase-like activity in physiological conditions. Surprisingly, the methylated form of AuNCs-NH2 (i.e., MAuNCs-N(+) R3 , where R = H or CH3 ) results in a dramatic recovery of the intrinsic peroxidase-like activity while blocking most primary and tertiary amines (1°- and 3°-amines) of dendrimers to form quaternary ammonium ions (4°-amines). However, the hidden peroxidase-like activity is also found in hydroxyl-terminated dendrimer-encapsulated AuNCs (AuNCs-OH, inside backbone with 3°-amines), indicating that 3°-amines are dominant in mediating the peroxidase-like activity. The possible mechanism is further confirmed that the enrichment of polymeric 3°-amines on the surface of dendrimer-encapsulated AuNCs provides sufficient suppression of the critical mediator •OH for the peroxidase-like activity. Finally, it is demonstrated that AuNCs-NH2 with diminished cytotoxicity have great potential for use in primary neuronal protection against oxidative damage. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Physicochemical and catalytic properties of Au nanorods micro-assembled in solvents of varying dipole moment and refractive index

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

Kaur, Rupinder; Pal, Bonamali, E-mail: bpal@thapar.edu

2015-02-15

Highlights: • Physicochemical activities of Au nanorods in water largely differ from organic solvents. • Au nanorods agglomeration increased with dipole moments of different polar solvents. • Refractive indexes of Au nanorods dispersion in various polar solvents are enhanced. • Electrokinetics significantly altered depending on agglomerated size of Au nanorods. • Catalysis or co-catalysis activity is varied as per the extent of Au nanorods coagulation. - Abstract: This paper deals with the impact of dipole moment (1.66–3.96 D) and refractive index (1.333–1.422) of the dispersion solvent on the plasmon absorption, surface charge, zeta potential, and adsorption properties of Au nanorodsmore » (AuNRs). AuNRs (length ≈ 53 nm and width ≈ 20 nm) undergo agglomeration (size 50–180 nm) with increase in the dipole moment of solvent (iPrOH < MeOH < DMF < DMSO). Whereas, no such coagulation occurs in H{sub 2}O and CCl{sub 4} suspension as confirmed by DLS and TEM size distribution. The electrostatic interaction of AuNRs with its surface adsorbed solvent dipoles leads to alteration of the their ionic state, absolute electronic charge and zeta potential (+49.79 mV in H{sub 2}O, +8.99 mV in DMF and −4.65 mV in MeOH dispersion) to a greater extent. This interaction distinctly modifies the adsorption behavior of polar molecules like p-nitrophenol and salicylic acid on AuNRs surface, as evidenced by the measured changes in their electro-kinetic parameters. As a result, we observe a substantial difference in catalytic and co-catalytic activities of AuNRs dispersed in various solvents as mentioned above because the catalytic properties of AuNRs are strongly dependent on the type of solvent in which they are dispersed.« less

Ultrastable BSA-capped gold nanoclusters with a polymer-like shielding layer against reactive oxygen species in living cells

NASA Astrophysics Data System (ADS)

Zhou, Wenjuan; Cao, Yuqing; Sui, Dandan; Guan, Weijiang; Lu, Chao; Xie, Jianping

2016-05-01

The prevalence of reactive oxygen species (ROS) production and the enzyme-containing intracellular environment could lead to the fluorescence quenching of bovine serum albumin (BSA)-capped gold nanoclusters (AuNCs). Here we report an efficient strategy to address this issue, where a polymer-like shielding layer is designed to wrap around the Au core to significantly improve the stability of AuNCs against ROS and protease degradation. The key of our design is to covalently incorporate a thiolated AuNC into the BSA-AuNC via carbodiimide-activated coupling, leading to the formation of a AuNC pair inside the cross-linked BSA molecule. The as-designed paired AuNCs in BSA (or BSA-p-AuNCs for short) show improved performances in living cells.The prevalence of reactive oxygen species (ROS) production and the enzyme-containing intracellular environment could lead to the fluorescence quenching of bovine serum albumin (BSA)-capped gold nanoclusters (AuNCs). Here we report an efficient strategy to address this issue, where a polymer-like shielding layer is designed to wrap around the Au core to significantly improve the stability of AuNCs against ROS and protease degradation. The key of our design is to covalently incorporate a thiolated AuNC into the BSA-AuNC via carbodiimide-activated coupling, leading to the formation of a AuNC pair inside the cross-linked BSA molecule. The as-designed paired AuNCs in BSA (or BSA-p-AuNCs for short) show improved performances in living cells. Electronic supplementary information (ESI) available: Detailed experimental materials, apparatus, experimental procedures and characterization data. See DOI: 10.1039/c6nr02178f

Rapid detection of protein phosphatase activity using Zn(II)-coordinated gold nanosensors based on His-tagged phosphopeptides.

PubMed

Lee, Jin Oh; Kim, Eun-Ji; Lim, Butaek; Kim, Tae-Wuk; Kim, Young-Pil

2015-01-20

We report a rapid colorimetric assay to detect protein phosphatase (PP) activity based on the controlled assembly and disassembly of gold nanoparticles (AuNPs) via Zn(II)-specific coordination in the presence of His6-tagged phosphopeptides. Among divalent metal ions including Ni(II), Cu(II), Co(II), Mg(II), Mn(II), and Zn(II), only Zn(II) triggered a strong association between phosphopeptides with hexahistidine at a single end and nitrilotriacetic acid (NTA)-modified AuNPs (21.3 nm in core diameter), leading to the self-assembly of AuNPs and consequently changes in color of the AuNP solution. In contrast, unphosphorylated peptides and His6-deficient phosphopeptides did not change the color of the AuNP solution. As a result, protein phosphatase 1 (PP1) activity and its inhibition were easily quantified with high sensitivity by determining the extinction ratio (E520/E700) of colloidal AuNPs. Most importantly, this method was capable of detecting protein phosphatase 2A (PP2A) activity in immunoprecipitated plant extracts. Because PPs play pivotal roles in mediating diverse signal transduction pathways as primary effectors of protein dephosphorylation, we anticipate that our method will be applied as a rapid format method to analyze the activities of various PPs and their inhibition.

Catalytic activity of nanostructured Au: Scale effects versus bimetallic/bifunctional effects in low-temperature CO oxidation on nanoporous Au

PubMed Central

Wang, Lu-Cun; Zhong, Yi; Jin, Haijun; Widmann, Daniel; Weissmüller, Jörg

2013-01-01

Summary The catalytic properties of nanostructured Au and their physical origin were investigated by using the low-temperature CO oxidation as a test reaction. In order to distinguish between structural effects (structure–activity correlations) and bimetallic/bifunctional effects, unsupported nanoporous gold (NPG) samples prepared from different Au alloys (AuAg, AuCu) by selective leaching of a less noble metal (Ag, Cu) were employed, whose structure (surface area, ligament size) as well as their residual amount of the second metal were systematically varied by applying different potentials for dealloying. The structural and chemical properties before and after 1000 min reaction were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The catalytic behavior was evaluated by kinetic measurements in a conventional microreactor and by dynamic measurements in a temporal analysis of products (TAP) reactor. The data reveal a clear influence of the surface contents of residual Ag and Cu species on both O2 activation and catalytic activity, while correlations between activity and structural parameters such as surface area or ligament/crystallite size are less evident. Consequences for the mechanistic understanding and the role of the nanostructure in these NPG catalysts are discussed. PMID:23503603

Near-unity thermally activated delayed fluorescence efficiency in three- and four-coordinate Au(i) complexes with diphosphine ligands.

PubMed

Osawa, Masahisa; Aino, Masa-Aki; Nagakura, Takaki; Hoshino, Mikio; Tanaka, Yuya; Akita, Munetaka

2018-05-14

The synthesis and photoluminescence properties of three-coordinate Au(i) complexes with rigid diphosphine ligands LMe {1,2-bis[bis(2-methylphenyl)phosphino]benzene}, LEt {1,2-bis[bis(2-ethylphenyl)phosphino]benzene}, and LiPr {1,2-bis[bis(2-isopropylphenyl)phosphino]benzene} are investigated. The LMe and LEt ligands afford two types of complexes: dinuclear complexes [μ-LMe(AuCl)2] (1d) and [μ-LEt(AuCl)2] (2d) with an Au(i)-Au(i) bond and mononuclear three-coordinate Au(i) complexes LMeAuCl (1) and LEtAuCl (2). On the other hand, the bulkiest ligand, LiPr, affords three-coordinate Au(i) complexes, LiPrAuCl (3) and LiPrAuI (4), but no dinuclear complexes. X-ray analysis suggests that both 3 and 4 possess a highly distorted trigonal planar geometry. Moreover, luminescence data reveal that at room temperature, 3 and 4 exhibit yellow-green thermally activated delayed fluorescence in the crystalline state with maximum emission wavelengths at 558 and 549 nm, respectively. The emission yields are close to unity. Quantum chemical calculations suggest that the emission of 4 originates from the (σ + X) → π* excited state that possesses strong intraligand charge-transfer character. The luminescent properties of four-coordinate Au(i) complex (5) possessing a tetrahedral geometry are discussed on the basis of the emission spectra and decay times measured in a temperature range of 309-77 K.

Facile synthesis of Au-ZnO plasmonic nanohybrids for highly efficient photocatalytic degradation of methylene blue

NASA Astrophysics Data System (ADS)

Kuriakose, Sini; Sahu, Kavita; Khan, Saif A.; Tripathi, A.; Avasthi, D. K.; Mohapatra, Satyabrata

2017-02-01

Au-ZnO plasmonic nanohybrids were synthesized by a facile two step process. In the first step, nanostructured ZnO thin films were prepared by carbothermal evaporation followed by thermal annealing in oxygen atmosphere. Deposition of ultrathin Au films onto the nanostructured ZnO thin films by sputtering combined with thermal annealing resulted in the formation of Au-ZnO plasmonic nanohybrid thin films. The structural, optical, plasmonic and photocatalytic properties of the Au-ZnO nanohybrid thin films were studied. XRD studies on the Au-ZnO hybrid thin films revealed the presence of Au and ZnO nanostructures. UV-visible absorption studies showed two peaks corresponding to the excitonic absorption of ZnO nanostructures in the UV region and the surface plasmon resonance (SPR) absorption of Au nanoparticles in the visible region. The Au-ZnO nanohybrid thin films annealed at 400 °C showed enhanced photocatalytic activity as compared to nanostructrured ZnO thin films towards sun light driven photocatalytic degradation of methylene blue (MB) dye in water. The observed enhanced photocatalytic activity of Au-ZnO plasmonic nanohybrids is attributed to the efficient suppression of the recombination of photogenerated charge carriers in ZnO due to the strong electron scavenging action of Au nanoparticles combined with the improved sun light utilization capability of Au-ZnO nanohybrids coming from the plasmonic response of Au nanoparticles decorating ZnO nanostructures.

Interfacial nanodroplets guided construction of hierarchical Au, Au-Pt, and Au-Pd particles as excellent catalysts

NASA Astrophysics Data System (ADS)

Ma, Aijing; Xu, Jie; Zhang, Xuehua; Zhang, Bin; Wang, Dayang; Xu, Haolan

2014-05-01

Interfacial nanodroplets were grafted to the surfaces of self-sacrificed template particles in a galvanic reaction system to assist the construction of 3D Au porous structures. The interfacial nanodroplets were formed via direct adsorption of surfactant-free emulsions onto the particle surfaces. The interfacial nanodroplets discretely distributed at the template particle surfaces and served as soft templates to guide the formation of porous Au structures. The self-variation of footprint sizes of interfacial nanodroplets during Au growth gave rise to a hierarchical pore size distribution of the obtained Au porous particles. This strategy could be easily extended to synthesize bimetal porous particles such as Au-Pt and Au-Pd. The obtained porous Au, Au-Pt, and Au-Pd particles showed excellent catalytic activity in catalytic reduction of 4-nitrophenol.

Cytotoxicity of various types of gold-mesoporous silica nanoparticles in human breast cancer cells

PubMed Central

Liu, Guomu; Li, Qiongshu; Ni, Weihua; Zhang, Nannan; Zheng, Xiao; Wang, Yingshuai; Shao, Dan; Tai, Guixiang

2015-01-01

Recently, gold nanoparticles (AuNPs) have shown promising biological applications due to their unique electronic and optical properties. However, the potential toxicity of AuNPs remains a major hurdle that impedes their use in clinical settings. Mesoporous silica is very suitable for the use as a coating material for AuNPs and might not only reduce the cytotoxicity of cetyltrimethylammonium bromide-coated AuNPs but might also facilitate the loading and delivery of drugs. Herein, three types of rod-like gold-mesoporous silica nanoparticles (termed bare AuNPs, core–shell Au@mSiO2NPs, and Janus Au@mSiO2NPs) were specially designed, and the effects of these AuNPs on cellular uptake, toxic behavior, and mechanism were then systematically studied. Our results indicate that bare AuNPs exerted higher toxicity than the Au@mSiO2NPs and that Janus Au@mSiO2NPs exhibited the lowest toxicity in human breast cancer MCF-7 cells, consistent with the endocytosis capacity of the nanoparticles, which followed the order, bare AuNPs > core–shell Au@mSiO2NPs > Janus Au@mSiO2NPs. More importantly, the AuNPs-induced apoptosis of MCF-7 cells exhibited features that were characteristic of intracellular reactive oxygen species (ROS) generation, activation of c-Jun-N-terminal kinase (JNK) phosphorylation, an enhanced Bax-to-Bcl-2 ratio, and loss of the mitochondrial membrane potential. Simultaneously, cytochrome c was released from mitochondria, and the caspase-3/9 cascade was activated. Moreover, both ROS scavenger (N-acetylcysteine) and JNK inhibitor (SP600125) partly blocked the induction of apoptosis in all AuNPs-treated cells. Taken together, these findings suggest that all AuNPs induce apoptosis through the ROS-/JNK-mediated mitochondrial pathway. Thus, Janus Au@mSiO2NPs exhibit the potential for applications in biomedicine, thus aiding the clinical translation of AuNPs. PMID:26491285

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

NASA Astrophysics Data System (ADS)

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

2014-09-01

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

Visual detection of telomerase activity with a tunable dynamic range by using a gold nanoparticle probe-based hybridization protection strategy

NASA Astrophysics Data System (ADS)

Wang, Jiasi; Wu, Li; Ren, Jinsong; Qu, Xiaogang

2014-01-01

We developed a novel telomere complementary (TC) oligonucleotide modified AuNP probe (TC-AuNPs) for colorimetric analysis of telomerase activity. The mechanism of this method is that the telomerase reaction products (TRP), which can hybridize with the TC-AuNPs, are able to protect the AuNPs from the aggregation induced by salt. It is demonstrated that the colorimetric method enabled the analysis of the telomerase activity in 1000 HeLa cells with the naked eye, and down to 100 HeLa cells with the aid of UV-Vis spectroscopy. This strategy is not only convenient and sensitive, but also has a tunable dynamic range. The platform is also applicable for the initial screening of a telomerase inhibitor to discover new anticancer drugs.We developed a novel telomere complementary (TC) oligonucleotide modified AuNP probe (TC-AuNPs) for colorimetric analysis of telomerase activity. The mechanism of this method is that the telomerase reaction products (TRP), which can hybridize with the TC-AuNPs, are able to protect the AuNPs from the aggregation induced by salt. It is demonstrated that the colorimetric method enabled the analysis of the telomerase activity in 1000 HeLa cells with the naked eye, and down to 100 HeLa cells with the aid of UV-Vis spectroscopy. This strategy is not only convenient and sensitive, but also has a tunable dynamic range. The platform is also applicable for the initial screening of a telomerase inhibitor to discover new anticancer drugs. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr05185d

Endo-symbiont mediated synthesis of gold nanobactericides and their activity against human pathogenic bacteria.

PubMed

Syed, Baker; M N, Nagendra Prasad; K, Mohan Kumar; B L, Dhananjaya; Satish, Sreedharamurthy

2017-06-01

Synthesis of gold nanobactericides (AuNBs) were achieved by treating 1mM chloroaurate with cell free supernatant of Aneurinibacillus migulanus. Formation of AuNBs was initially was monitored with change in colour to ruby red. Further confirmation was assessed with UV-visible spectra with maximum absorption occurring at 510nm. Transmission electron microscopy (TEM) analysis revealed the polydispersity of AuNBs with size distribution ranging from 10 to 60nm with an average size of 30nm. Crystalline nature was studied using X-ray diffraction which exhibited characteristic peaks indexed to Bragg's reflection at 2θ angle which confers (111), (200), (220), and (311) planes suggesting AuNBs were face-centred cubic. Fourier transform infrared spectroscopy (FTIR) analysis revealed absorption peaks occurring at 3341cm -1 , 1635cm -1 and 670cm -1 which corresponds to functional groups attributing to synthesis. The antibacterial efficacy of AuNBs was tested against selective human pathogenic bacteria and activity was measured as zone of inhibition by using disc and well diffusion. Bactericidal activity was interpreted with standard antibiotics gentamicin and kanamycin. Micro broth dilution assay expressed the minimal concentration of AuNBs to inhibit the growth of test pathogens. Highest activity was observed against Pseudomonas aeruginosa (MTCC 7903) with 21.00±0.57mm compared to other pathogens. The possible mode of action of AuNBs on DNA was carried out with in vitro assay as preliminary test against pathogenic DNA isolated from P. aeruginosa. Further studies will be interesting enough to reveal the exact interactive mechanism of AuNBs with DNA. Overall study contributes towards biogenic synthesis of AuNBs as one of the alternative in combating drug resistant pathogens. Copyright © 2017 Elsevier B.V. All rights reserved.

Hierarchically assembled Au microspheres and sea urchin-like architectures: formation mechanism and SERS study

NASA Astrophysics Data System (ADS)

Wang, Xiansong; Yang, Da-Peng; Huang, Peng; Li, Min; Li, Chao; Chen, Di; Cui, Daxiang

2012-11-01

The hierarchically assembled Au microspheres/sea urchin-like structures have been synthesized in aqueous solution at room temperature with and without proteins (bovine serum albumin, BSA) as mediators. The average diameter of an individual Au microsphere is 300-600 nm, which is composed of some compact nanoparticles with an average diameter of about 15 nm. Meanwhile, the sea urchin-like Au architecture exhibits an average diameter of 600-800 nm, which is made up of some nanopricks with an average length of 100-200 nm. These products are characterized by means of scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electronic microscopy (TEM). It is found that the BSA and ascorbic acid (AA) have great effects on the morphology of the resulting products. Two different growth mechanisms are proposed. The study on surface enhanced Raman scattering (SERS) activities is also carried out between Au microspheres and Au sea urchin-like architectures. It is found that Au urchin-like architectures possess much higher SERS activity than the Au microspheres. Our work may shed light on the design and synthesis of hierarchically self-assembled 3D micro/nano-architectures for SERS, catalysis and biosensors.The hierarchically assembled Au microspheres/sea urchin-like structures have been synthesized in aqueous solution at room temperature with and without proteins (bovine serum albumin, BSA) as mediators. The average diameter of an individual Au microsphere is 300-600 nm, which is composed of some compact nanoparticles with an average diameter of about 15 nm. Meanwhile, the sea urchin-like Au architecture exhibits an average diameter of 600-800 nm, which is made up of some nanopricks with an average length of 100-200 nm. These products are characterized by means of scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electronic microscopy (TEM). It is found that the BSA and ascorbic acid (AA) have great effects on the morphology of the resulting products. Two different growth mechanisms are proposed. The study on surface enhanced Raman scattering (SERS) activities is also carried out between Au microspheres and Au sea urchin-like architectures. It is found that Au urchin-like architectures possess much higher SERS activity than the Au microspheres. Our work may shed light on the design and synthesis of hierarchically self-assembled 3D micro/nano-architectures for SERS, catalysis and biosensors. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr32405a

A nanoparticle-based epigenetic modulator for efficient gene modulation

NASA Astrophysics Data System (ADS)

Pongkulapa, Thanapat

Modulation of gene expression through chromatin remodeling involves epigenetic mechanisms, such as histone acetylation. Acetylation is tightly regulated by two classes of enzymes, histone acetyltransferases (HATs) and histone deacetylases (HDACs). Molecules that can regulate these enzymes by altering (activating or inhibiting) their functions have become a valuable tool for understanding cell development and diseases. HAT activators, i.e. N-(4-Chloro-(3-trifluoromethyl)phenyl)-2-ethoxybenzamide (CTB), have shown a therapeutic potential for many diseases, including cancer and neurodegeneration. However, these compounds encounter a solubility and a membrane permeability issue, which restricts their full potential for practical usage, especially for in vivo applications. To address this issue, in this work, we developed a nanoparticle-based HAT activator CTB, named Au-CTB, by incorporating a new CTB analogue onto gold nanoparticles (AuNPs) along with a poly(ethylene glycol) moiety and a nuclear localization signal (NLS) peptide to assist with solubility and membrane permeability. We found that our new CTB analogue and Au-CTB could activate HAT activity. Significantly, an increase in potency to activate HAT activity by Au-CTB proved the effectiveness of using the nanoparticle delivery platform. In addition, the versatility of Au-CTB platform permits the attachment of multiple ligands with tunable ratios on the nanoparticle surface via facile surface functionalization of gold nanoparticles. Due to its high delivery efficiency and versatility, Au-CTB can be a powerful platform for applications in epigenetic regulation of gene expression.

Surface Modifications during a Catalytic Reaction: A Combined APT and FIB/SEM Analysis of Surface Segregation

DOE PAGES

Barroo, Cedric; Janvelyan, Nare; Zugic, Branko; ...

2016-07-25

To improve the understanding of catalytic processes, the surface structure and composition of the active materials need to be determined before and after reaction. Morphological changes may occur under reaction conditions and can dramatically influence the reactivity and/or selectivity of a catalyst. Goldbased catalysts with different architectures are currently being developed for selective oxidation reactions at low temperatures. Specifically, nanoporous Au (npAu) with a composition of Au 97-Ag 3 is obtained by dealloying a Ag 70-Au 30 bulk alloy. Recent studies highlight the efficiency of npAu catalysts for methanol oxidation using ozone to activate the catalysts before methanol oxidation. Inmore » this paper, we studied the morphological and compositional changes occurring at the surface of Au-based catalysts in certain conditions.« less

Long Term Measurement of the Vapor Pressure of Gold in the Au-C System

NASA Technical Reports Server (NTRS)

Copland, Evan H.

2009-01-01

Incorporating the {Au(s,l) + graphite} reference in component activity measurements made with the multiple effusion-cell vapor source mass spectrometry (multicell KEMS) technique provides a fixed temperature defining ITS-90 (T(sub mp)(Au) = 1337.33K) and a systematic method to check accuracy. Over a 2 year period delta H sub(298)Au was determined by the 2nd and 3rd law methods in 25 separate experiments and were in the ranges 362.2 plus or minus 3.3 kJmol(sup -1) and 367.8 plus or minus 1.1 kJmol(sup -1), respectively. This 5 kJmol-1 discrepancy is transferred directly to the measured activities. This is unacceptable and the source of this discrepancy needs to be understood and corrected. Accepting the 2nd law value increases p(Au) by about 50 percent, brings the 2nd and 3rd law values into agreement and removes the T dependence in the 3rd law values. While compelling, there is no way to independently determine instrument sensitivities, S(sub Au), with T in a single experiment with KEMS. This lack of capability is stopping a deeper understanding of this problem. In addition, the Au-C phase diagram suggests a eutectic invariant reaction: L-Au(4.7at%C) = FCC-Au(0.08at%C) + C(graphite) at T(sub e) approximately 1323K. This high C concentration in Au(l) must reduce p(Au) in equilibrium with {Au(s,l) + graphite} and raises some critical questions about the Gibbs free energy functions of Au(s,l) and the Au fixed point (T(sub mp)(Au) = 1337.33K) which is always measured in graphite.

Enhanced photocatalytic H{sub 2} evolution over CdS/Au/g-C{sub 3}N{sub 4} composite photocatalyst under visible-light irradiation

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

Ding, Xiaoling; University of Chinese Academy of Sciences, Beijing 100049; Li, Yingxuan, E-mail: yxli@ms.xjb.ac.cn, E-mail: cywang@ms.xjb.ac.cn

2015-10-01

A novel heterojunction structured composite photocatalyst CdS/Au/g-C{sub 3}N{sub 4} has been developed by depositing CdS/Au with a core (Au)-shell (CdS) structure on the surface of g-C{sub 3}N{sub 4}. The photocatalytic hydrogen production activity of the developed photocatalyst was evaluated under visible-light irradiation (λ > 420 nm) using methanol as a sacrificial reagent. As a result, its activity is about 125.8 times higher than that of g-C{sub 3}N{sub 4} and is even much higher than that of Pt/g-C{sub 3}N{sub 4}. The enhancement in photocatalytic activity is attributed to efficient separation of the photoexcited charges due to the anisotropic junction in themore » CdS/Au/g-C{sub 3}N{sub 4} system.« less

Theophylline-assisted, eco-friendly synthesis of PtAu nanospheres at reduced graphene oxide with enhanced catalytic activity towards Cr(VI) reduction.

PubMed

Hu, Ling-Ya; Chen, Li-Xian; Liu, Meng-Ting; Wang, Ai-Jun; Wu, Lan-Ju; Feng, Jiu-Ju

2017-05-01

Theophylline as a naturally alkaloid is commonly employed to treat asthma and chronic obstructive pulmonary disorder. Herein, a facile theophylline-assisted green approach was firstly developed for synthesis of PtAu nanospheres/reduced graphene oxide (PtAu NSs/rGO), without any surfactant, polymer, or seed involved. The obtained nanocomposites were applied for the catalytic reduction and removal of highly toxic chromium (VI) using formic acid as a model reductant at 50°C, showing the significantly enhanced catalytic activity and improved recyclability when compared with commercial Pt/C (50%) and home-made Au nanocrystals supported rGO (Au NCs/rGO). It demonstrates great potential applications of the catalyst in wastewater treatment and environmental protection. The eco-friendly route provides a new platform to fabricate other catalysts with enhanced catalytic activity. Copyright © 2016 Elsevier Inc. All rights reserved.

A density functional theory study on the acetylene cyclotrimerization on Pd-modified Au(111) surface

NASA Astrophysics Data System (ADS)

Ren, Bohua; Dong, Xiuqin; Yu, Yingzhe; Zhang, Minhua

2017-10-01

Calculations based on the first-principle density functional theory were carried out to study the possible acetylene cyclotrimerization reactions on Pd-Au(111) surface and to investigate the effect of Au atom alloying with Pd. The adsorption of C2H2, C4H4, C6H6 and the PDOS of 4d orbitals of surface Pd and Au atoms were studied. The comparison of d-band center of Pd and Au atom before and after C2H2 or C4H4 adsorption suggests that these molecules affect the activity of Pd-Au(111) surface to some degree due to the high binding energy of the adsorption. In our study, the second neighboring Pd ensembles on Pd-Au(111) surface can adsorb two acetylene molecules on parallel-bridge site of two Au atoms and one Pd atom, respectively. Csbnd C bonds are parallel to each other and two acetylenes are adsorbed face to face to produce four-membered ring C4H4 firstly. The geometric effect and electronic effect of Pd-Au(111) surface with the second neighboring Pd ensembles both help to reduce this activation barrier.

A facile construction of Au nanoparticles stabilized by thermo-responsive polymer-tethered carbon dots for enhanced catalytic performance

NASA Astrophysics Data System (ADS)

Li, Li; Zhang, Tianyi; Lü, Jianhua; Lü, Changli

2018-10-01

Carbon dots (CDs), the youngest member in the carbon nanomaterial family, have drawn considerable attention due to their interesting optical, physicochemical and electronic properties as well as broad promising applications. Here, we developed a facile and effective strategy for the preparation of Au nanoparticles stabilized by thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) functionalized carbon dots (Au@CD@P) under the gentle water media. The as-designed dopamine(DA)-terminated PNIPAM can be easily anchored to CDs via mussel-inspired chemistry route. Both CD@P and CDs could well stabilize the Au nanoparticles with interesting assembled structure. The as-prepared Au@CD and Au@CD@P nanohybrids with good dispersibility and stability exhibited the intriguing catalytic activity for reduction of p-nitrophenol (p-NP). Especially, Au@CD@P as catalyst also played a switching role in regulating the catalytic rate by temperature. In addition, Au@CD@P exhibited excellent recyclability which may have potential in green chemical industry for developing high-activity catalysts and easy production methods.

Bimetallic Pt-Au Nanocatalysts on ZnO/Al2O3/Monolith for Air Pollution Control.

PubMed

Kim, Ki-Joong; Ahn, Ho-Geun

2015-08-01

The catalytic activity of a monolithic catalyst with nanosized Pt and Au particles on ZnO/Al2O3 (Pt-Au/ZnO/Al2O3/M) prepared by a wash-coat method was examined, specifically for toluene oxidation. Scanning electron microscopy image showed clearly the formation of a ZnO/Al2O3 layer on the monolith. Nanosized Pt-Au particles on ZnO/Al2O3/M with different sizes could be found in the Pt-Au/ZnO/Al2O3/M catalyst. The conversion of toluene decreased with increasing toluene concentration and was also largely affected by the feed flow rate. The Pt-Au/ZnO/Al2O3/M catalysts prepared in this work have almost the same activity (molecules of toluene per second) compared with a powder Pt-Au/ZnO/Al2O3 catalyst with the same loadings of Pt and Au components; thus this catalyst could be used in controlling air pollution with very low concentrations and high flow rate.

A further insight into the biosorption mechanism of Au(III) by infrared spectrometry

PubMed Central

2011-01-01

Background The interactions of microbes with metal ions form an important basis for our study of biotechnological applications. Despite the recent progress in studying some properties of Au(III) adsorption and reduction by Bacillus megatherium D01 biomass, there is still a need for additional data on the molecular mechanisms of biosorbents responsible for their interactions with Au(III) to have a further insight and to make a better exposition. Results The biosorption mechanism of Au(III) onto the resting cell of Bacillus megatherium D01 biomass on a molecular level has been further studied here. The infrared (IR) spectroscopy on D01 biomass and that binding Au(III) demonstrates that the molecular recognition of and binding to Au(III) appear to occur mostly with oxygenous- and nitrogenous-active groups of polysaccharides and proteins in cell wall biopolymers, such as hydroxyl of saccharides, carboxylate anion of amino-acid residues (side-chains of polypeptide backbone), peptide bond (amide I and amide II bands), etc.; and that the active groups must serve as nucleation sites for Au(0) nuclei growth. A further investigation on the interactions of each of the soluble hydrolysates of D01, Bacillus licheniformis R08, Lactobacillus sp. strain A09 and waste Saccharomyces cerevisiae biomasses with Au(III) by IR spectrometry clearly reveals an essential biomacromolecule-characteristic that seems the binding of Au(III) to the oxygen of the peptide bond has caused a significant, molecular conformation-rearrangement in polypeptide backbones from β-pleated sheet to α-helices and/or β-turns of protein secondary structure; and that this changing appears to be accompanied by the occurrence, in the peptide bond, of much unbound -C=O and H-N- groups, being freed from the inter-molecular hydrogen-bonding of the β-pleated sheet and carried on the helical forms, as well as by the alternation in side chain steric positions of protein primary structure. This might be reasonably expected to result in higher-affinity interactions of peptide bond and side chains with Au(III). Conclusions The evidence suggests that the polypeptides appear to be activated by the intervention of Au(III) via the molecular reconformation and in turn react upon Au(III) actively and exert profound impacts on the course of Au(0) nucleation and crystal growth. PMID:22032692

On the Effect of Native SiO2 on Si over the SPR-mediated Photocatalytic Activities of Au and Ag Nanoparticles.

PubMed

Wang, Jiale; de Freitas, Isabel C; Alves, Tiago V; Ando, Romulo A; Fang, Zebo; Camargo, Pedro H C

2017-05-29

In hybrid materials containing plasmonic nanoparticles such as Au and Ag, charge-transfer processes from and to Au or Ag can affect both activities and selectivity in plasmonic catalysis. Inspired by the widespread utilization of commercial Si wafers in surface-enhanced Raman spectroscopy (SERS) studies, we investigated herein the effect of the native SiO 2 layer on Si wafers over the surface plasmon resonance (SPR)-mediated activities of the Au and Ag nanoparticles (NPs). We prepared SERS-active plasmonic comprised of Au and Ag NPs deposited onto a Si wafer. Here, two kinds of Si wafers were employed: Si with a native oxide surface layer (Si/SiO 2 ) and Si without a native oxide surface layer (Si). This led to Si/SiO 2 /Au, Si/SiO 2 /Ag, Si/Au, and Si/Ag NPs. The SPR-mediated oxidation of p-aminothiophenol (PATP) to p,p'-dimercaptoazobenzene (DMAB) was employed as a model transformation. By comparing the performances and band structures for the Si/Au and Si/Ag relative to Si/SiO 2 /Au and Si/SiO 2 /Ag NPs, it was found that the presence of a SiO 2 layer was crucial to enable higher SPR-mediated PATP to DMAB conversions. The SiO 2 layer acts to prevent the charge transfer of SPR-excited hot electrons from Au or Ag nanoparticles to the Si substrate. This enabled SPR-excited hot electrons to be transferred to adsorbed O 2 molecules, which then participate in the selective oxidation of PATP to DMAB. In the absence of a SiO 2 layer, SPR-excited hot electrons are preferentially transferred to Si instead of adsorbed O 2 molecules, leading to much lower PATP oxidation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced selective photocatalytic reduction of CO2 to CH4 over plasmonic Au modified g-C3N4 photocatalyst under UV-vis light irradiation

NASA Astrophysics Data System (ADS)

Li, Hailong; Gao, Yan; Xiong, Zhuo; Liao, Chen; Shih, Kaimin

2018-05-01

A series of Au-g-C3N4 (Au-CN) catalysts were prepared through a NaBH4-reduction method using g-C3N4 (CN) from pyrolysis of urea as precursor. The catalysts' surface area, crystal structure, surface morphology, chemical state, functional group composition and optical properties were characterized by X-ray diffraction, transmission electron microscope, X-ray photoelectron spectroscopy, ultraviolet visible (UV-vis) diffuse reflectance spectra, fourier transform infrared, photoluminescence and transient photocurrent analysis. The carbon dioxide (CO2) photoreduction activities under ultraviolet visible (UV-vis) light irradiation were significantly enhanced when gold (Au) was loaded on the surface of CN. 2Au-CN catalyst with Au to CN mole ratio of 2% showed the best catalytic activity. After 2 h UV-vis light irradiation, the methane (CH4) yield over the 2Au-CN catalyst was 9.1 times higher than that over the pure CN. The CH4 selectivity also greatly improved for the 2Au-CN compared to the CN. The deposited Au nanoparticles facilitated the separation of electron-hole pairs on the CN surface. Moreover, the surface plasmon resonance effect of Au further promoted the generation of hot electrons and visible light absorption. Therefore, Au loading significantly improved CO2 photoreduction performance of CN under UV-vis light irradiation.

Regulating Surface Facets of Metallic Aerogel Electrocatalysts by Size-dependent Localized Ostwald Ripening.

PubMed

Wenchao, Duan; Zhang, Peina; Xiahou, Yujiao; Song, Yahui; Bi, Cuixia; Zhan, Jie; Du, Wei; Huang, Lihui; Möhwald, Helmuth; Xia, Haibing

2018-06-21

It is well known that the activity and stability of electrocatalysts are largely dependent on their surface facets. In this work, we have successfully regulated surface facets of three-dimensional (3D) metallic Au m-n aerogels by salt-induced assembly of citrate-stabilized gold nanoparticles (Au NPs) of two different sizes and further size-dependent localized Ostwald ripening at controlled particle-number ratios, where m and n represent the size of Au NPs, respectively. In addition, 3D Au m-n @Pd aerogels were further synthesized on the basis of Au m-n aerogels and also bear controlled surface facets due to the formation of ultrathin Pd layers on Au m-n aerogels. Taking the electrooxidation of small organic molecules (such as methanol and ethanol) by the resulting Au m-n and Au m-n @Pd aerogels as examples, it is found that surface facets of metallic aerogels with excellent performance can be regulated to realize preferential surface facets for methanol oxidation and ethanol oxidation, respectively. Moreover, they also indeed simultaneously bear high activity and excellent stability. Furthermore, their activities and stability are also highly dependent on the area ratio of active facets and inactive facets on their surfaces, respectively, and these ratios are varied via the mismatch of sizes of adjacent nanoparticles. Thus, this work not only demonstrates the realization of the regulation of the surface facets of metallic aerogels by size-dependent localized Ostwald ripening, but also will open up a new way to improve electrocatalytic performance of three-dimensional metallic aerogels by surface regulation.

An evidence on G2/M arrest, DNA damage and caspase mediated apoptotic effect of biosynthesized gold nanoparticles on human cervical carcinoma cells (HeLa)

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

Jeyaraj, M.; Arun, R.; Sathishkumar, G.

2014-04-01

Highlights: • Gold nanoparticles (AuNPs) have been synthesized using Podophyllum hexandrum L. • AuNPs induces the oxidative stress to cell death in human cervical carcinoma cells. • It activates the caspase-cascade to cellular death. • It is actively blocks G2/M phase of cell cycle. - Abstract: Current prospect of nanobiotechnology involves in the greener synthesis of nanostructured materials particularly noble metal nanoparticles for various biomedical applications. In this study, biologically (Podophyllum hexandrum L.) synthesized crystalline gold nanoparticles (AuNPs) with the size range between 5 and 35 nm were screened for its anticancereous potential against human cervical carcinoma cells (HeLa). Stoichiometricmore » proportion of the reaction mixture and conditions were optimized to attain stable nanoparticles with narrow size range. Different high throughput techniques like transmission electron microscope (TEM), X-ray diffraction (XRD) and UV–vis spectroscopy were adopted for the physio-chemical characterization of AuNPs. Additionally, Fourier transform infrared spectroscopy (FTIR) study revealed that the water soluble fractions present in the plant extract solely influences the reduction of AuNPs. Sublimely, synthesized AuNPs exhibits an effective in vitro anticancer activity against HeLa cells via induction of cell cycle arrest and DNA damage. Furthermore, it was evidenced that AuNPs treated cells are undergone apoptosis through the activation of caspase cascade which subsequently leads to mitochondrial dysfunction. Thereby, this study proves that biogenic colloidal AuNPs can be developed as a promising drug candidature for human cervical cancer therapy.« less

Catalytic reduction of 4-nitrophenol using gold nanoparticles biosynthesized by cell-free extracts of Aspergillus sp. WL-Au.

PubMed

Shen, Wenli; Qu, Yuanyuan; Pei, Xiaofang; Li, Shuzhen; You, Shengnan; Wang, Jingwei; Zhang, Zhaojing; Zhou, Jiti

2017-01-05

A facile one-pot eco-friendly process for synthesis of gold nanoparticles (AuNPs) with high catalytic activity was achieved using cell-free extracts of Aspergillus sp. WL-Au as reducing, capping and stabilizing agents. The surface plasmon resonance band of UV-vis spectrum at 532nm confirmed the presence of AuNPs. Transmission electron microscopy images showed that quite uniform spherical AuNPs were synthesized and the average size of nanoparticles increased from 4nm to 29nm with reaction time. X-ray diffraction analysis verified the formation of nano-crystalline gold particles. Fourier transform infrared spectra showed the presence of functional groups on the surface of biosynthesized AuNPs, such as OH, NH, CO, CH, COH and COC groups, which increased the stability of AuNPs. The biogenic AuNPs could serve as a highly efficient catalyst for 4-nitrophenol reduction. The reaction rate constant was linearly correlated with the concentration of AuNPs, which increased from 0.59min -1 to 1.51min -1 with the amount of AuNPs increasing form 1.46×10 -6 to 17.47×10 -6 mmol. Moreover, the as-synthesized AuNPs exhibited a remarkable normalized catalytic activity (4.04×10 5 min -1 mol -1 ), which was much higher than that observed for AuNPs synthesized by other biological and conventional chemical methods. Copyright © 2016 Elsevier B.V. All rights reserved.

Sunlight-Induced photochemical synthesis of Au nanodots on α-Fe2O3@Reduced graphene oxide nanocomposite and their enhanced heterogeneous catalytic properties.

PubMed

Bharath, G; Anwer, Shoaib; Mangalaraja, R V; Alhseinat, Emad; Banat, Fawzi; Ponpandian, N

2018-04-09

In this present study, we report the synthesis of Au nanodots on α-Fe 2 O 3 @reduced graphene oxide (RGO) based hetero-photocatalytic nanohybrids through a chlorophyll mediated photochemical synthesis. In this process, chlorophyll induces a rapid reduction (30 min) of Au 3+ ions to Au° metallic nanodots on α-Fe 2 O 3 @RGO surface under sunlight irradiation. The nucleation growth process, photo-induced electron-transfer mechanism and physico-chemical properties of the Au@α-Fe 2 O 3 @RGO ternary nanocomposites were systematically studied with various analytical techniques. This novel photochemical synthesis process is a cost-effective, convenient, surfactant-less, and scalable method. Moreover, the prepared ternary nanocomposites enhanced catalytic activity as compared to pure α-Fe 2 O 3 and α-Fe 2 O 3 @RGO. The advantages and synergistic effect of Au@α-Fe 2 O 3 @RGO exhibit, (i) a broader range of visible-light absorption due to visible light band gap of α-Fe 2 O 3 , (ii) lower recombination possibility of photo-generated electrons and holes due to effect of Au and (iii) faster electron transfer due to higher conductivity of RGO. Therefore, the prepared Au@α-Fe 2 O 3 @RGO hetero-photocatalytic nanohybrids exhibited a remarkable photocatalytic activity, thus enabling potential active hetero-photocatalyst for industrial and environmental applications.

Role of Au-C Interactions on the Catalytic Activity of Au Nanoparticles Supported on TiC(001) Towards Molecular Oxygen Dissociation

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

Rodriguez, J.A.; Feria, L.; Jirsak, T.

2010-03-10

High-resolution photoemission and density functional calculations on realistic slab surface models were used to study the interaction and subsequent dissociation of O{sub 2} with Au nanoparticles supported on TiC(001). The photoemission results indicate that at 150 K O{sub 2} adsorbs molecularly on the supported gold nanoparticles, and upon heating to temperatures above 200 K the O{sub 2} {yields} 2O reaction takes place with migration of atomic oxygen to the TiC(001) substrate. The addition of Au to TiC(001) substantially enhances the rate of O{sub 2} dissociation at room temperature. The reactivity of Au nanoparticles supported on TiC(001) toward O{sub 2} dissociationmore » is much larger than that of similar nanoparticles supported either on TiO{sub 2}(110) or MgO(001) surfaces, where the cleavage of O-O bonds is very difficult. Density functional calculations carried out on large supercells show that the contact of Au with TiC(001) is essential for charge polarization and an enhancement in the chemical activity of Au. Small two-dimensional particles which expose Au atoms in contact with TiC(001) are the most reactive. While O{sub 2} prefers binding to Au sites, the O atoms interact more strongly with the TiC(001) surface. The oxygen species active during the low-temperature (<200 K) oxidation of carbon monoxide on Au/TiC(001) is chemisorbed O{sub 2}. Once atomic O binds to TiC(001), the chemisorption bond is so strong that temperatures well above 400 K are necessary to remove the O adatoms from the TiC(001) substrate by direct reaction with CO. The high reactivity of Au/TiC(001) toward O{sub 2} at low-temperature opens the route for the transformation of alcohols and amines on the supported Au nanoparticles.« less

Role of Au-C Interactions on the Catalytic Activity of Au Nanoparticles Supported on TiC(001) toward Molecular Oxygen Dissociation

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

Rodriguez, J.; Feria, L; Jirsak, T

2010-01-01

High-resolution photoemission and density functional calculations on realistic slab surface models were used to study the interaction and subsequent dissociation of O{sub 2} with Au nanoparticles supported on TiC(001). The photoemission results indicate that at 150 K O{sub 2} adsorbs molecularly on the supported gold nanoparticles, and upon heating to temperatures above 200 K the O{sub 2} {yields} 2O reaction takes place with migration of atomic oxygen to the TiC(001) substrate. The addition of Au to TiC(001) substantially enhances the rate of O{sub 2} dissociation at room temperature. The reactivity of Au nanoparticles supported on TiC(001) toward O{sub 2} dissociationmore » is much larger than that of similar nanoparticles supported either on TiO{sub 2}(110) or MgO(001) surfaces, where the cleavage of O-O bonds is very difficult. Density functional calculations carried out on large supercells show that the contact of Au with TiC(001) is essential for charge polarization and an enhancement in the chemical activity of Au. Small two-dimensional particles which expose Au atoms in contact with TiC(001) are the most reactive. While O{sub 2} prefers binding to Au sites, the O atoms interact more strongly with the TiC(001) surface. The oxygen species active during the low-temperature (<200 K) oxidation of carbon monoxide on Au/TiC(001) is chemisorbed O{sub 2}. Once atomic O binds to TiC(001), the chemisorption bond is so strong that temperatures well above 400 K are necessary to remove the O adatoms from the TiC(001) substrate by direct reaction with CO. The high reactivity of Au/TiC(001) toward O{sub 2} at low-temperature opens the route for the transformation of alcohols and amines on the supported Au nanoparticles.« less

Analysis of groundwater discharge with a lumped-parameter model, using a case study from Tajikistan

NASA Astrophysics Data System (ADS)

Pozdniakov, S. P.; Shestakov, V. M.

A lumped-parameter model of groundwater balance is proposed that permits an estimate of discharge variability in comparison with the variability of recharge, by taking into account the influence of aquifer parameters. Recharge-discharge relationships are analysed with the model for cases of deterministic and stochastic recharge time-series variations. The model is applied to study the temporal variability of groundwater discharge in a river valley in the territory of Tajikistan, an independent republic in Central Asia. Résumé Un modèle global de bilan d'eau souterraine a été développé pour estimer la variabilité de l'écoulement par rapport à celle de la recharge, en prenant en compte l'influence des paramètres de l'aquifère. Les relations entre recharge et écoulement sont analysées à l'aide du modèle pour des variations des chroniques de recharge soit déterministes, soit stochastiques. Le modèle est appliquéà l'étude de la variabilité temporelle de l'écoulement souterrain vers une rivière, dans le Tadjikistan, une république indépendante d'Asie centrale. Resumen Se propone un modelo de parámetros concentrados para realizar el balance de aguas subterráneas, el cual permite estimar la variabilidad en la descarga con respecto a la variabilidad en la recarga, en función de los parámetros que caracterizan el acuífero. Las relaciones entre recarga y descarga se analizan con el modelo para distintos casos de series temporales de recarga, tanto deterministas como estocásticas. El modelo se aplica al estudio de la variabilidad temporal de la descarga en un valle aluvial de Tadyikistán, una república independiente del Asia Central.

Facile Photochemical Synthesis of Au/Pt/g-C3N4 with Plasmon-Enhanced Photocatalytic Activity for Antibiotic Degradation.

PubMed

Xue, Jinjuan; Ma, Shuaishuai; Zhou, Yuming; Zhang, Zewu; He, Man

2015-05-13

A novel plasmonic photocatalyst, Au/Pt/g-C3N4, was prepared by a facile calcination-photodeposition technique. The samples were characterized by X-ray diffraction, energy-dispersive spectroscopy, transmission electron microscopy, and UV-vis diffuse reflectance spectroscopy, and the results demonstrated that the Au and Pt nanoparticles (7-15 nm) were well-dispersed on the surfaces of g-C3N4. The Au/Pt codecorated g-C3N4 heterostructure displayed enhanced photocatalytic activity for antibiotic tetracycline hydrochloride (TC-HCl) degradation, and the degradation rate was 3.4 times higher than that of pure g-C3N4 under visible light irradiation. The enhancement of photocatalytic activity could be attributed to the surface plasmon resonance effect of Au and electron-sink function of Pt nanoparticles, which improve the optical absorption property and photogenerated charge carriers separation of g-C3N4, synergistically facilitating the photocatalysis process. Finally, a possible photocatalytic mechanism for degrading TC-HCl by Au/Pt/g-C3N4 heterostructure was tentatively proposed.

Gallic acid-capped gold nanoparticles inhibit EGF-induced MMP-9 expression through suppression of p300 stabilization and NFκB/c-Jun activation in breast cancer MDA-MB-231 cells

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

Chen, Ying-Jung; Lee, Yuan-Chin; Huang, Chia-Hui

Triple-negative breast cancers (TNBCs) are highly invasive and have a higher rate of distant metastasis. Matrix metalloproteinase-9 (MMP-9) plays a crucial role in EGF/EGFR-mediated malignant progression and metastasis of TNBCs. Various studies have revealed that treatment with gallic acid down-regulates MMP-9 expression in cancer cells, and that conjugation of phytochemical compounds with gold nanoparticles (AuNPs) increases the anti-tumor activity of the phytochemical compounds. Thus, the effect of gallic acid-capped AuNPs (GA-AuNPs) on MMP-9 expression in EGF-treated TNBC MDA-MB-231 cells was analyzed in the present study. The so-called green synthesis of AuNPs by means of gallic acid was performed at pHmore » 10, and the resulting GA-AuNPs had spherical shape with an average diameter of approximately 50 nm. GA-AuNPs notably suppressed migration and invasion of EGF-treated cells, and inhibited EGF-induced MMP-9 up-regulation. GA-AuNPs abrogated EGF-induced Akt/p65 and ERK/c-Jun phosphorylation, leading to down-regulation of MMP-9 mRNA and protein expression in EGF-treated cells. Meanwhile, EGF-induced p300 stabilization was found to be involved in MMP-9 expression, whereas GA-AuNPs inhibited the EGF-promoted stability of the p300 protein. Although GA-AuNPs and gallic acid suppressed EGF-induced MMP-9 up-regulation via the same signaling pathway, the effective concentration of gallic acid was approximately 100-fold higher than that of GA-AuNPs for inhibition of MMP-9 expression in EGF-treated cells to a similar extent. Collectively, our data indicate that, in comparison with gallic acid, GA-AuNPs have a superior ability to inhibit EGF/EGFR-mediated MMP-9 expression in TNBC MDA-MB-231 cells. Our findings also point to a way to improve the anti-tumor activity of gallic acid. - Highlights: • Gallic acid-capped gold nanoparticles inhibit EGF-induced MMP-9 expression. • EGF-induced MMP-9 expression via p300 stabilization and NFκB/c-Jun activation. • Gallic acid-capped gold nanoparticles inhibit EGF-modulated p300 stabilization. • Gallic acid-capped gold nanoparticles abrogate EGF-induced NFκB/c-Jun activation.« less

Simultaneous electrochemical detection of dopamine and uric acid over ceria supported three dimensional gold nanoclusters

NASA Astrophysics Data System (ADS)

Palanisamy, Sivakumar

2014-12-01

CeO2 is well known for being an active material to support the growth of Au nanoclusters (Au NCs). In this work, three dimensional (3D) Au NCs were deposited on three different shaped CeO2 nanostructures such as nanoparticles (NPs), nanorod arrays (NRAs) and nanoflowers (NFs) modified Ti substrate for electrochemical simultaneous detection of dopamine (DA) and uric acid (UA). The electrodeposition of 3D Au NCs were carried out via cyclic voltammetric (CV) method at over-potential, while CeO2 nanostructures were deposited by galvanostatic constant current method under the optimized conditions. The morphology and elemental composition analysis of 3D Au NCs with CeO2 nanostructures were characterized by SEM, XRD, XPS and EDAX measurements. The electrocatalytic activity of 3D Au NCs on different CeO2 supports were thoroughly investigated by using voltammetric and amperometric techniques. According to the obtained results, CeO2 NPs supported 3D Au NCs (3D Au NCs@CeO2 NPs) displayed strong signal for DA as compared to that of CeO2 NRAs (3D Au NCs@CeO2 NRAs) and CeO2 NFs supported 3D Au NCs (3D Au NCs@CeO2 NFs). In addition, the 3D Au NCs@CeO2 NPs electrode resulted in more sensitive and simultaneous detection of DA in the presence of excess UA. Thus, the 3D Au NCs@CeO2 NPs electrode can practically be applied for the detection of DA using biological samples.

Ozone-Activated Nanoporous Gold: A Stable and Storable Material for Catalytic Oxidation

DOE PAGES

Personick, Michelle L.; Zugic, Branko; Biener, Monika M.; ...

2015-05-28

We report a new method for facile and reproducible activation of nanoporous gold (npAu) materials of different forms for the catalytic selective partial oxidation of alcohols under ambient pressure, steady flow conditions. This method, based on the surface cleaning of npAu ingots with ozone to remove carbon documented in ultrahigh vacuum conditions, produces active npAu catalysts from ingots, foils, and shells by flowing an ozone/dioxygen mixture over the catalyst at 150 °C, followed by a temperature ramp from 50 to 150 °C in a flowing stream of 10% methanol and 20% oxygen. With this treatment, all three materials (ingots, foils,more » and shells) can be reproducibly activated, despite potential carbonaceous poisons resulting from their synthesis, and are highly active for the selective oxidation of primary alcohols over prolonged periods of time. The npAu materials activated in this manner exhibit catalytic behavior substantially different from those activated under different conditions previously reported. Once activated in this manner, they can be stored and easily reactivated by flow of reactant gases at 150 °C for a few hours. They possess improved selectivity for the coupling of higher alcohols, such as 1-butanol, and are not active for carbon monoxide oxidation. As a result, this ozone-treated npAu is a functionally new catalytic material.« less

Ozone-Activated Nanoporous Gold: A Stable and Storable Material for Catalytic Oxidation

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

Personick, Michelle L.; Zugic, Branko; Biener, Monika M.

We report a new method for facile and reproducible activation of nanoporous gold (npAu) materials of different forms for the catalytic selective partial oxidation of alcohols under ambient pressure, steady flow conditions. This method, based on the surface cleaning of npAu ingots with ozone to remove carbon documented in ultrahigh vacuum conditions, produces active npAu catalysts from ingots, foils, and shells by flowing an ozone/dioxygen mixture over the catalyst at 150 °C, followed by a temperature ramp from 50 to 150 °C in a flowing stream of 10% methanol and 20% oxygen. With this treatment, all three materials (ingots, foils,more » and shells) can be reproducibly activated, despite potential carbonaceous poisons resulting from their synthesis, and are highly active for the selective oxidation of primary alcohols over prolonged periods of time. The npAu materials activated in this manner exhibit catalytic behavior substantially different from those activated under different conditions previously reported. Once activated in this manner, they can be stored and easily reactivated by flow of reactant gases at 150 °C for a few hours. They possess improved selectivity for the coupling of higher alcohols, such as 1-butanol, and are not active for carbon monoxide oxidation. As a result, this ozone-treated npAu is a functionally new catalytic material.« less

Fabrication of Te and Te-Au Nanowires-Based Carbon Fiber Fabrics for Antibacterial Applications

PubMed Central

Chou, Ting-Mao; Ke, Yi-Yun; Tsao, Yu-Hsiang; Li, Ying-Chun; Lin, Zong-Hong

2016-01-01

Pathogenic bacteria that give rise to diseases every year remain a major health concern. In recent years, tellurium-based nanomaterials have been approved as new and efficient antibacterial agents. In this paper, we developed the approach to directly grow tellurium nanowires (Te NWs) onto commercial carbon fiber fabrics and demonstrated their antibacterial activity. Those Te NWs can serve as templates and reducing agents for gold nanoparticles (Au NPs) to deposit. Three different Te-Au NWs with varied concentration of Au NPs were synthesized and showed superior antibacterial activity and biocompability. These results indicate that the as-prepared carbon fiber fabrics with Te and Te-Au NWs can become antimicrobial clothing products in the near future. PMID:26861380

Enhanced activity of CaFeMg layered double hydroxides-supported gold nanodendrites for the electrochemical evolution of oxygen and hydrogen in alkaline media

NASA Astrophysics Data System (ADS)

Havakeshian, Elaheh; Salavati, Hossein; Taei, Masoumeh; Hasheminasab, Fatemeh; Seddighi, Mohadeseh

2018-02-01

In this study, Au was electrodeposited on a support of CaFeMg layered double hydroxide and then, its catalytic activity was investigated for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Field emission scanning electron microscopy images showed that a uniform porous film of aggregated nano-particles of the LDH has been decorated with Au nanodendrite-like structures (AuNDs@LDH). The results obtained from polarization curves, Tafel plots and electrochemical impedance spectroscopy showed that the AuNDs@LDH exhibits lower overpotential, higher current density, faster kinetics and enhanced stability for both of the OER and HER, in comparison with the single AuNPs and LDH catalysts.

Self assembly of acetylcholinesterase on a gold nanoparticles–graphene nanosheet hybrid for organophosphate pesticide detection using polyelectrolyte as a linker

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

Wang, Ying; Zhang, Sheng; Du, Dan

A nanohybrid of gold nanoparticles (Au NPs) and chemically reduced graphene oxide nanosheets (cr-Gs) was synthesized by in situ growth of Au NPs on the surface of graphene nanosheets in the presence of poly(diallyldimethylammonium chloride) (PDDA), which not only improved the dispersion of Au NPs but also stabilized cholinesterase with high activity and loading efficiency. The obtained nanohybrid was characterized by TEM, XRD, XPS, and electrochemistry. Then an enzyme nanoassembly (AChE/Au NPs/cr-Gs) was prepared by self-assembling acetylcholinesterase (AChE) on Au NP/cr-Gs nanohybrid. An electrochemical sensor based on AChE/Au NPs/cr-Gs was further developed for ultrasensitive detection of organophosphate pesticide. The resultsmore » demonstrate that the developed approach provides a promising strategy to improve the sensitivity and enzyme activity of electrochemical biosensors.« less

Au plasmonics in a WS{sub 2}-Au-CuInS{sub 2} photocatalyst for significantly enhanced hydrogen generation

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

Cheng, Zhongzhou; School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083; Wang, Zhenxing, E-mail: wangzx@nanoctr.cn, E-mail: hej@nanoctr.cn

2015-11-30

Promoting the activities of photocatalysts is still the critical challenge in H{sub 2} generation area. Here, a Au plasmon enhanced photocatalyst of WS{sub 2}-Au-CuInS{sub 2} is developed by inserting Au nanoparticles between WS{sub 2} nanotubes and CuInS{sub 2} (CIS) nanoparticles. Due to the localized surface plasmonic resonance properties from Au nanoparticles, WS{sub 2}-Au-CIS shows the best performance as compared to Au-CIS, CIS, WS{sub 2}-CIS, CIS-Au, WS{sub 2}-Au, and WS{sub 2}-CIS-Au. The surface plasmonic resonance effects dramatically intensify the absorption of visible light and help to inject hot electrons into the semiconductors. Our findings open up an efficient method to optimizemore » the type-II structures for photocatalytic water splitting.« less

Gelatin-modified gold nanoparticles for direct detection of urinary total gelatinase activity: Diagnostic value in bladder cancer.

PubMed

Nossier, Ahmed I; Mohammed, Ola S; Fakhr El-Deen, Rasha R; Zaghloul, Ashraf S; Eissa, Sanaa

2016-12-01

Matrix metalloproteinases (MMPs), in particularly gelatinases (MMP-2 and MMP-9) were reported as urinary markers of bladder cancer. In this work, we developed a simple colorimetric gold nanoparticle (AuNP) assay for rapid and sensitive detection of urinary total gelatinase activity based on the surface plasmon resonance (SPR) property of AuNPs. Gelatin-modified AuNPs were stably suspended in solution even upon addition of an aggregation inducer as 6-mercaptohexan-1-ol (6-MCH). Gelatinases digest gelatin capping. Subsequently, addition of 6-MCH leads to AuNPs aggregation with red to blue color shift. In a pilot study, results of the developed AuNP assay were consistent with zymography for qualitative detection of urinary total gelatinase activity. The sensitivity and specificity of both assays were 80% and 90.9% respectively. The absorption ratios, A 625 /A 530 of the reacted AuNP solutions were used to quantify the total gelatinase concentration. The best cut off value was 0.01895ng/μg protein, at which the sensitivity was 87.5% and the specificity was 86.4%. The developed AuNP assay is simple, low-cost and can aid non-invasive diagnosis of bladder cancer. Copyright © 2016 Elsevier B.V. All rights reserved.

Reliability Assessment and Activation Energy Study of Au and Pd-Coated Cu Wires Post High Temperature Aging in Nanoscale Semiconductor Packaging.

PubMed

Gan, C L; Hashim, U

2013-06-01

Wearout reliability and high temperature storage life (HTSL) activation energy of Au and Pd-coated Cu (PdCu) ball bonds are useful technical information for Cu wire deployment in nanoscale semiconductor device packaging. This paper discusses the influence of wire type on the wearout reliability performance of Au and PdCu wire used in fine pitch BGA package after HTSL stress at various aging temperatures. Failure analysis has been conducted to identify the failure mechanism after HTSL wearout conditions for Au and PdCu ball bonds. Apparent activation energies (Eaa) of both wire types are investigated after HTSL test at 150 °C, 175 °C and 200 °C aging temperatures. Arrhenius plot has been plotted for each ball bond types and the calculated Eaa of PdCu ball bond is 0.85 eV and 1.10 eV for Au ball bond in 110 nm semiconductor device. Obviously Au ball bond is identified with faster IMC formation rate with IMC Kirkendall voiding while PdCu wire exhibits equivalent wearout and or better wearout reliability margin compare to conventional Au wirebond. Lognormal plots have been established and its mean to failure (t 50 ) have been discussed in this paper.

Mixed Valence Perovskite Cs2 Au2 I6 : A Potential Material for Thin-Film Pb-Free Photovoltaic Cells with Ultrahigh Efficiency.

PubMed

Debbichi, Lamjed; Lee, Songju; Cho, Hyunyoung; Rappe, Andrew M; Hong, Ki-Ha; Jang, Min Seok; Kim, Hyungjun

2018-03-01

New light is shed on the previously known perovskite material, Cs 2 Au 2 I 6 , as a potential active material for high-efficiency thin-film Pb-free photovoltaic cells. First-principles calculations demonstrate that Cs 2 Au 2 I 6 has an optimal band gap that is close to the Shockley-Queisser value. The band gap size is governed by intermediate band formation. Charge disproportionation on Au makes Cs 2 Au 2 I 6 a double-perovskite material, although it is stoichiometrically a single perovskite. In contrast to most previously discussed double perovskites, Cs 2 Au 2 I 6 has a direct-band-gap feature, and optical simulation predicts that a very thin layer of active material is sufficient to achieve a high photoconversion efficiency using a polycrystalline film layer. The already confirmed synthesizability of this material, coupled with the state-of-the-art multiscale simulations connecting from the material to the device, strongly suggests that Cs 2 Au 2 I 6 will serve as the active material in highly efficient, nontoxic, and thin-film perovskite solar cells in the very near future. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

La-doped Al2O3 supported Au nanoparticles: highly active and selective catalysts for PROX under PEMFC operation conditions.

PubMed

Lin, Qingquan; Qiao, Botao; Huang, Yanqiang; Li, Lin; Lin, Jian; Liu, Xiao Yan; Wang, Aiqin; Li, Wen-Cui; Zhang, Tao

2014-03-14

La-doped γ-Al2O3 supported Au catalysts show high activity and selectivity for the PROX reaction under PEMFC operation conditions. The superior performance is attributed to the formation of LaAlO3, which suppresses H2 oxidation and strengthens CO adsorption on Au sites, thereby improving competitive oxidation of CO at elevated temperature.

A facile approach for reducing the working voltage of Au/TiO2/Au nanostructured memristors by enhancing the local electric field

NASA Astrophysics Data System (ADS)

Arab Bafrani, Hamidreza; Ebrahimi, Mahdi; Bagheri Shouraki, Saeed; Moshfegh, Alireza Z.

2018-01-01

Memristor devices have attracted tremendous interest due to different applications ranging from nonvolatile data storage to neuromorphic computing units. Exploring the role of surface roughness of the bottom electrode (BE)/active layer interface provides useful guidelines for the optimization of the memristor switching performance. This study focuses on the effect of surface roughness of the BE electrode on the switching characteristics of Au/TiO2/Au three-layer memristor devices. An optimized wet-etching treatment condition was found to modify the surface roughness of the Au BE where the measurement results indicate that the roughness of the Au BE is affected by both duration time and solution concentrations of the wet-etching process. Then we fabricated arrays of TiO2-based nanostructured memristors sandwiched between two sets of cross-bar Au electrode lines (junction area 900 μm2). The results revealed a reduction in the working voltages in current-voltage characteristic of the device performance when increasing the surface roughness at the Au(BE)/TiO2 active layer interface. The set voltage of the device (Vset) significantly decreased from 2.26-1.93 V when we increased the interface roughness from 4.2-13.1 nm. The present work provides information for better understanding the switching mechanism of titanium-dioxide-based devices, and it can be inferred that enhancing the roughness of the Au BE/TiO2 active layer interface leads to a localized non-uniform electric field distribution that plays a vital role in reducing the energy consumption of the device.

Efficient Removal of Methane over Cobalt-Monoxide-Doped AuPd Nanocatalysts.

PubMed

Xie, Shaohua; Liu, Yuxi; Deng, Jiguang; Zang, Simiao; Zhang, Zhenhua; Arandiyan, Hamidreza; Dai, Hongxing

2017-02-21

To overcome deactivation of Pd-based catalysts at high temperatures, we herein design a novel pathway by introducing a certain amount of CoO to the supported Au-Pd alloy nanoparticles (NPs) to generate high-performance Au-Pd-xCoO/three-dimensionally ordered macroporous (3DOM) Co 3 O 4 (x is the Co/Pd molar ratio) catalysts. The doping of CoO induced the formation of PdO-CoO active sites, which was beneficial for the improvement in adsorption and activation of CH 4 and catalytic performance. The Au-Pd-0.40CoO/3DOM Co 3 O 4 sample performed the best (T 90% = 341 °C at a space velocity of 20 000 mL g -1 h -1 ). Deactivation of the 3DOM Co 3 O 4 -supported Au-Pd, Pd-CoO, and Au-Pd-xCoO nanocatalysts resulting from water vapor addition was due to the formation and accumulation of hydroxyl on the catalyst surface, whereas deactivation of the Pd-CoO/3DOM Co 3 O 4 catalyst at high temperatures (680-800 °C) might be due to decomposition of the PdO y active phase into aggregated Pd 0 NPs. The Au-Pd-xCoO/3DOM Co 3 O 4 nanocatalysts exhibited better thermal stability and water tolerance ability compared to the 3DOM Co 3 O 4 -supported Au-Pd and Pd-CoO nanocatalysts. We believe that the supported Au-Pd-xCoO nanomaterials are promising catalysts in practical applications for organic combustion.

Green Synthesis and Catalytic Activity of Gold Nanoparticles Synthesized by Artemisia capillaris Water Extract

NASA Astrophysics Data System (ADS)

Lim, Soo Hyeon; Ahn, Eun-Young; Park, Youmie

2016-10-01

Gold nanoparticles were synthesized using a water extract of Artemisia capillaris (AC-AuNPs) under different extract concentrations, and their catalytic activity was evaluated in a 4-nitrophenol reduction reaction in the presence of sodium borohydride. The AC-AuNPs showed violet or wine colors with characteristic surface plasmon resonance bands at 534 543 nm that were dependent on the extract concentration. Spherical nanoparticles with an average size of 16.88 ± 5.47 29.93 ± 9.80 nm were observed by transmission electron microscopy. A blue shift in the maximum surface plasmon resonance was observed with increasing extract concentration. The face-centered cubic structure of AC-AuNPs was confirmed by high-resolution X-ray diffraction analysis. Based on phytochemical screening and Fourier transform infrared spectra, flavonoids, phenolic compounds, and amino acids present in the extract contributed to the reduction of Au ions to AC-AuNPs. The average size of the AC-AuNPs decreased as the extract concentration during the synthesis was increased. Higher 4-nitrophenol reduction reaction rate constants were observed for smaller sizes. The extract in the AC-AuNPs was removed by centrifugation to investigate the effect of the extract in the reduction reaction. Interestingly, the removal of extracts greatly enhanced their catalytic activity by up to 50.4 %. The proposed experimental method, which uses simple centrifugation, can be applied to other metallic nanoparticles that are green synthesized with plant extracts to enhance their catalytic activity.

Selective Catalysis in Nanoparticle Metal-Organic Framework Composites

NASA Astrophysics Data System (ADS)

Stephenson, Casey Justin

The design of highly selective catalysts are becoming increasingly important, especially as chemical and pharmaceutical industries seek to improve atom economy and minimize energy intensive separations that are often required to separate side products from the desired product. Enzymes are among the most selective of all catalysts, generally operating through molecular recognition whereby an active site analogous to a lock and the substrate is analogous to a key. The assembly of a porous, crystalline material around a catalytically active metal particle could serve as an artificial enzyme. In this vein, we first synthesized the polyvinylpyrrolidone (PVP) coated nanoparticles of interest and then encapsulated them within zeolitic imidazolate framework 8 or ZIF-8. 2.8 nm Pt-PVP nanoparticles, which were encapsulated within ZIF-8 to form Pt ZIF-8 composite. Pt ZIF-8 was inactive for the hydrogenation of cyclic olefins such as cis-cyclooctene and cis-cyclohexene while the composite proved to be a highly selective catalyst for the hydrogenation of terminal olefins, hydrogenating trans-1,3-hexadiene to 3-hexene in 95% selectivity after 24 hours under 1 bar H2. We extended our encapsulation method to sub-2 nm Au nanoparticles to form Au ZIF-8. Au ZIF-8 served as a highly chemoselective catalyst for the hydrogenation of crotonaldehyde an alpha,beta-unsaturated aldehyde, to crotyl alcohol an alpha,beta-unsaturated alcohol, in 90-95% selectivity. In order to investigate nanoparticle size effects on selectivity, 6-10 nm Au nanoparticles were encapsulated within ZIF-8 to form Au6 ZIF-8. Control catalysts with nanoparticles supported on the surface of ZIF-8 were synthesized as well, Au/ZIF-8 and Au6/ZIF-8. Au6 ZIF-8 hydrogenated crotonaldehyde in 85% selectivity towards the unsaturated alcohol. Catalysts with nanoparticles supported on the exterior of ZIF-8 were far less selective towards the unsaturated alcohol. Post-catalysis transmission electron microscopy analysis of Au ZIF-8 and Au/ZIF-8 shows that the nanoparticles of Au ZIF-8 remain within experimental uncertainty and unchanged, whereas Au nanoparticles of Au/ZIF suffered from server sintering. We performed solvent assisted linker exchange, a single-crystal to single-crystal transformation, on Pt ZIF-8 to exchange the 2-methylimidazole linkers with imidazole to form Pt SALEM-2. Since Pt SALEM-2 should have larger apertures than Pt ZIF-8, we investigated Pt ZIF-8 and Pt SALEM-2 as catalysts for the hydrogenation of substrates with increasingly larger kinetic diameter: 1-octene, cis-cyclohexene, and beta-pinene. Both catalysts were active for the hydrogenation of 1-octene, while only Pt SALEM-2 was active for cis-cyclohexene hydrogenation. Neither catalyst was active for the hydrogenation of beta-pinene, indicating that the Pt nanoparticles remained well encapsulated throughout the SALE process.

DFT study on stability and H2 adsorption activity of bimetallic Au79-nPdn (n = 1-55) clusters

NASA Astrophysics Data System (ADS)

Liu, Xuejing; Tian, Dongxu; Meng, Changgong

2013-03-01

The stability and H2 adsorption activity of bimetallic Au79-nPdn (n = 1-55) clusters were studied by density functional theory with GGA-PW91 functional. The stability order for four Pd substitution types is face > mid-edge > corner > edge, and the stability is improved with increasing Pd content. In contrast with the stability order, H2 adsorption activity is corner ≈ edge > mid-edge > face. The Au36Pd43 (3) with Au:Pd ≈ 1:1 ratio and twenty-four Pd substitutions at (1 1 1) facets and nineteen Pd substitutions at subshell sites shows high stability and H2 non-activated dissociation activity. The partial density of d-states and d band center revealed that the electronic properties are closely associated with the geometric characteristic and adsorption activity. Correlating the d band center ɛd and the adsorption energies, the ɛd order agrees with the adsorption activity that the Pd substitution at edge and corner sites are more active than at face and mid-edge sites.

Biological characterization of cetuximab-conjugated gold nanoparticles in a tumor animal model

NASA Astrophysics Data System (ADS)

Kao, Hao-Wen; Lin, Yi-Yu; Chen, Chao-Cheng; Chi, Kwan-Hwa; Tien, Der-Chi; Hsia, Chien-Chung; Lin, Wuu-Jyh; Chen, Fu-Du; Lin, Ming-Hsien; Wang, Hsin-Ell

2014-07-01

Gold nanoparticles (AuNPs) are widely applied to the diagnosis and treatment of cancer and can be modified to contain target-specific ligands via gold-thiolate bonding. This study investigated the pharmacokinetics and microdistribution of antibody-mediated active targeting gold nanoparticles in mice with subcutaneous lung carcinoma. We conjugated AuNPs with cetuximab (C225), an antibody-targeting epidermal growth factor receptor (EGFR), and then labeled with In-111, which created EGFR-targeted AuNPs. In vitro studies showed that after a 2 h incubation, the uptake of C225-conjugated AuNPs in high EGFR-expression A549 cells was 14.9-fold higher than that of PEGylated AuNPs; furthermore, uptake was also higher at 3.8-fold when MCF7 cells with lower EGFR-expression were used. MicroSPECT/CT imaging and a biodistribution study conducted by using a A549 tumor xenograft mouse model provided evidence of elevated uptake of the C225-conjugated AuNPs into the tumor cells as a result of active targeting. Moreover, the microdistribution of PEGylated AuNPs revealed that a large portion of AuNPs remained in the tumor interstitium, whereas the C225-conjugated AuNPs displayed enhanced internalization via antibody-mediated endocytosis. Our findings suggest that the anti-EGFR antibody-conjugated AuNPs are likely to be a plausible nano-sized vehicle for drug delivery to EGFR-expressing tumors.

Water inhibits CO oxidation on gold cations in the gas phase. Structures and binding energies of the sequential addition of CO, H2O, O2, and N2 onto Au.

PubMed

Reveles, J Ulises; Saoud, Khaled M; El-Shall, M Samy

2016-10-19

We report a detailed experimental and theoretical study of the gas phase reactivity of Au + with CO, O 2 , N 2 and their mixtures in the presence of a trace amount of water impurity. The gold cation is found to strongly interact with CO and H 2 O molecules via successive addition reactions until reaching saturation. The stoichiometry of the formed complex is determined by the strength of the binding energy of the neutral molecule to the gold cation. CO binds the strongest to Au + , followed by H 2 O, N 2 and then O 2 . We found that the gold cation (Au + ) can activate the O 2 molecule within the Au + (CO) 2 (O 2 ) complex which could react with another CO molecule to form Au + (CO)(CO 2 ) + CO 2 . The product Au + (CO)(CO 2 ) is observed experimentally with a small intensity at room temperature. However, the presence of water leads to the formation of Au + (CO)(H 2 O)(O 2 ) instead of Au + (CO) 2 (O 2 ) due to the strong interaction between Au + and water. The current experiments and calculations might lead to a molecular level understanding of the interactions between the active sites, reactants and impurities which could pave the way for the design of efficient nanocatalysts.

Dewetting process of Au films on SiO2 nanowires: Activation energy evaluation

NASA Astrophysics Data System (ADS)

Ruffino, F.; Grimaldi, M. G.

2015-05-01

SiO2 nanowires gain scientific and technological interest in application fields ranging from nano-electronics, optics and photonics to bio-sensing. Furthermore, the SiO2 nanowires chemical and physical properties, and so their performances in devices, can be enhanced if decorated by metal nanoparticles (such Au) due to local plasmonic effects. In the present paper, we propose a simple, low-cost and high-throughput three-steps methodology for the mass-production of Au nanoparticles coated SiO2 nanowires. It is based on (1) production of the SiO2 nanowires on Si surface by solid state reaction of an Au film with the Si substrate at high temperature; (2) sputtering deposition of Au on the SiO2 nanowires to obtain the nanowires coated by an Au film; and (3) furnace annealing processes to induce the Au film dewetting on the SiO2 nanowires surface. Using scanning electron microscopy analyses, we followed the change of the Au nanoparticles mean versus the annealing time extracting values for the characteristic activation energy of the dewetting process of the Au film on the SiO2 nanowires surface. Such a study can allow the tuning of the nanowires/nanoparticles sizes for desired technological applications.

Au@TiO2 yolk-shell nanostructures for enhanced performance in both photoelectric and photocatalytic solar conversion

NASA Astrophysics Data System (ADS)

He, Qinrong; Sun, Hang; Shang, Yinxing; Tang, Yanan; She, Ping; Zeng, Shan; Xu, Kongliang; Lu, Guolong; Liang, Song; Yin, Shengyan; Liu, Zhenning

2018-05-01

Solar energy conversion is an important field gaining increasing interest. Herein, bio-inspired Au@TiO2 yolk-shell nanoparticles (NPs) have been prepared via a facial one-pot hydrothermal approach. The Au@TiO2 yolk-shell NPs can self-assemble into 3D-structure to form photoelectrode for photoelectric conversion. The obtained photoelectrode demonstrates a swift and stable photocurrent of 3.5 μA/cm2, which is 4.2 and 1.6 times higher than those of the photocurrents generated by the counterparts of commercial TiO2 and Au@TiO2 core-shell NPs, respectively. Moreover, compared to the commercial TiO2 and Au@TiO2 core-shell NPs, the Au@TiO2 yolk-shell NPs also exhibit superior photocatalytic activity, delivering a H2 evolution rate of 4.92 mmol/g h. The performance improvement observed for the Au@TiO2 yolk-shell NPs is likely contributed by two synergistic factors, i.e. the incorporation of AuNPs and the unique hollow structure, which benefit the activity by simultaneously enhancing light utilization, charge separation and reaction site accessibility. The rational design and fabrication of Au@TiO2 yolk-shell NPs hold great promise for future application in efficient solar energy conversion.

Chemically reduced graphene oxide-P25-Au nanocomposite materials and their photoelectrocatalytic and photocatalytic applications.

PubMed

Praveen, Raju; Ramaraj, Ramasamy

2016-10-05

Visible light active photocatalysts consisting of gold nanoparticle (Au NP) decorated chemically reduced graphene oxide-P25 nanocomposite materials (CRGO-P25-Au NCMs) were prepared through a one-pot chemical reduction method. The nanocomposite materials were characterized using diffuse reflectance spectroscopy (DRS), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and electrochemical impedance spectroscopy (EIS) analyses. The performances of CRGO-P25-Au NCM modified ITO electrodes were evaluated towards the photoelectrochemical oxidation of methanol. The photoelectrode fabricated using CRGO-P25-Au NCM exhibited a higher photocurrent of 293 μA cm -2 compared to other control electrodes. The CRGO-P25-Au NCMs were also used for the photocatalytic reduction of highly toxic chromium(vi) ions to chromium(iii) ions in the presence of oxalic acid as a sacrificial electron donor. The results showed that around 75% of the Cr(vi) ions were photocatalytically reduced to Cr(iii) ions by the CRGO-P25-Au NCM within the light irradiation time of 1 h. In both applications, the enhanced catalytic activity of the CRGO-P25-Au NCM was attributed to the improved visible light absorption and the reduced charge recombination exerted by the interaction of CRGO and Au NPs with P25 and their synergistic effects.

Porous Nanocrystalline Silicon Supported Bimetallic Pd-Au Catalysts: Preparation, Characterization, and Direct Hydrogen Peroxide Synthesis

PubMed Central

Potemkin, Dmitriy I.; Maslov, Dmitry K.; Loponov, Konstantin; Snytnikov, Pavel V.; Shubin, Yuri V.; Plyusnin, Pavel E.; Svintsitskiy, Dmitry A.; Sobyanin, Vladimir A.; Lapkin, Alexei A.

2018-01-01

Bimetallic Pd-Au catalysts were prepared on the porous nanocrystalline silicon (PSi) for the first time. The catalysts were tested in the reaction of direct hydrogen peroxide synthesis and characterized by standard structural and chemical techniques. It was shown that the Pd-Au/PSi catalyst prepared from conventional H2[PdCl4] and H[AuCl4] precursors contains monometallic Pd and a range of different Pd-Au alloy nanoparticles over the oxidized PSi surface. The PdAu2/PSi catalyst prepared from the [Pd(NH3)4][AuCl4]2 double complex salt (DCS) single-source precursor predominantly contains bimetallic Pd-Au alloy nanoparticles. For both catalysts the surface of bimetallic nanoparticles is Pd-enriched and contains palladium in Pd0 and Pd2+ states. Among the catalysts studied, the PdAu2/PSi catalyst was the most active and selective in the direct H2O2 synthesis with H2O2 productivity of 0.5 mol gPd-1 h-1 at selectivity of 50% and H2O2 concentration of 0.023 M in 0.03 M H2SO4-methanol solution after 5 h on stream at −10°C and atmospheric pressure. This performance is due to high activity in the H2O2 synthesis reaction and low activities in the undesirable H2O2 decomposition and hydrogenation reactions. Good performance of the PdAu2/PSi catalyst was associated with the major part of Pd in the catalyst being in the form of the bimetallic Pd-Au nanoparticles. Porous silicon was concluded to be a promising catalytic support for direct hydrogen peroxide synthesis due to its inertness with respect to undesirable side reactions, high thermal stability, and conductivity, possibility of safe operation at high temperatures and pressures and a well-established manufacturing process. PMID:29637068

Porous nanocrystalline silicon supported bimetallic Pd-Au catalysts: preparation, characterization and direct hydrogen peroxide synthesis

NASA Astrophysics Data System (ADS)

Potemkin, Dmitriy I.; Maslov, Dmitry K.; Loponov, Konstantin; Snytnikov, Pavel V.; Shubin, Yuri V.; Plyusnin, Pavel E.; Svintsitskiy, Dmitry A.; Sobyanin, Vladimir A.; Lapkin, Alexei A.

2018-03-01

Bimetallic Pd-Au catalysts were prepared on the porous nanocrystalline silicon (PSi) for the first time. The catalysts were tested in the reaction of direct hydrogen peroxide synthesis and characterised by standard structural and chemical techniques. It was shown that the Pd-Au/PSi catalyst prepared from conventional H2[PdCl4] and H[AuCl4] precursors contains monometallic Pd and a range of different Pd-Au alloy nanoparticles over the oxidized PSi surface. The PdAu2/PSi catalyst prepared from the [Pd(NH3)4][AuCl4]2 double complex salt single-source precursor predominantly contains bimetallic Pd-Au alloy nanoparticles. For both catalysts the surface of bimetallic nanoparticles is Pd-enriched and contains palladium in Pd0 and Pd2+ states. Among the catalysts studied, the PdAu2/PSi catalyst was the most active and selective in the direct H2O2 synthesis with H2O2 productivity of 0.5 at selectivity of 50 % and H2O2 concentration of 0.023 M in 0.03 M H2SO4-methanol solution after 5 h on stream at -10 °C and atmospheric pressure. This performance is due to high activity in the H2O2 synthesis reaction and low activities in the undesirable H2O2 decomposition and hydrogenation reactions. Good performance of the PdAu2/PSi catalyst was associated with the major part of Pd in the catalyst being in the form of the bimetallic Pd-Au nanoparticles. Porous silicon was concluded to be a promising catalytic support for direct hydrogen peroxide synthesis due to its inertness with respect to undesirable side reactions, high thermal stability and conductivity, possibility of safe operation at high temperatures and pressures and a well-established manufacturing process.

Hierarchically assembled Au microspheres and sea urchin-like architectures: formation mechanism and SERS study.

PubMed

Wang, Xiansong; Yang, Da-Peng; Huang, Peng; Li, Min; Li, Chao; Chen, Di; Cui, Daxiang

2012-12-21

The hierarchically assembled Au microspheres/sea urchin-like structures have been synthesized in aqueous solution at room temperature with and without proteins (bovine serum albumin, BSA) as mediators. The average diameter of an individual Au microsphere is 300-600 nm, which is composed of some compact nanoparticles with an average diameter of about 15 nm. Meanwhile, the sea urchin-like Au architecture exhibits an average diameter of 600-800 nm, which is made up of some nanopricks with an average length of 100-200 nm. These products are characterized by means of scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electronic microscopy (TEM). It is found that the BSA and ascorbic acid (AA) have great effects on the morphology of the resulting products. Two different growth mechanisms are proposed. The study on surface enhanced Raman scattering (SERS) activities is also carried out between Au microspheres and Au sea urchin-like architectures. It is found that Au urchin-like architectures possess much higher SERS activity than the Au microspheres. Our work may shed light on the design and synthesis of hierarchically self-assembled 3D micro/nano-architectures for SERS, catalysis and biosensors.

RGO/AuNR/HA-5FU nanocomposite with multi-stage release behavior and efficient antitumor activity for synergistic therapy.

PubMed

Yang, Ying; Wang, Yunlong; Zhu, Manzhou; Chen, Yan; Xiao, Yazhong; Shen, Yuhua; Xie, Anjian

2017-05-02

A reduced graphene oxide (RGO)/gold nanorod (AuNR)/hydroxyapatite (HA) nanocomposite was designed and successfully synthesized for the first time. An anticancer drug, 5-fluorouracil (5FU), was chosen as a model drug to be loaded in RGO/AuNR/HA. The fabricated RGO/AuNR/HA-5FU showed robust, selective targeting and penetrating efficiency against HeLa cells due to the good compatibility and nontoxicity of HA, and showed excellent synergetic antitumor effects through combined chemotherapy (CT) by 5FU and photothermal therapy (PTT) by both RGO and AuNRs under near-infrared (NIR) laser irradiation. More importantly, this synergistic dual therapy based on RGO/AuNR/HA can also minimize side effects in normal cells and exhibits greater antitumor activity because of a multi-stage drug release ability triggered by the pH sensitivity of HA in the first stage and the combined photothermal conversion capabilities of RGO and AuNRs by means of the NIR laser irradiation in the second stage. This study suggests that the novel RGO/AuNR/HA multi-stage drug delivery system may represent a promising potential application of multifunctional composite materials in the biomedical field.

Formation, Migration, and Reactivity of Au CO Complexes on Gold Surfaces

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

Wang, Jun; McEntee, Monica; Tang, Wenjie

2016-01-12

Here, we report experimental as well as theoretical evidence that suggests Au CO complex formation upon the exposure of CO to active sites (step edges and threading dislocations) on a Au(111) surface. Room-temperature scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy, transmission infrared spectroscopy, and density functional theory calculations point to Au CO complex formation and migration. Room-temperature STM of the Au(111) surface at CO pressures in the range from 10^ 8 to 10^ 4 Torr (dosage up to 10^6 langmuir) indicates Au atom extraction from dislocation sites of the herringbone reconstruction, mobile Au CO complex formation and diffusion, and Aumore » adatom cluster formation on both elbows and step edges on the Au surface. The formation and mobility of the Au CO complex result from the reduced Au Au bonding at elbows and step edges leading to stronger Au CO bonding and to the formation of a more positively charged CO (CO +) on Au. These studies indicate that the mobile Au CO complex is involved in the Au nanoparticle formation and reactivity, and that the positive charge on CO increases due to the stronger adsorption of CO at Au sites with lower coordination numbers.« less

Effects of antirheumatic gold compounds on the conversion of xanthine dehydrogenase to oxidase in rabbit liver cytosol in vitro.

PubMed

Sakuma, Satoru; Gotoh, Kyohko; Sadatoku, Namiko; Fujita, Tadashi; Fujimoto, Yohko

2004-07-23

Effects of auranofin (AUR), aurothioglucose (AuTG) and aurothiomalate (AuTM) on the conversion of xanthine dehydrogenase (XD) to oxidase (XO) in the cytosolic fraction from rabbit liver were examined. AUR had no effect on the conversion of XD to XO at concentrations up to 50 microM, whereas at concentrations ranging from 10 to 25 microM, AuTG and AuTM induced the conversion of XD to XO. The constituents of AuTG and AuTM, aurous ion (Au+), but not mercaptosuccinic acid and 1-thio-beta-D-glucose, converted XD to XO in a similar degree to AuTG and AuTM. This means that Au (I) moiety has an important role in the AuTG- and AuTM-induced conversion of XD to XO. Furthermore, N-acetyl-L-cysteine (NAC) and British anti-Lewisite (BAL) reconverted AuTG and AuTM-induced XO to XD, implying that clinical activity of NAC and BAL against toxic reactions of AuTG and AuTM is partially due to the XO reconversion. These results suggest that AuTG and AuTM have the potential to convert XD to its reactive oxygen species-generating form, XO, and that this effect may be correlated with cytotoxic actions of these drugs.

In situ formation of the active sites in Pd-Au bimetallic nanocatalysts for CO oxidation: NAP (near ambient pressure) XPS and MS study.

PubMed

Bukhtiyarov, A V; Prosvirin, I P; Saraev, A A; Klyushin, A Yu; Knop-Gericke, A; Bukhtiyarov, V I

2018-06-07

Model bimetallic Pd-Au/HOPG catalysts have been investigated in the CO oxidation reaction using a combination of NAP XPS and MS techniques. The samples have shown catalytic activity at temperatures above 150 °C. The redistribution of Au and Pd on the surface depending on the reaction conditions has been demonstrated using NAP XPS. The Pd enrichment of the bimetallic particles' surface under reaction gas mixture has been shown. Apparently, CO adsorption induces Pd segregation on the surface. Heating the sample under reaction conditions above 150 °C decomposes the Pd-CO state due to CO desorption and reaction and simultaneous Pd-Au alloy formation on the surface takes place. Cooling back down to RT results in reversible Pd segregation due to Pd-CO formation and the sample becomes inactive. It has been shown that in situ studies are necessary for investigation of the active sites in Pd-Au bimetallic systems.

Cross section of the 197Au(n,2n)196Au reaction

NASA Astrophysics Data System (ADS)

Kalamara, A.; Vlastou, R.; Kokkoris, M.; Diakaki, M.; Serris, M.; Patronis, N.; Axiotis, M.; Lagoyannis, A.

2017-09-01

The 197Au(n,2n)196Au reaction cross section has been measured at two energies, namely at 17.1 MeV and 20.9 MeV, by means of the activation technique, relative to the 27Al(n,α)24Na reference reaction cross section. Quasi-monoenergetic neutron beams were produced at the 5.5 MV Tandem T11/25 accelerator laboratory of NCSR "Demokritos", by means of the 3H(d,n)4He reaction, implementing a new Ti-tritiated target of ˜ 400 GBq activity. The induced γ-ray activity at the targets and reference foils has been measured with HPGe detectors. The cross section for the population of the second isomeric (12-) state m2 of 196Au was independently determined. Auxiliary Monte Carlo simulations were performed using the MCNP code. The present results are in agreement with previous experimental data and with theoretical calculations of the measured reaction cross sections, which were carried out with the use of the EMPIRE code.

Catalytic Gas-Phase Glycerol Processing over SiO2-, Cu-, Ni- and Fe- Supported Au Nanoparticles

PubMed Central

Kapkowski, Maciej; Siudyga, Tomasz; Sitko, Rafal; Lelątko, Józef; Szade, Jacek; Balin, Katarzyna; Klimontko, Joanna; Bartczak, Piotr; Polanski, Jaroslaw

2015-01-01

In this study, we investigated different metal pairings of Au nanoparticles (NPs) as potential catalysts for glycerol dehydration for the first time. All of the systems preferred the formation of hydroxyacetone (HYNE). Although the bimetallics that were tested, i.e., Au NPs supported on Ni, Fe and Cu appeared to be more active than the Au/SiO2 system, only Cu supported Au NPs gave high conversion (ca. 63%) and selectivity (ca. 70%) to HYNE. PMID:26580400

Ultrasonication-assisted synthesis of high aspect ratio gold nanowires on a graphene template and investigation of their growth mechanism.

PubMed

Xin, Wenbo; De Rosa, Igor M; Cao, Yang; Yin, Xunqian; Yu, Hang; Ye, Peiyi; Carlson, Larry; Yang, Jenn-Ming

2018-04-19

We report a facile synthesis of Au nanowires (AuNWs) with a high aspect ratio (l/D) of up to 5000 on a plasma activated graphene template with ultrasound assistance. We demonstrate that the ultrasonication induced symmetry breaking of Au clusters facilitates the growth of AuNWs from the embryonic stages. Furthermore, the growth mechanism of AuNWs is systematically investigated using high resolution electron transmission microscopy (HRTEM), which reveals the unique role of the defective graphene template in directing the growth of AuNWs.

AuScope VLBI Project and Hobart 26-m Antenna

NASA Technical Reports Server (NTRS)

Lovell, Jim; Dickey, John; Reid, Brett; McCallum, Jamie; Shabala, Stas; Watson, Christopher; Ellingsen, Simon; Memin, Anthony

2013-01-01

This is a report on the activities carried out at the three AuScope VLBI observatories and the Hobart 26-m antenna. In 2012 the three AuScope 12-m antennas at Hobart (Hb), Katherine (Ke), and Yarragadee (Yg) completed their first full year of operations as an array. The Hobart 26-m antenna (Ho) continued to make a contribution to IVS, providing overlap with the Hb time series. In total the AuScope antennas and the Hobart 26 m observed for 146 antenna days in 2012. In this report we also briefly highlight our research activities during 2012 and our plans for 2013.

The relationship of alcohol use and physical activity from an ecologic perspective.

PubMed

Bigelow, April; Villarruel, Antonia; Ronis, David L

2014-01-01

To determine the predictors of alcohol use (AU) and their relationship to physical activity (PA) among adolescents and to examine differences among groups using an ecologic model. Cross sectional secondary analysis of 11,432 adolescents (51% 8th and 49% 10th graders). Attitude, perception of risk, and academic performance were the strongest predictors of AU. PA did not moderate, but it had a positive influence on AU in 10th graders. Differences were observed among groups. Nurses can address individual and school factors in an effort to decrease AU and guide nurses in creating an individualized plan. © 2013, Wiley Periodicals, Inc.

A novel dual-functional biosensor for fluorometric detection of inorganic pyrophosphate and pyrophosphatase activity based on globulin stabilized gold nanoclusters.

PubMed

Xu, Shenghao; Feng, Xiuying; Gao, Teng; Wang, Ruizhi; Mao, Yaning; Lin, Jiehua; Yu, Xijuan; Luo, Xiliang

2017-03-15

A novel ultrasensitive dual-functional biosensor for highly sensitive detection of inorganic pyrophosphate (PPi) and pyrophosphatase (PPase) activity was developed based on the fluorescent variation of globulin protected gold nanoclusters (Glo@Au NCs) with the assistance of Cu 2+ . Glo@Au NCs and PPi were used as the fluorescent indicator and substrate for PPase activity evaluation, respectively. In the presence of Cu 2+ , the fluorescence of the Glo@Au NCs will be quenched owing to the formation of Cu 2+ -Glo@Au NCs complex, while PPi can restore the fluorescence of the Cu 2+ -Glo@Au NCs complex because of its higher binding affinity with Cu 2+ . As PPase can catalyze the hydrolysis of PPi, it will lead to the release of Cu 2+ and re-quench the fluorescence of the Glo@Au NCs. Based on this mechanism, quantitative evaluation of the PPi and PPase activity can be achieved ranging from 0.05 μM to 218.125 μM for PPi and from 0.1 to 8 mU for PPase, with detection limits of 0.02 μM and 0.04 mU, respectively, which is much lower than that of other PPi and PPase assay methods. More importantly, this ultrasensitive dual-functional biosensor can also be successfully applied to evaluate the PPase activity in human serum, showing great promise for practical diagnostic applications. Copyright © 2016 Elsevier B.V. All rights reserved.

pH-Responsive Mercaptoundecanoic Acid Functionalized Gold Nanoparticles and Applications in Catalysis

PubMed Central

Ansar, Siyam M.; Chakraborty, Saptarshi

2018-01-01

Mercaptoundecanoic acid (MUA) functionalized gold nanoparticles (AuNP-MUA) were synthesized and demonstrated to possess pH-triggered aggregation and re-dispersion, as well as the capability of phase transfer between aqueous and organic phases in response to changes in pH. The pH of aggregation for AuNP-MUA is consistent with the pKa of MUA (pH ~4) in solution, while AuNP-MUA phase transition between aqueous and organic phases occurs at pH ~9. The ion pair formation between the amine group in octadecylamine (ODA), the carboxylate group in MUA, and the hydrophobic alkyl chain of ODA facilitates the phase transfer of AuNP-MUA into an organic medium. The AuNP-MUA were investigated as a reusable catalyst in the catalytic reduction of 4-nitrophenol by borohydride—a model reaction for AuNPs. It was determined that 100% MUA surface coverage completely inhibits the catalytic activity of AuNPs. Decreasing the surface coverage was shown to increase catalytic activity, but this decrease also leads to decreased colloidal stability, recoverability, and reusability in subsequent reactions. At 60% MUA surface coverage, colloidal stability and catalytic activity were achieved, but the surface coverage was insufficient to enable redispersion following pH-induced recovery. A balance between AuNP colloidal stability, recoverability, and catalytic activity with reusability was achieved at 90% MUA surface coverage. The AuNP-MUA catalyst can also be recovered at different pH ranges depending on the recovery method employed. At pH ~4, protonation of the MUA results in reduced surface charge and aggregation. At pH ~9, ODA will form an ion-pair with the MUA and induce phase transfer into an immiscible organic phase. Both the pH-triggered aggregation/re-dispersion and aqueous/organic phase transfer methods were employed for catalyst recovery and reuse in subsequent reactions. The ability to recover and reuse the AuNP-MUA catalyst by two different methods and different pH regimes is significant, based on the fact that nanoparticle-catalyzed reactions may occur under different pH conditions. PMID:29772775

Gold nanoparticles induce transcriptional activity of NF-κB in a B-lymphocyte cell line

NASA Astrophysics Data System (ADS)

Sharma, Monita; Salisbury, Richard L.; Maurer, Elizabeth I.; Hussain, Saber M.; Sulentic, Courtney E. W.

2013-04-01

Gold nanoparticles (Au-NPs) have been designated as superior tools for biological applications owing to their characteristic surface plasmon absorption/scattering and amperometric (electron transfer) properties, in conjunction with low or no immediate toxicity towards biological systems. Many studies have shown the ease of designing application-based tools using Au-NPs but the interaction of this nanosized material with biomolecules in a physiological environment is an area requiring deeper investigation. Immune cells such as lymphocytes circulate through the blood and lymph and therefore are likely cellular components to come in contact with Au-NPs. The main aim of this study was to mechanistically determine the functional impact of Au-NPs on B-lymphocytes. Using a murine B-lymphocyte cell line (CH12.LX), treatment with citrate-stabilized 10 nm Au-NPs induced activation of an NF-κB-regulated luciferase reporter, which correlated with altered B lymphocyte function (i.e. increased antibody expression). TEM imaging demonstrated that Au-NPs can pass through the cellular membrane and therefore could interact with intracellular components of the NF-κB signaling pathway. Based on the inherent property of Au-NPs to bind to -thiol groups and the presence of cysteine residues on the NF-κB signal transduction proteins IκB kinases (IKK), proteins specifically bound to Au-NPs were extracted from CH12.LX cellular lysate exposed to 10 nm Au-NPs. Electrophoresis identified several bands, of which IKKα and IKKβ were immunoreactive. Further evaluation revealed activation of the canonical NF-κB signaling pathway as evidenced by IκBα phosphorylation at serine residues 32 and 36 followed by IκBα degradation and increased nuclear RelA. Additionally, expression of an IκBα super-repressor (resistant to proteasomal degradation) reversed Au-NP-induced NF-κB activation. Altered NF-κB signaling and cellular function in B-lymphocytes suggests a potential for off-target effects with in vivo applications of gold nanomaterials and underscores the need for more studies evaluating the interactions of nanomaterials with biomolecules and cellular components.

An amplified electrochemiluminescent aptasensor using Au nanoparticles capped by 3,4,9,10-perylene tetracarboxylic acid-thiosemicarbazide functionalized C60 nanocomposites as a signal enhancement tag

NASA Astrophysics Data System (ADS)

Ma, Meng-Nan; Zhang, Xia; Zhuo, Ying; Chai, Ya-Qin; Yuan, Ruo

2015-01-01

A novel electrochemiluminescent (ECL) signal tag of Au nanoparticles capped by 3,4,9,10-perylene tetracarboxylic acid-thiosemicarbazide functionalized C60 nanocomposites (AuNPs/TSC-PTC/C60NPs) was developed for thrombin (TB) aptasensor construction based on the peroxydisulfate/oxygen (S2O82-/O2) system. For signal tag fabrication, the C60 nanoparticles (C60NPs) were prepared and then coated with 3,4,9,10-perylene tetracarboxylic acid (PTCA) by π-π stacking interactions. Afterwards, thiosemicarbazide (TSC) was linked with PTCA functionalized C60NPs via amidation for further assembling Au nanoparticles (AuNPs). Finally, detection aptamer of thrombin (TBA 2) was labeled on the ECL signal amplification tag of AuNPs/TSC-PTC/C60NPs. Herein, TSC, with the active groups of -NH2 and -SH, was selected and introduced into the ECL S2O82-/O2 system for the first time, which could not only offer the active groups of -SH to absorb AuNPs for TBA 2 anchoring but also remarkably enhance the ECL signal of the S2O82-/O2 system by the formation of TSC-PTC/C60NPs for signal amplification. Meanwhile, the sensing interface of a glassy carbon electrode (GCE) was modified by AuNPs/graphene (AuNPs/GR) nanocomposites with the large specific surface area and the active sites, followed by immobilization of thiol-terminated thrombin capture aptamer (TBA 1). With the formation of the sandwich-type structure of TBA 1, TB, and TBA 2 signal probes, a desirable enhanced ECL signal was measured in the testing buffer of an S2O82-/O2 solution for detecting TB. The aptasensor exhibited a good linear relationship for TB detection in the range of 1 × 10-5-10 nM with a detection limit of 3.3 fM.A novel electrochemiluminescent (ECL) signal tag of Au nanoparticles capped by 3,4,9,10-perylene tetracarboxylic acid-thiosemicarbazide functionalized C60 nanocomposites (AuNPs/TSC-PTC/C60NPs) was developed for thrombin (TB) aptasensor construction based on the peroxydisulfate/oxygen (S2O82-/O2) system. For signal tag fabrication, the C60 nanoparticles (C60NPs) were prepared and then coated with 3,4,9,10-perylene tetracarboxylic acid (PTCA) by π-π stacking interactions. Afterwards, thiosemicarbazide (TSC) was linked with PTCA functionalized C60NPs via amidation for further assembling Au nanoparticles (AuNPs). Finally, detection aptamer of thrombin (TBA 2) was labeled on the ECL signal amplification tag of AuNPs/TSC-PTC/C60NPs. Herein, TSC, with the active groups of -NH2 and -SH, was selected and introduced into the ECL S2O82-/O2 system for the first time, which could not only offer the active groups of -SH to absorb AuNPs for TBA 2 anchoring but also remarkably enhance the ECL signal of the S2O82-/O2 system by the formation of TSC-PTC/C60NPs for signal amplification. Meanwhile, the sensing interface of a glassy carbon electrode (GCE) was modified by AuNPs/graphene (AuNPs/GR) nanocomposites with the large specific surface area and the active sites, followed by immobilization of thiol-terminated thrombin capture aptamer (TBA 1). With the formation of the sandwich-type structure of TBA 1, TB, and TBA 2 signal probes, a desirable enhanced ECL signal was measured in the testing buffer of an S2O82-/O2 solution for detecting TB. The aptasensor exhibited a good linear relationship for TB detection in the range of 1 × 10-5-10 nM with a detection limit of 3.3 fM. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr05918b

Nevirapine Loaded Core Shell Gold Nanoparticles by Double Emulsion Solvent Evaporation: In vitro and In vivo Evaluation.

PubMed

Dalvi, Bhagyashree R; Siddiqui, Ejaz A; Syed, Asad S; Velhal, Shilpa M; Ahmad, Absar; Bandivdekar, Atmaram B; Devarajan, Padma V

2016-01-01

HIV/AIDS is a macrophage resident infection localized in the reticuloendothelial system and remote locations of brain and bone marrow. We present core shell nanoparticles of gold(AuNPs) and nevirapine(NVP) for targeted delivery to the multiple HIV reservoirs. The aim of the study was to design core shell NVP loaded AuNPs with high drug loading and to evaluate biodistribution of the nanoparticles in possible HIV reservoirs in vivo. A specific objective was to assess the possible synergy of AuNPs with NVP on anti-HIV activity in vitro. Core shell nanoparticles were prepared by double emulsion solvent evaporation method and characterized. Glyceryl monostearate-nevirapine-gold nanoparticles(GMS-NVP-AuNPs) revealed high entrapment efficiency (>70%), high loading (~40%), particle size <250 nm and zeta potential -35.9± 1.41mv and exhibited sustained release with good stability. Surface plasmon resonance indicated shell formation while SEM coupled EDAX confirmed the presence of Au. TEM confirmed formation of spherical core shell nanoparticles. GMS-NVP-AuNPs revealed low hemolysis (<10 %) and serum stability upto 6 h. GMS-NVP-AuNPs exhibited rapid, high and sustained accumulation in the possible HIV reservoir organs, including the major organs of liver, spleen, lymph nodes, thymus and also remote locations of brain, ovary and bone marrow. High cell viability and enhanced uptake in PBMC's and TZM-bl cells were observed. While uptake in PBMC's proposed monocytes/macrophages enabled brain delivery. GMS-NVP-AuNPs demonstrated synergistic anti-HIV activity. The superior anti-HIV activity in vitro coupled with extensive localization of the nanoparticles in multiple HIV reservoirs suggests great promise of the core shell GMS-NVP-AuNPs for improved therapy of HIV.

Bimetallic Pt-Au nanocatalysts electrochemically deposited on boron-doped diamond electrodes for nonenzymatic glucose detection.

PubMed

Nantaphol, Siriwan; Watanabe, Takeshi; Nomura, Naohiro; Siangproh, Weena; Chailapakul, Orawon; Einaga, Yasuaki

2017-12-15

The enormous demand for medical diagnostics has encouraged the fabrication of high- performance sensing platforms for the detection of glucose. Nonenzymatic glucose sensors are coming ever closer to being used in practical applications. Bimetallic catalysts have been shown to be superior to single metal catalysts in that they have greater activity and selectivity. Here, we demonstrate the preparation, characterization, and electrocatalytic characteristics of a new bimetallic Pt/Au nanocatalyst. This nanocatalyst can easily be synthesized by electrodeposition by sequentially depositing Au and Pt on the surface of a boron-doped diamond (BDD) electrode. We characterized the nanocatalyst by scanning electron microscopy (SEM), X-ray diffraction (XRD), and voltammetry. The morphology and composition of the nanocatalyst can be easily controlled by adjusting the electrodeposition process and the molar ratio between the Pt and Au precursors. The electrocatalytic characteristics of a Pt/Au/BDD electrode for the nonenzymatic oxidation of glucose were systematically investigated by cyclic voltammetry. The electrode exhibits higher catalytic activity for glucose oxidation than Pt/BDD and Au/BDD electrodes. The best catalytic activity and stability was obtained with a Pt:Au molar ratio of 50:50. Moreover, the presence of Au can significantly enhance the long-term stability and poisoning tolerance during the electro-oxidation of glucose. Measurements of glucose using the Pt/Au/BDD electrode were linear in the range from 0.01 to 7.5mM, with a detection limit of 0.0077mM glucose. The proposed electrode performs selective electrochemical analysis of glucose in the presence of common interfering species (e.g., acetaminophen, uric and ascorbic acids), avoiding the generation of overlapping signals from such species. Copyright © 2017 Elsevier B.V. All rights reserved.

Preparation and characterization of mesoporous TiO2-sphere-supported Au-nanoparticle catalysts with high activity for CO oxidation at ambient temperature

NASA Astrophysics Data System (ADS)

Wang, Lili; Huang, Shouying; Zhu, Baolin; Zhang, Shoumin; Huang, Weiping

2016-11-01

Mesoporous TiO2-sphere-supported Au-nanoparticles (Au/m-TiO2-spheres) catalysts have been synthesized by a simple method using tetrabutyl titanate as TiO2 precursor and characterized with XRD, BET, ICP, SEM, TEM, UV-Vis DRS, XPS, as well as FT-IR. The samples with the size in the range of 200-400 nm were almost perfectly spherical. The average diameter of pores was about 3.6 nm, and the mesopore size distribution was in the range of 2-6 nm with a narrow distribution. When the catalyst was calcined at 300 °C, the Au NPs with the size ca. 5 nm were highly dispersed on the surfaces of m-TiO2 spheres and partially embedded in the supports. Remarkably, the specific surface area of the Au/m-TiO2-spheres was as high as 117 m2 g-1. The CO-adsorbed catalyst showed an apparent IR adsorption peak at 1714 cm-1 that matched with bridging model CO. It means the catalysts should be of high catalytic activity for the CO oxidation due to they could adsorb and activate CO commendably. When Au-content was 0.48 wt.%, the Au/m-TiO2-spheres could convert CO completely into CO2 at ambient temperature.

DNA-templated synthesis of PtAu bimetallic nanoparticle/graphene nanocomposites and their application in glucose biosensor

PubMed Central

2014-01-01

In this paper, single-stranded DNA (ss-DNA) is demonstrated to functionalize graphene (GR) and to further guide the growth of PtAu bimetallic nanoparticles (PtAuNPs) on GR with high densities and dispersion. The obtained nanocomposites (PtAuNPs/ss-DNA/GR) were characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectrometer (EDS), and electrochemical techniques. Then, an enzyme nanoassembly was prepared by self-assembling glucose oxidase (GOD) on PtAuNP/ss-DNA/GR nanocomposites (GOD/PtAuNPs/ss-DNA/GR). The nanocomposites provided a suitable microenvironment for GOD to retain its biological activity. The direct and reversible electron transfer process between the active site of GOD and the modified electrode was realized without any extra electron mediator. Thus, the prepared GOD/PtAuNP/ss-DNA/GR electrode was proposed as a biosensor for the quantification of glucose. The effects of pH, applied potential, and temperature on the performance of the biosensor were discussed in detail and were optimized. Under optimal conditions, the biosensor showed a linearity with glucose concentration in the range of 1.0 to 1,800 μM with a detection limit of 0.3 μM (S/N = 3). The results demonstrate that the developed approach provides a promising strategy to improve the sensitivity and enzyme activity of electrochemical biosensors. PMID:24572068

Direct detection of hyaluronidase in urine using cationic gold nanoparticles: a potential diagnostic test for bladder cancer.

PubMed

Nossier, Ahmed Ibrahim; Eissa, Sanaa; Ismail, Manal Fouad; Hamdy, Mohamed Ahmed; Azzazy, Hassan Mohamed El-Said

2014-04-15

Hyaluronidase (HAase) was reported as a urinary marker of bladder cancer. In this study, a simple colorimetric gold nanoparticle (AuNP) assay was developed for rapid and sensitive detection of urinary HAase activity. Charge interaction between polyanionic hyaluronic acid (HA) and cationic AuNPs stabilized with cetyl trimethyl ammonium bromide (CTAB) led to formation of gold aggregates and a red to blue color shift. HAase digests HA into small fragments preventing the aggregation of cationic AuNPs. The nonspecific aggregation of AuNPs in urine samples was overcome by pre-treatment of samples with the polycationic chitosan that was able to agglomerate all negatively charged interfering moieties before performing the assay. The developed AuNP assay was compared with zymography for qualitative detection of urinary HAase activity in 40 bladder carcinoma patients, 11 benign bladder lesions patients and 15 normal individuals, the assay sensitivity was 82.5% vs. 65% for zymography, while the specificity for both assays was 96.1%. The absorption ratio, A530/A620 of the reacted AuNP solution was used to quantify the HAase activity. The best cut off value was 93.5 μU/ng protein, at which the sensitivity was 90% and the specificity was 80.8%.The developed colorimetric AuNP HAase assay is simple, inexpensive, and can aid noninvasive diagnosis of bladder cancer. © 2013 Elsevier B.V. All rights reserved.

Gold core/ceria shell-based redox active nanozyme mimicking the biological multienzyme complex phenomenon

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

Bhagat, Stuti; Srikanth Vallabani, N. V.; Shutthanandan, Vaithiyalingam

Catalytically active individual gold (Au) and cerium oxide (CeO2) nanoparticles are well known to exhibit specific enzyme-like activities, such as natural catalase, oxidase, superoxide dismutase, and peroxidase enzymes. These activities have been maneuvered to design several biological applications such as immunoassays, glucose detection, radiation and free radical protection and tissue engineering. A functional nanozyme depicting multienzyme like properties that functions as a synthetic super enzyme has eluded the researchers in the nanoscience community for past decade. In current report, we have designed a functional multienzyme in the form of Gold (core)-CeO2 (shell) nanoparticles (Au@CeO2 CSNPs) exhibiting excellent peroxidase, catalase andmore » superoxide dismutase enzyme-like activities that are controlled simply by tuning the pH. The reaction kinetic parameters reveal that the peroxidase-like activity of this core shell nanozyme is comparable to natural HRP enzyme. Unlike peroxidase-like activity exhibited by other nanomaterials, Au@CeO2 CSNPs showed decrease in hydroxyl radical formation, suggesting that the bio catalytic reactions are performed by efficient electron transfers. A significant enzyme-like activity of this core shell nanoparticle was conserved at extreme pH (2 – 11) and temperatures (up to 90 °C), clearly suggesting the superiority over natural enzymes. Further, the utility of peroxidase-like activity of this core shell nanoparticles was extended for the detection of glucose, which showed a linear range of detection between (100 µM – 1 mM). It is hypothesized that the proximity of the redox potentials of Au+/Au and Ce (III)/Ce (IV) may result in a redox couple promoting the multienzyme activity of core shell nanoparticles. Au@CeO2 CSNPs may open new directions for development of single platform sensors in multiple biosensing applications.« less

Nonenzymatic free-cholesterol detection via a modified highly sensitive macroporous gold electrode with platinum nanoparticles.

PubMed

Lee, Yi-Jae; Park, Jae-Yeong

2010-12-15

A sensitive macroporous Au electrode with a highly rough surface obtained through the use of with Pt nanoparticles (macroporous Au-/nPts) is reported. It has been designed for nonenzymatic free-cholesterol biosensor applications. A macroporous Au-/nPts electrode was fabricated by electroplating Pt nanoparticles onto a coral-like shaped macroporous Au electrode structure. The macroporous Au-/nPts electrode was physically characterized by field emission scanning electron microscopy (FESEM). It was confirmed that the Pt nanoparticles were well deposited on the surface of the macroporous Au electrode. The porosity and window pore size of the macroporous Au electrode were 50% and 100-300 nm, respectively. The electroplated Pt nanoparticle size was approximately 10-20 nm. Electrochemical experiments showed that the macroporous Au-/nPts exhibited a much larger surface activation area (roughness factor (RF)=2024.7) than the macroporous Au electrode (RF=46.07). The macroporous Au-/nPts also presented a much stronger electrocatalytic activity towards cholesterol oxidation than does the macroporous Au electrode. At 0.2 V, the electrode responded linearly up to a 5 mM cholesterol concentration in a neutral media, with a detection limit of 0.015 mM and detection sensitivity of 226.2 μA mM(-1) cm(-2). Meanwhile, interfering species such as ascorbic acid (AA), acetaminophen (AP), and uric acid (UA), were effectively avoided. This novel nonenzymatic detection electrode has strong applications as an electrochemically based cholesterol biosensor. Copyright © 2010 Elsevier B.V. All rights reserved.

Highly sensitive aptasensor based on synergetic catalysis activity of MoS2-Au-HE composite using cDNA-Au-GOD for signal amplification.

PubMed

Song, Hai-Yan; Kang, Tian-Fang; Lu, Li-Ping; Cheng, Shui-Yuan

2017-03-01

Single or few-layer nanosheets of MoS 2 (MoS 2 nanosheets) and a composite composed of MoS 2 nanosheets, Au nanoparticles (AuNPs) and hemin (HE) (denoted as MoS 2 -Au-HE) were prepared. The composites possessed high synergetic catalysis activity towards the electroreduction of hydrogen peroxide. Furthermore, glucose oxidase (GOD) and AuNPs were used as marker of the complementary DNA (cDNA) strand of kanamycin aptamer to prepare a conjugate (reffered as cDNA-Au-GOD) that was designed as the signal probe. Both cDNA-Au-GOD and MoS 2 -Au-HE were applied to fabricate aptasensor for kanamycin. MoS 2 -Au-HE acted as solid platform for kanamycin aptamer and signal transmitters. AuNPs were employed as the supporter of cDNA and GOD which catalyze dissolved oxygen to produce hydrogen peroxide in the presence of glucose. Then cathodic peak current of H 2 O 2 was recorded by differential pulse voltammetry (DPV). The electrochemical reduction of H 2 O 2 was catalyzed by MoS 2 -Au-HE that was modified onto the surface of a glassy carbon electrode (GCE). The cathodic peak current of H 2 O 2 was highly linearly decreased with an increase of kanamycin concentrations from 1.0ng/L to 1.0×10 5 ng/L, with a detection limit of 0.8ng/L. This aptasensor can be used to detect kanamycin in milk with high specificity, sensitivity and selectivity. Copyright © 2016 Elsevier B.V. All rights reserved.

Label-free okadaic acid detection using growth of gold nanoparticles in sensor gaps as a conductive tag.

PubMed

Pan, Yuxiang; Wan, Zijian; Zhong, Longjie; Li, Xueqin; Wu, Qi; Wang, Jun; Wang, Ping

2017-06-01

Okadaic acid (OA) is a marine toxin ingested by shellfish. In this work, a simple, sensitive and label-free gap-based electrical competitive bioassay has been developed for this biotoxin detection. The gap-electrical biosensor is constructed by modifying interdigitated microelectrodes with gold nanoparticles (AuNPs) and using the self-catalytic growth of AuNPs as conductive bridges. In this development, the AuNPs growth is realized in the solution of glucose and chloroauric acid, with glucose oxidation used as the catalysis for growth of the AuNPs. The catalytic reaction product H 2 O 2 in turn reduces chloroauric acid to make the AuNPs grow. The conductance signal amplification is directly determined by the growth efficiency of AuNPs and closely related to the catalytic activity of AuNPs upon their interaction with OA molecule and OA aptamer. In the absence of OA molecule, the OA aptamer can absorb onto the surfaces of AuNPs due to electrostatic interaction, and the catalytically active sites of AuNPs are fully blocked. Thus the AuNPs growth would not happen. In contrast, the presence of OA molecule can hinder the interaction of OA aptamer and AuNPs. Then the AuNPs sites are exposed and the catalytic growth induces the conductance signal change. The results demonstrated that developed biosensor was able to specifically respond to OA ranging from 5 ppb to 80 ppb, providing limit of detection of 1 ppb. The strategy is confirmed to be effective for OA detection, which indicates the label-free OA biosensor has great potential to offer promising alternatives to the traditional analytical and immunological methods for OA detection.

Synthesis, crystal structure and antimicrobial activities of two isomeric gold(I) complexes with nitrogen-containing heterocycle and triphenylphosphine ligands, [Au(L)(PPh3)] (HL = pyrazole and imidazole).

PubMed

Nomiya, K; Noguchi, R; Ohsawa, K; Tsuda, K; Oda, M

2000-03-01

Two isomeric gold(I)-triphenylphosphine complexes with nitrogen-containing heterocycles, [Au(L)(PPh3) (HL = pyrazole (1), imidazole (2)) were isolated as colorless cubic crystals for 1 and colorless plate crystals for 2, respectively. The crystal structures of 1 and 2 were determined by single-crystal X-ray diffraction. These complexes were also fully characterized by complete elemental analyses, thermogravimetric/differential thermal analyses (TG/DTA) and FT-IR in the solid state and by solution NMR (31P, 1H and 13C) spectroscopy and molecular weight measurements in acetone solution. These complexes consisted of a monomeric 2-coordinate AuNP core both in the solid state and in solution. The molecular structures of 1 and 2 were compared with those of related gold(I) complexes, [Au(1,2,3-triz)(PPh3)] (3, Htriz = triazole), [Au(1,2,4-triz)(PPh3)]2 (4) as a dimer through a gold(I)-gold(I) bond in the solid state, and [Au(tetz)(PPh3)] (5, Htetz = tetrazole). Selective and effective antimicrobial activities against two gram-positive bacteria (B. subtilis, S. aureus) and modest activities against one yeast (C. albicans) found in these gold(I) complexes 1-4 are noteworthy, in contrast to poor activities observed in the corresponding silver(I) complexes.

Starch-templated bio-synthesis of gold nanoflowers for in vitro antimicrobial and anticancer activities

NASA Astrophysics Data System (ADS)

Borah, D.; Hazarika, M.; Tailor, P.; Silva, A. R.; Chetia, B.; Singaravelu, G.; Das, P.

2018-05-01

We describe an in situ method of synthesizing highly branched gold nanoflower (AuNFs) using aqueous seed extract of Syzygium cumini (L.) Skeels as reductant in the presence of 0.3% starch. Surprisingly, when the same reaction was carried out in the absence of starch or with starch at a lower concentration (0.15%), instead of flower-like morphology quasi-spherical or polyhedral nanoparticles (AuNPs) are obtained. The nanomaterials were extensively characterized by HRTEM, FESEM, UV-Vis, FTIR, XRD, XPS and TGA analysis. The biological activities of the materials were investigated for antimicrobial activities against four bacterial strains that include one Gram positive (Staphylococcus aureus MTCC 121), two Gram negative (Escherichia coli MTCC 40 and Pseudomonas aeruginosa MTCC 4673) and one fungi (Candida albicans MTCC 227). The nanoparticles functioned as effective antimicrobial and anti-biofilm agents against all the strains under study. Controlled study revealed that, the AuNFs showed improved efficacy over conventional polyhedral AuNPs against all the microbes under study which might be attributed to the larger surface-to-volume ratio of the nanoflowers. The AuNFs also showed effective in vitro anticancer activity against a human liver cancer cell line (HepG2) with no significant cytotoxicity. Our data suggest that the AuNFs can significantly reduce the cancer cell growth with IC50 value of 20 µg mL-1.

Very Green Photosynthesis of Gold Nanoparticles by a Living Aquatic Plant: Photoreduction of AuIII by the Seaweed Ulva armoricana.

PubMed

Mukhoro, Ofhani C; Roos, Wiets D; Jaffer, Mohammed; Bolton, John J; Stillman, Martin J; Beukes, Denzil R; Antunes, Edith

2018-02-01

Light-assisted in vivo synthesis of gold nanoparticles (NPs) from aqueous solutions of dilute Au III salts by a living green marine seaweed (Ulva armoricana) is reported for the first time. NPs synthesised using typical procedures have many associated environmental hazards. The reported methods involve green, nontoxic, eco-friendly synthetic procedures. The formation of AuNPs was extremely rapid (≈15 min) following illumination of the living U. armoricana, while the rate of NP formation in the dark was very slow (over 2 weeks). The properties of the AuNPs formed were confirmed using a battery of spectroscopic techniques. U. armoricana were found to be very efficient in Au 0 uptake, and this, together with the rapid formation of AuNPs under illumination, indicated that the seaweed remained living during NP formation. The TEM images supported this, revealing that the thylakoid membranes and cell structure remained intact. The AuNPs formed on the surface of U. armoricana thallus, along the cell walls and in the chloroplasts. Without further workup, the dried, U. armoricana-supported AuNPs were efficient in the catalytic reduction of 4-nitrophenol, demonstrating the completely green cycle of AuNP formation and catalytic activity. The results mean that an aquatic plant growing in water rich in gold salts could bio-accumulate AuNPs from its aquatic environment, simply with the activation of sunlight. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Size-dependent tissue kinetics of PEG-coated gold nanoparticles

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

Cho, Wan-Seob; Department of Toxicological Research, National Institute of Food and Drug Safety Evaluation, Korea Food and Drug Administration, Seoul 122-704; Cho, Minjung

2010-05-15

Gold nanoparticles (AuNPs) can be used in various biomedical applications, however, very little is known about their size-dependent in vivo kinetics. Here, we performed a kinetic study in mice with different sizes of PEG-coated AuNPs. Small AuNPs (4 or 13 nm) showed high levels in blood for 24 h and were cleared by 7 days, whereas large (100 nm) AuNPs were completely cleared by 24 h. All AuNPs in blood re-increased at 3 months, which correlated with organ levels. Levels of small AuNPs were peaked at 7 days in the liver and spleen and at 1 month in the mesentericmore » lymph node, and remained high until 6 months, with slow elimination. In contrast, large AuNPs were taken up rapidly (approx 30 min) into the liver, spleen, and mesenteric lymph nodes with less elimination phase. TEM showed that AuNPs were entrapped in cytoplasmic vesicles and lysosomes of Kupffer cells and macrophages of spleen and mesenteric lymph node. Small AuNPs transiently activated CYP1A1 and 2B, phase I metabolic enzymes, in liver tissues from 24 h to 7 days, which mirrored with elevated gold levels in the liver. Large AuNPs did not affect the metabolic enzymes. Thus, propensity to accumulate in the reticuloendothelial organs and activation of phase I metabolic enzymes, suggest that extensive further studies are needed for practical in vivo applications.« less

Folic acid bio-inspired route for facile synthesis of AuPt nanodendrites as enhanced electrocatalysts for methanol and ethanol oxidation reactions

NASA Astrophysics Data System (ADS)

Wang, Ai-Jun; Ju, Ke-Jian; Zhang, Qian-Li; Song, Pei; Wei, Jie; Feng, Jiu-Ju

2016-09-01

Folic acid (FA), as an important biomolecule in cell division and growth, is firstly employed as the structure director and stabilizing agent for controlled synthesis of uniform Au65Pt35 nanodendrites (NDs) by a one-pot wet-chemical bio-inspired route at room temperature. No pre-seed, template, organic solvent, polymer, surfactant or complex instrument is involved. The products are mainly characterized by transmission electron microscopy (TEM), high angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray diffraction (XRD), and X-Ray photoelectron spectroscopy (XPS). The architectures have enlarged electrochemically active surface area (60.6 m2 gPt-1), enhanced catalytic activity and durability for methanol and ethanol oxidation in contrast with commercial Pt black and the other AuPt alloys by tuning the molar ratios of Au to Pt (e.g., Au31Pt69 and Au82Pt18 nanoparticles). This strategy would be applied to fabricate other bimetallic nanocatalysts in fuel cells.

Development of chitosan-coated gold nanoflowers as SERS-active probes

NASA Astrophysics Data System (ADS)

Xu, Dan; Gu, Jiangjiang; Wang, Weina; Yu, Xuehai; Xi, Kai; Jia, Xudong

2010-09-01

Surface-enhanced Raman scattering (SERS) has been intensely researched for many years as a potential technique for highly sensitive detection. This work, through the reduction of HAuCl4 with pyrrole in aqueous solutions, investigated a facile one-pot synthesis of flower-like Au nanoparticles with rough surfaces. The formation process of the Au nanoflowers (AuNFs) was carefully studied, and a spontaneous assembly mechanism was proposed based on the time-course experimental results. The key synthesis strategy was to use pyrrole as a weak particle stabilizing and reducing agent to confine crystal growth in the limited ligand protection region. The nanometer-scale surface roughness of AuNFs provided several hot spots on a single particle, which significantly increased SERS enhancement. Good biocompatible stable Raman-active probes were synthesized by coating AuNFs with chitosan. The conservation of the SERS effects in living cells suggested that the chitosan-capped AuNFs could be suitable for highly sensitive detection and have potential for targeting of tumors in vivo.

SERS-active Au/SiO2 clouds in powder for rapid ex vivo breast adenocarcinoma diagnosis

PubMed Central

Cepeda-Pérez, Elisa; López-Luke, Tzarara; Salas, Pedro; Plascencia-Villa, Germán; Ponce, Arturo; Vivero-Escoto, Juan; José-Yacamán, Miguel; de la Rosa, Elder

2016-01-01

In the present work, we report a dry-based application technique of Au/SiO2 clouds in powder for rapid ex vivo adenocarcinoma diagnosis through surface-enhanced Raman scattering (SERS); using low laser power and an integration time of one second. Several characteristic Raman peaks frequently used for the diagnosis of breast adenocarcinoma in the range of the amide III are successfully enhanced by breading the tissue with Au/SiO2 powder. The SERS activity of these Au/SiO2 powders is attributed to their rapid rehydration upon contact with the wet tissues, which promotes the formation of gold nanoparticle aggregates. The propensity of the Au/SiO2 cloud structures to adsorb biomolecules in the vicinity of the gold nanoparticle clusters promotes the necessary conditions for SERS detection. In addition, electron microscopy, together with elemental analysis, have been used to confirm the structure of the new Au/SiO2 cloud material and to investigate its distribution in breast tissues. PMID:27375955

Investigating the Synthesis, Structure, and Catalytic Properties of Versatile Gold-Based Nanocatalvsts

NASA Astrophysics Data System (ADS)

Pretzer, Lori A.

Transition metal nanomaterials are used to catalyze many chemical reactions, including those key to environmental, medicinal, and petrochemical fields. Improving their catalytic properties and lifetime would have significant economic and environmental rewards. Potentially expedient options to make such advancements are to alter the shape, size, or composition of transition metal nanocatalysts. This work investigates the relationships between structure and catalytic properties of synthesized Au, Pd-on-Au, and Au-enzyme model transition metal nanocatalysts. Au and Pd-on-Au nanomaterials were studied due to their wide-spread application and structure-dependent electronic and geometric properties. The goal of this thesis is to contribute design procedures and synthesis methods that enable the preparation of more efficient transition metal nanocatalysts. The influence of the size and composition of Pd-on-Au nanoparticles (NPs) was systematically investigated and each was found to affect the catalyst's surface structure and catalytic properties. The catalytic hydrodechlorination of trichloroethene and reduction of 4-nitrophenol by Pd-on-Au nanoparticles were investigated as these reactions are useful for environmental and pharmaceutical synthesis applications, respectively. Structural characterization revealed that the dispersion and oxidation state of surface Pd atoms are controlled by the Au particle size and concentration of Pd. These structural changes are correlated with observed Pd-on-Au NP activities for both probe reactions, providing new insight into the structure-activity relationships of bimetallic nanocatalysts. Using the structure-dependent electronic properties of Au NPs, a new type of light-triggered biocatalyst was prepared and used to remotely control a model biochemical reaction. This biocatalyst consists of a model thermophilic glucokinase enzyme covalently attached to the surface of Au nanorods. The rod-like shape of the Au nanoparticles made the thermophilic-enzyme complexes responsive to near infrared electromagnetic radiation, which is absorbed minimally by biological tissues. When enzyme-Au nanorod complexes are illuminated with a near-infrared laser, thermal energy is generated which activates the thermophilic enzyme. Enzyme-Au nanorod complexes encapsulated in calcium alginate are reusable and stable for several days, making them viable for industrial applications. Lastly, highly versatile Au nanoparticles with diameters of ~3-12 nm were prepared using carbon monoxide (CO) to reduce a Au salt precursor onto preformed catalytic Au particles. Compared to other reducing agents used to generate metallic NPs, CO can be used at room temperature and its oxidized form does not interfere with the colloidal stability of NPs suspended in water. Controlled synthesis of different sized particles was verified through detailed ultraviolet-visible spectroscopy, small angle X-ray scattering, and transmission electron microscopy measurements. This synthesis method should be extendable to other monometallic and multimetallic compositions and shapes, and can be improved by using preformed particles with a narrower size distribution.

Elucidation of Active Sites for the Reaction of Ethanol on TiO 2 /Au(111)

DOE PAGES

Boyle, David T.; Wilke, Jeremy A.; Palomino, Robert M.; ...

2017-03-17

Obtaining a molecular-level understanding of the reaction of alcohols with heterogeneous model catalysts is critical for improving industrial catalytic processes, such as the production of H 2 from alcohols. Gold has been shown to be an excellent oxidation catalyst once oxygen is added to it. The use of reducible oxides provides a source of oxygen on Au(111) for the reaction of ethanol, which is easily regenerated in the presence of an oxygen background. In this work, ethanol operates as a probe molecule to investigate the role of Au(111), TiO 2 nanoparticles, and TiO 2/Au interfacial surface sites on the catalyticmore » properties of TiO 2/Au(111). Ultrahigh vacuum temperature-programmed desorption (TPD) studies with ethanol/Au(111) elucidate previously unreported adsorption sites for ethanol. Ethanol molecularly adsorbs to Au terrace sites, step edges, and undercoordinated kink sites with adsorption energies of -51.7, -55.8, and -65.1 kJ/mol, respectively. In a TPD coverage study of ethanol on TiO 2/Au(111) indicates ethanol undergoes dissociative adsorption to form H*(a) and CH 3CH 2O*(a) on the inverse model catalyst surface. The desorption temperature of low coverages of ethanol from TiO2/Au(111) (Tdes ≈ 235 K) is at an intermediate temperature between the desorption temperatures from bulk Au(111) and TiO 2(110), indicating both Au and TiO 2 play a role in the adsorption of ethanol. Both low-temperature adsorption and high-temperature reactions are studied and indicate that ethanol-derived products such as acetaldehyde and ethylene desorb from TiO 2/Au(111) at ~500 K. Here, we report the identification of catalytically active sites on TiO 2/Au(111) as interfacial sites between the oxide and Au(111) surface through the use of temperature-programmed desorption and infrared reflection absorption spectroscopy.« less

Elucidation of Active Sites for the Reaction of Ethanol on TiO 2 /Au(111)

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

Boyle, David T.; Wilke, Jeremy A.; Palomino, Robert M.

Obtaining a molecular-level understanding of the reaction of alcohols with heterogeneous model catalysts is critical for improving industrial catalytic processes, such as the production of H 2 from alcohols. Gold has been shown to be an excellent oxidation catalyst once oxygen is added to it. The use of reducible oxides provides a source of oxygen on Au(111) for the reaction of ethanol, which is easily regenerated in the presence of an oxygen background. In this work, ethanol operates as a probe molecule to investigate the role of Au(111), TiO 2 nanoparticles, and TiO 2/Au interfacial surface sites on the catalyticmore » properties of TiO 2/Au(111). Ultrahigh vacuum temperature-programmed desorption (TPD) studies with ethanol/Au(111) elucidate previously unreported adsorption sites for ethanol. Ethanol molecularly adsorbs to Au terrace sites, step edges, and undercoordinated kink sites with adsorption energies of -51.7, -55.8, and -65.1 kJ/mol, respectively. In a TPD coverage study of ethanol on TiO 2/Au(111) indicates ethanol undergoes dissociative adsorption to form H*(a) and CH 3CH 2O*(a) on the inverse model catalyst surface. The desorption temperature of low coverages of ethanol from TiO2/Au(111) (Tdes ≈ 235 K) is at an intermediate temperature between the desorption temperatures from bulk Au(111) and TiO 2(110), indicating both Au and TiO 2 play a role in the adsorption of ethanol. Both low-temperature adsorption and high-temperature reactions are studied and indicate that ethanol-derived products such as acetaldehyde and ethylene desorb from TiO 2/Au(111) at ~500 K. Here, we report the identification of catalytically active sites on TiO 2/Au(111) as interfacial sites between the oxide and Au(111) surface through the use of temperature-programmed desorption and infrared reflection absorption spectroscopy.« less

Synthesis and electrocatalytic activity of Au/Pt bimetallic nanodendrites for ethanol oxidation in alkaline medium.

PubMed

Han, Xinyi; Wang, Dawei; Liu, Dong; Huang, Jianshe; You, Tianyan

2012-02-01

Gold/Platinum (Au/Pt) bimetallic nanodendrites were successfully synthesized through seeded growth method using preformed Au nanodendrites as seeds and ascorbic acid as reductant. Cyclic voltammograms (CVs) of a series of Au/Pt nanodendrites modified electrodes in 1M KOH solution containing 1M ethanol showed that the electrocatalyst with a molar ratio (Au:Pt) of 3 exhibited the highest peak current density and the lowest onset potential. The peak current density of ethanol electro-oxidation on the Au(3)Pt(1) nanodendrites modified glassy carbon electrode (Au(3)Pt(1) electrode) is about 16, 12.5, and 4.5 times higher than those on the polycrystalline Pt electrode, polycrystalline Au electrode, and Au nanodendrites modified glassy carbon electrode (Au dendrites electrode), respectively. The oxidation peak potential of ethanol electro-oxidation on the Au(3)Pt(1) electrode is about 299 and 276 mV lower than those on the polycrystalline Au electrode and Au dendrites electrode, respectively. These results demonstrated that the Au/Pt bimetallic nanodendrites may find potential application in alkaline direct ethanol fuel cells (ADEFCs). Copyright © 2011 Elsevier Inc. All rights reserved.

Eco-friendly approach for nanoparticles synthesis and mechanism behind antibacterial activity of silver and anticancer activity of gold nanoparticles.

PubMed

Patil, Maheshkumar Prakash; Kim, Gun-Do

2017-01-01

This review covers general information about the eco-friendly process for the synthesis of silver nanoparticles (AgNP) and gold nanoparticles (AuNP) and focuses on mechanism of the antibacterial activity of AgNPs and the anticancer activity of AuNPs. Biomolecules in the plant extract are involved in reduction of metal ions to nanoparticle in a one-step and eco-friendly synthesis process. Natural plant extracts contain wide range of metabolites including carbohydrates, alkaloids, terpenoids, phenolic compounds, and enzymes. A variety of plant species and plant parts have been successfully extracted and utilized for AgNP and AuNP syntheses. Green-synthesized nanoparticles eliminate the need for a stabilizing and capping agent and show shape and size-dependent biological activities. Here, we describe some of the plant extracts involved in nanoparticle synthesis, characterization methods, and biological applications. Nanoparticles are important in the field of pharmaceuticals for their strong antibacterial and anticancer activity. Considering the importance and uniqueness of this concept, the synthesis, characterization, and application of AgNPs and AuNPs are discussed in this review.

Enhancing CO2 Electroreduction with the Metal-Oxide Interface.

PubMed

Gao, Dunfeng; Zhang, Yi; Zhou, Zhiwen; Cai, Fan; Zhao, Xinfei; Huang, Wugen; Li, Yangsheng; Zhu, Junfa; Liu, Ping; Yang, Fan; Wang, Guoxiong; Bao, Xinhe

2017-04-26

The electrochemical CO 2 reduction reaction (CO 2 RR) typically uses transition metals as the catalysts. To improve the efficiency, tremendous efforts have been dedicated to tuning the morphology, size, and structure of metal catalysts and employing electrolytes that enhance the adsorption of CO 2 . We report here a strategy to enhance CO 2 RR by constructing the metal-oxide interface. We demonstrate that Au-CeO x shows much higher activity and Faradaic efficiency than Au or CeO x alone for CO 2 RR. In situ scanning tunneling microscopy and synchrotron-radiation photoemission spectroscopy show that the Au-CeO x interface is dominant in enhancing CO 2 adsorption and activation, which can be further promoted by the presence of hydroxyl groups. Density functional theory calculations indicate that the Au-CeO x interface is the active site for CO 2 activation and the reduction to CO, where the synergy between Au and CeO x promotes the stability of key carboxyl intermediate (*COOH) and thus facilitates CO 2 RR. Similar interface-enhanced CO 2 RR is further observed on Ag-CeO x , demonstrating the generality of the strategy for enhancing CO 2 RR.

The application of aberration-corrected electron microscopy to the characterization of gold-based catalysts

NASA Astrophysics Data System (ADS)

Herzing, Andrew A.

Electron microscopy has long been used to study the morphology of heterogeneous catalysts. Recent advances in electron optics now allow for the correction of the inherent spherical aberration (Cs) produced by the objective lens in the scanning transmission electron microscope (STEM, resulting in a significantly improved spatial resolution as well as the ability to use a much larger probe-current than was previously possible. In this thesis, the combination of high-angle annular dark-field (HAADF) imaging and microanalysis by x-ray energy dispersive spectroscopy (XEDS) in an aberration-corrected STEM has been applied for the first time to the characterization of gold-based heterogeneous catalysts. Multi-variate statistical analysis (MSA) has been employed in order to further improve the STEM-XEDS spectrum image data acquired with this technique. In addition, supplemental analysis using electron-energy loss spectroscopy (EELS) and energy-filtered transmission electron microscopy (EFTEM) in an aberration-corrected instrument has also been attempted. These techniques have proven extremely valuable in providing complimentary information to more traditional catalyst characterization techniques such as x-ray photoelectron spectroscopy and x-ray diffraction in four specific problems relating to catalysis. Firstly, the atomic-scale resolution of Cs-corrected HAADF imaging has been utilized to study Au/FeOx catalysts in order to determine the size and structure of the Au clusters present on the support surface. It was discovered that, while both inactive and active catalysts for low-temperature CO oxidation contained large Au particles (> 5 nm) and individual Au atoms, the active catalyst also contained sub-nm clusters comprised of only a few Au atoms. Secondly, novel CeO2 support materials for Au and Au-Pd catalysts were synthesized by precipitation with supercritical CO2. These supports were found to produce significantly more active catalysts than those based on CeO2 prepared using more traditional methods. The combination of STEM-HAADF imaging and XEDS mapping has been used to characterize these catalysts and a strong correlation between the catalytic activity and the enhanced degree of metal dispersion over the support is demonstrated. Thirdly, a systematic series of Au-Pd/Al2O3 catalysts has been studied in order to characterize the effects of various heat treatments on the development of core-shell morphologies within the bi-metallic particles and its subsequent effect on their catalytic performance for H2O 2 synthesis. STEM-XEDS spectrum imaging was employed in order to determine the degree of alloying and segregation behavior within the individual Au-Pd particles as a function of calcination/reduction temperature. It was found that the as prepared catalyst contained homogeneous Au-Pd alloy particles and that a Pd-rich shell/Au-rich core morphology gradually developed upon calcination. Subsequent reduction of the catalyst caused a large fraction of the particles to invert and form Pd-rich core/Au-rich shell structures. These changes are related to both the activity and stability of the catalyst. Finally, the washing of activated carbon support materials in acid was found to be extremely beneficial for producing Au-Pd catalysts for the direct synthesis of H2O2. STEM-HAADF imaging revealed that the acid-washing treatment increased the dispersion of the metal on the carbon supports. Aberration-corrected STEM-XEDS spectrum imaging demonstrated a strong size dependence of the Au-Pd particle composition. Crucially, the acid-washing pre-treatment enhanced the alloying of Au and Pd by suppressing the formation of large (> 25 nm) Au-rich particles. In summary, the application of aberration-corrected HAADF imaging and STEM-XEDS spectrum imaging to the characterization of Au-based catalysts has enhanced the understanding of the structural and chemical features that determine their catalytic behavior. Specifically, they have allowed us to achieve the following: (a) image individual metal atoms and clusters of just a few atoms dispersed in a real, high surface area catalyst, (b) detect and follow the development of core-shell structures in Au-Pd bi-metallic catalysts, (c) determine composition/size correlations in Au-Pd catalysts, (d) detect minor alloying elements in bi-metallic catalysts, (e) and chemically map atomic or near atomic dispersions of metals on oxide supports.

Elucidating the Influence of Gold Nanoparticles on the Binding of Salvianolic Acid B and Rosmarinic Acid to Bovine Serum Albumin

PubMed Central

Peng, Xin; Qi, Wei; Huang, Renliang; Su, Rongxin; He, Zhimin

2015-01-01

Salvianolic acid B and rosmarinic acid are two main water-soluble active ingredients from Salvia miltiorrhiza with important pharmacological activities and clinical applications. The interactions between salvianolic acid B (or rosmarinic acid) and bovine serum albumin (BSA) in the presence and absence of gold nanoparticles (Au NPs) with three different sizes were investigated by using biophysical methods for the first time. Experimental results proved that two components quenched the fluorescence of BSA mainly through a static mechanism irrespective of the absence or presence of Au NPs. The presence of Au NPs decreased the binding constants of salvianolic acid B with BSA from 27.82% to 10.08%, while Au NPs increased the affinities of rosmarinic acid for BSA from 0.4% to 14.32%. The conformational change of BSA in the presence of Au NPs (caused by a noncompetitive binding between Au NPs and drugs at different albumin sites) induced changeable affinity and binding distance between drugs and BSA compared with no Au NPs. The competitive experiments revealed that the site I (subdomain IIA) of BSA was the primary binding site for salvianolic acid B and rosmarinic acid. Additionally, two compounds may induce conformational and micro-environmental changes of BSA. The results would provide valuable binding information between salvianolic acid B (or rosmarinic acid) and BSA, and also indicated that the Au NPs could alter the interaction mechanism and binding capability of drugs to BSA, which might be beneficial to understanding the pharmacokinetics and biological activities of the two drugs. PMID:25861047

Unconventional route to encapsulated ultrasmall gold nanoparticles for high-temperature catalysis.

PubMed

Zhang, Tingting; Zhao, Hongyu; He, Shengnan; Liu, Kai; Liu, Hongyang; Yin, Yadong; Gao, Chuanbo

2014-07-22

Ultrasmall gold nanoparticles (us-AuNPs, <3 nm) have been recently recognized as surprisingly active and extraordinarily effective green catalysts. Their stability against sintering during reactions, however, remains a serious issue for practical applications. Encapsulating such small nanoparticles in a layer of porous silica can dramatically enhance the stability, but it has been extremely difficult to achieve using conventional sol-gel coating methods due to the weak metal/oxide affinity. In this work, we address this challenge by developing an effective protocol for the synthesis of us-AuNP@SiO2 single-core/shell nanospheres. More specifically, we take an alternative route by starting with ultrasmall gold hydroxide nanoparticles, which have excellent affinity to silica, then carrying out controllable silica coating in reverse micelles, and finally converting gold hydroxide particles into well-protected us-AuNPs. With a single-core/shell configuration that prevents sintering of nearby us-AuNPs and amino group modification of the Au/SiO2 interface that provides additional coordinating interactions, the resulting us-AuNP@SiO2 nanospheres are highly stable at high temperatures and show high activity in catalytic CO oxidation reactions. A dramatic and continuous increase in the catalytic activity has been observed when the size of the us-AuNPs decreases from 2.3 to 1.5 nm, which reflects the intrinsic size effect of the Au nanoparticles on an inert support. The synthesis scheme described in this work is believed to be extendable to many other ultrasmall metal@oxide nanostructures for much broader catalytic applications.

Generation of reactive oxygen species and charge carriers in plasmonic photocatalytic Au@TiO2 nanostructures with enhanced activity.

PubMed

He, Weiwei; Cai, Junhui; Jiang, Xiumei; Yin, Jun-Jie; Meng, Qingbo

2018-06-13

The combination of semiconductor and plasmonic nanostructures, endowed with high efficiency light harvesting and surface plasmon confinement, has been a promising way for efficient utilization of solar energy. Although the surface plasmon resonance (SPR) assisted photocatalysis has been extensively studied, the photochemical mechanism, e.g. the effect of SPR on the generation of reactive oxygen species and charge carriers, is not well understood. In this study, we take Au@TiO2 nanostructures as a plasmonic photocatalyst to address this critical issue. The Au@TiO2 core/shell nanostructures with tunable SPR property were synthesized by the templating method with post annealing thermal treatment. It was found that Au@TiO2 nanostructures exhibit enhanced photocatalytic activity in either sunlight or visible light (λ > 420 nm). Electron spin resonance spectroscopy with spin trapping and spin labeling was used to investigate the enhancing effect of Au@TiO2 on the photo-induced reactive oxygen species and charge carriers. The formation of Au@TiO2 core/shell nanostructures resulted in a dramatic increase in light-induced generation of hydroxyl radicals, singlet oxygen, holes and electrons, as compared with TiO2 alone. This enhancement under visible light (λ > 420 nm) irradiation may be dominated by SPR induced local electrical field enhancement, while the enhancement under sunlight irradiation is dominated by the higher electron transfer from TiO2 to Au. These results unveiled that the superior photocatalytic activity of Au@TiO2 nanostructures correlates with enhanced generation of reactive oxygen species and charge carriers.

Gold nano-particle formation from crystalline AuCN: Comparison of thermal, plasma- and ion-beam activated decomposition

NASA Astrophysics Data System (ADS)

Beck, Mihály T.; Bertóti, Imre; Mohai, Miklós; Németh, Péter; Jakab, Emma; Szabó, László; Szépvölgyi, János

2017-02-01

In this work, in addition to the conventional thermal process, two non-conventional ways, the plasma and ion beam activations are described for preparing gold nanoparticles from microcrystalline AuCN precursor. The phase formation at plasma and ion beam treatments was compared with that at thermal treatments and the products and transformations were characterized by thermogravimetry-mass-spectrometry (TG-MS), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). TG-MS measurements in Ar atmosphere revealed that AuCN decomposition starts at 400 °C and completes at ≈700 °C with evolution of gaseous (CN)2. XPS and TEM show that in heat treatment at 450 °C for 1 h in Ar, loss of nitrogen and carbon occurs and small, 5-30 nm gold particles forms. Heating at 450 °C for 10 h in sealed ampoule, much larger, 60-200 nm size and well faceted Au particles develop together with a fibrous (CN)n polymer phase, and the Au crystallites are covered by a 3-5 nm thick polymer shell. Low pressure Ar plasma treatment at 300 eV energy results in 4-20 nm size Au particles and removes most of the nitrogen and part of carbon. During Ar+ ion bombardment with 2500 eV energy, 5-30 nm size Au crystallites form already in 10 min, with preferential loss of nitrogen and with increased amount of carbon residue. The results suggest that plasma and ion beam activation, acting similarly to thermal treatment, may be used to prepare Au nanoparticles from AuCN on selected surface areas either by depositing AuCN precursors on selected regions or by focusing the applied ionized radiation. Thus they may offer alternative ways for preparing tailor-made catalysts, electronic devices and sensors for different applications.

Effects of temperature and operation parameters on the galvanic corrosion of Cu coupled to Au in organic solderability preservatives process

NASA Astrophysics Data System (ADS)

Oh, SeKwon; Kim, YoungJun; Jung, KiMin; Kim, JongSoo; Shon, MinYoung; Kwon, HyukSang

2017-03-01

In this work, we quantitatively examined the effects of temperature and operation parameters such as anode (Cu) to cathode (Au) area ratio, stirring speed, and Cu ion concentration on the galvanic corrosion kinetics of Cu coupled to Au (icouple ( Cu-Au)) on print circuit board in organic solderability preservative (OSP) soft etching solution. With the increase of temperature, galvanic corrosion rate (icouple ( Cu-Au) was increased; however, the degree of galvanic corrosion rate (icouple ( Cu-Au) - icorr (Cu)) was decreased owing to the lower activation energy of Cu coupled to Au, than that of Cu alone. With the increase of area ratio (cathode/anode), stirring speed of the system, icouple ( Cu-Au) was increased by the increase of cathodic reaction kinetics. And icouple ( Cu-Au) was decreased by the increase of the Cu-ion concentration in the OSP soft etching solution.

Development of dihydrochalcone-functionalized gold nanoparticles for augmented antineoplastic activity

PubMed Central

Moolani, Harsh V; Tockstein, Sarah; Thompson, David H; Dakshinamurthy, Rajalingam

2018-01-01

Background Phloridzin, an antidiabetic and antineoplastic agent usually found in fruit trees, is a dihydrochalcone constituent that has a clinical/pharmaceutical significance as a sodium-glucose linked transport 2 (SGLT2) inhibitor. While the aglycone metabolite of phloridzin, phloretin, displays a reduced capacity of SGLT2 inhibition, this nutraceutical displays enhanced antineoplastic activity in comparison to phloridzin. Purpose The objective of this study was to develop gold nanoparticle (AuNP) mediated delivery of phloridzin and phloretin and explore their anticancer mechanism through conjugation of the dihydrochalcones and the AuNP cores. Methods Phloridzin and phloretin conjugated AuNPs (Phl-AuNP and Pht-AuNP) were synthesized in single-step, rapid, biofriendly processes. The synthesized AuNPs morphology was characterized via transmission electron microscopy and ultraviolet-visible spectroscopy. The presence of phloridzin or phloretin was confirmed using scanning electron microscopy-energy dispersive x-ray spectroscopy. The percentage of organic component (phloridzin/phloretin) onto AuNPs surface was characterized using thermogravimetric analysis. Assessment of the antineoplastic potency of the dihydrochalcones conjugated AuNPs against cancerous cell lines (HeLa) was accomplished through monitoring via flow cytometry. Results The functionalized AuNPs were synthesized via a single-step method that relied only upon the redox potential of the conjugate itself and required no toxic chemicals. The synthesized Phl-AuNPs were found to be in the size range of 15±5 nm, whereas the Pht-AuNP were found to be 8±3 nm, placing both conjugated AuNPs well within the size range necessary for successful pharmaceutical applications. These assays demonstrate a significant increase in the cancerous cell toxicities as a result of the conjugation of the drugs to AuNPs, as indicated by the 17.45-fold increase in the efficacy of Pht-AuNPs over pure phloretin, and the 4.49-fold increase in efficacy of Phl-AuNP over pure phloridzin. Conclusion We report a simple, biofriendly process using the reducing and capping potential of the dihydrochalcones, phloridzin and phloretin, to synthesize stable AuNPs that have promising futures as potential antineoplastic agents. PMID:29636609

Development of dihydrochalcone-functionalized gold nanoparticles for augmented antineoplastic activity.

PubMed

Payne, Jason N; Badwaik, Vivek D; Waghwani, Hitesh K; Moolani, Harsh V; Tockstein, Sarah; Thompson, David H; Dakshinamurthy, Rajalingam

2018-01-01

Phloridzin, an antidiabetic and antineoplastic agent usually found in fruit trees, is a dihydrochalcone constituent that has a clinical/pharmaceutical significance as a sodium-glucose linked transport 2 (SGLT2) inhibitor. While the aglycone metabolite of phloridzin, phloretin, displays a reduced capacity of SGLT2 inhibition, this nutraceutical displays enhanced antineoplastic activity in comparison to phloridzin. The objective of this study was to develop gold nanoparticle (AuNP) mediated delivery of phloridzin and phloretin and explore their anticancer mechanism through conjugation of the dihydrochalcones and the AuNP cores. Phloridzin and phloretin conjugated AuNPs (Phl-AuNP and Pht-AuNP) were synthesized in single-step, rapid, biofriendly processes. The synthesized AuNPs morphology was characterized via transmission electron microscopy and ultraviolet-visible spectroscopy. The presence of phloridzin or phloretin was confirmed using scanning electron microscopy-energy dispersive x-ray spectroscopy. The percentage of organic component (phloridzin/phloretin) onto AuNPs surface was characterized using thermogravimetric analysis. Assessment of the antineoplastic potency of the dihydrochalcones conjugated AuNPs against cancerous cell lines (HeLa) was accomplished through monitoring via flow cytometry. The functionalized AuNPs were synthesized via a single-step method that relied only upon the redox potential of the conjugate itself and required no toxic chemicals. The synthesized Phl-AuNPs were found to be in the size range of 15±5 nm, whereas the Pht-AuNP were found to be 8±3 nm, placing both conjugated AuNPs well within the size range necessary for successful pharmaceutical applications. These assays demonstrate a significant increase in the cancerous cell toxicities as a result of the conjugation of the drugs to AuNPs, as indicated by the 17.45-fold increase in the efficacy of Pht-AuNPs over pure phloretin, and the 4.49-fold increase in efficacy of Phl-AuNP over pure phloridzin. We report a simple, biofriendly process using the reducing and capping potential of the dihydrochalcones, phloridzin and phloretin, to synthesize stable AuNPs that have promising futures as potential antineoplastic agents.

Forming a Highly Active, Homogeneously Alloyed AuPt Co-catalyst Decoration on TiO2 Nanotubes Directly During Anodic Growth.

PubMed

Bian, Haidong; Nguyen, Nhat Truong; Yoo, JeongEun; Hejazi, Seyedsina; Mohajernia, Shiva; Müller, Julian; Spiecker, Erdmann; Tsuchiya, Hiroaki; Tomanec, Ondrej; Sanabria-Arenas, Beatriz E; Zboril, Radek; Li, Yang Yang; Schmuki, Patrik

2018-05-30

Au and Pt do not form homogeneous bulk alloys as they are thermodynamically not miscible. However, we show that anodic TiO 2 nanotubes (NTs) can in situ be uniformly decorated with homogeneous AuPt alloy nanoparticles (NPs) during their anodic growth. For this, a metallic Ti substrate containing low amounts of dissolved Au (0.1 atom %) and Pt (0.1 atom %) is used for anodizing. The matrix metal (Ti) is converted to oxide, whereas at the oxide/metal interface direct noble metal particle formation and alloying of Au and Pt takes place; continuously these particles are then picked up by the growing nanotube wall. In our experiments, the AuPt alloy NPs have an average size of 4.2 nm, and at the end of the anodic process, these are regularly dispersed over the TiO 2 nanotubes. These alloyed AuPt particles act as excellent co-catalyst in photocatalytic H 2 generation, with a H 2 production rate of 12.04 μL h -1 under solar light. This represents a strongly enhanced activity as compared to TiO 2 NTs decorated with monometallic particles of Au (7 μL h -1 ) or Pt (9.96 μL h -1 ).

Dynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles

DOE PAGES

Wang, Yanggang; Mei, Donghai; Glezakou, Vassiliki Alexandra; ...

2015-03-04

Ab initio Molecular Dynamics simulations and static Density Functional Theory calculations have been performed to investigate the reaction mechanism of CO oxidation on Au/CeO 2 catalyst. It is found that under reaction condition CO adsorption significantly labializes the surface atoms of the Au cluster and leads to the formation of isolated Au+-CO species that resides on the support in the vicinity of the Au particle. In this context, we identified a dynamic single-atom catalytic mechanism at the interfacial area for CO oxidation on Au/CeO 2 catalyst, which is a lower energy pathway than that of CO oxidation at the interfacemore » with the metal particle. This results from the ability of the single atom site to strongly couple with the redox properties of the support in a synergistic manner thereby lowering the barrier for redox reactions. We find that the single Au+ ion, which only exists under reaction conditions, breaks away from the Au cluster to catalyze CO oxidation and returns to the Au cluster after the catalytic cycle is completed. Generally, our study highlights the importance of the dynamic creation of active sites under reaction conditions and their essential role in a catalytic process.« less

Au-HKUST-1 Composite Nanocapsules: Synthesis with a Coordination Replication Strategy and Catalysis on CO Oxidation.

PubMed

Liu, Yongxin; Zhang, Jiali; Song, Lingxiao; Xu, Wenyuan; Guo, Zanru; Yang, Xiaomin; Wu, Xiaoxin; Chen, Xi

2016-09-07

A novel coordination replication of Cu2O redox-template strategy is reported to efficiently fabricate Au-HKUST-1 composite nanocapsule, with a HKUST-1 sandwich shell and an embedded Au nanoparticles layer. The novel synthesis procedure involves forming Au nanoparticles on the surface of Cu2O, transforming partial Cu2O into HKUST-1 shell via coordination replication, and removing the residual Cu2O by acid. The as-prepared Au-HKUST-1 composite nanocapsules displayed high catalytic activity on CO oxidation.

Au functionalized ZnO rose-like hierarchical structures and their enhanced NO2 sensing performance

NASA Astrophysics Data System (ADS)

Shingange, K.; Swart, H. C.; Mhlongo, G. H.

2018-04-01

Herein, we present ZnO rose-like hierarchical nanostructures employed as support to Au nanoparticles to produce Au functionalized three dimensional (3D) ZnO hierarchical nanostructures (Au/ZnO) for NO2 detection using a microwave-assisted method. Comparative analysis of NO2 sensing performance between the pristine ZnO and Au/ZnO rose-like structures at 300 °C revealed improved NO2 response and rapid response-recovery times with Au incorporation owing to a combination of high surface accessibility induced by hierarchical nanostructure design and catalytic activity of the small Au nanoparticles. Structural and optical analyses acquired from X-ray diffraction, scanning electron microscopy, transmission electron microscope and photoluminescence spectroscopy were also performed.

Photoelectron spectroscopic and computational study of (M-CO2)- anions, M = Cu, Ag, Au

NASA Astrophysics Data System (ADS)

Zhang, Xinxing; Lim, Eunhak; Kim, Seong K.; Bowen, Kit H.

2015-11-01

In a combined photoelectron spectroscopic and computational study of (M-CO2)-, M = Au, Ag, Cu, anionic complexes, we show that (Au-CO2)- forms both the chemisorbed and physisorbed isomers, AuCO 2- and Au-(CO2), respectively; that (Ag-CO2)- forms only the physisorbed isomer, Ag-(CO2); and that (Cu-CO2)- forms only the chemisorbed isomer, CuCO 2- . The two chemisorbed complexes, AuCO 2- and CuCO 2- , are covalently bound, formate-like anions, in which their CO2 moieties are significantly reduced. These two species are examples of electron-induced CO2 activation. The two physisorbed complexes, Au-(CO2) and Ag-(CO2), are electrostatically and thus weakly bound.

Multimetallic nanoparticle catalysts with enhanced electrooxidation

DOEpatents

Sun, Shouheng; Zhang, Sen; Zhu, Huiyuan; Guo, Shaojun

2015-07-28

A new structure-control strategy to optimize nanoparticle catalysis is provided. The presence of Au in FePtAu facilitates FePt structure transformation from chemically disordered face centered cubic (fcc) structure to chemically ordered face centered tetragonal (fct) structure, and further promotes formic acid oxidation reaction (FAOR). The fct-FePtAu nanoparticles show high CO poisoning resistance, achieve mass activity as high as about 2810 mA/mg Pt, and retain greater than 90% activity after a 13 hour stability test.

Manipulation of surface plasmon resonance of a graphene-based Au aperture antenna in visible and near-infrared regions

NASA Astrophysics Data System (ADS)

Wan, Yuan; An, Yashuai; Tao, Zhi; Deng, Luogen

2018-03-01

Behaviors of surface plasmon resonance (SPR) of a graphene-based Au aperture antenna are investigated in visible and near-infrared (vis-NIR) regions. Compared with the SPR wavelength of a traditional Au aperture antenna, the SPR wavelength of the graphene-based Au aperture antenna shows a remarkable blue shift due to the redistribution of the electric field in the proposed structure. The electric field of the graphene-based Au aperture antenna is highly localized on the surface of the graphene in the aperture and redistributed to be a standing wave. Moreover, the SPR of a graphene-based Au aperture antenna is sensitive to the thickness and the refractive index of the dielectric layer, the graphene Fermi energy, the refractive index of the environment and the polarization direction of the incident light. Finally, we find the wavelength, intensity and phase of the reflected light of the graphene-based Au aperture antenna array can be actively modulated by varying the graphene Fermi energy. The proposed structure provides a promising platform for realizing a tunable optical filter, a highly sensitive refractive index sensor, and other actively tunable optical and optoelectronic devices.

Understanding and controlling the structure and segregation behaviour of AuRh nanocatalysts

PubMed Central

Piccolo, Laurent; Li, Z. Y.; Demiroglu, Ilker; Moyon, Florian; Konuspayeva, Zere; Berhault, Gilles; Afanasiev, Pavel; Lefebvre, Williams; Yuan, Jun; Johnston, Roy L.

2016-01-01

Heterogeneous catalysis, which is widely used in the chemical industry, makes a great use of supported late-transition-metal nanoparticles, and bimetallic catalysts often show superior catalytic performances as compared to their single metal counterparts. In order to optimize catalyst efficiency and discover new active combinations, an atomic-level understanding and control of the catalyst structure is desirable. In this work, the structure of catalytically active AuRh bimetallic nanoparticles prepared by colloidal methods and immobilized on rutile titania nanorods was investigated using aberration-corrected scanning transmission electron microscopy. Depending on the applied post-treatment, different types of segregation behaviours were evidenced, ranging from Rh core – Au shell to Janus via Rh ball – Au cup configuration. The stability of these structures was predicted by performing density-functional-theory calculations on unsupported and titania-supported Au-Rh clusters; it can be rationalized from the lower surface and cohesion energies of Au with respect to Rh, and the preferential binding of Rh with the titania support. The bulk-immiscible AuRh/TiO2 system can serve as a model to understand similar supported nanoalloy systems and their synergistic behaviour in catalysis. PMID:27739480

Different behaviors in the transformation of PATP adsorbed on Ag or Au nanoparticles investigated by surface-enhanced Raman spectroscopy - A study of the effects from laser energy and annealing

NASA Astrophysics Data System (ADS)

Xu, Jian-Fang; Luo, Shi-Yi; Liu, Guo-Kun

2015-05-01

In order to explore the key role of surface plasmon resonance (SPR) and active 3O2 for the chemical transformation to 4,4-dimercaptoazobenzene (DMAB) from p-aminothiophenol (PATP) adsorbed on Ag or Au NPs, we systematically investigated the laser wavelength and temperature dependent surface-enhanced Raman spectra of PATP capped Ag and Au NPs. DMAB can be easily observed at the 514.5 nm laser for Ag NPs but at the 632.8 nm laser for Au NPs, indicating that a suitable energy level is necessary for the formation of DMAB. The tendency is consistent with the wavelength dependent SPR properties of Ag or Au NPs accordingly. With the energy provided by annealing, the transformation of PATP to DMAB is much easier on Ag NPs at a lower temperature, and more DMAB can be observed at the same temperature, compared to the case of Au NPs under the same condition. It is mainly due to the active 3O2 on Ag surfaces could be more easily formed than that on Au surfaces.

Gallic acid-capped gold nanoparticles inhibit EGF-induced MMP-9 expression through suppression of p300 stabilization and NFκB/c-Jun activation in breast cancer MDA-MB-231 cells.

PubMed

Chen, Ying-Jung; Lee, Yuan-Chin; Huang, Chia-Hui; Chang, Long-Sen

2016-11-01

Triple-negative breast cancers (TNBCs) are highly invasive and have a higher rate of distant metastasis. Matrix metalloproteinase-9 (MMP-9) plays a crucial role in EGF/EGFR-mediated malignant progression and metastasis of TNBCs. Various studies have revealed that treatment with gallic acid down-regulates MMP-9 expression in cancer cells, and that conjugation of phytochemical compounds with gold nanoparticles (AuNPs) increases the anti-tumor activity of the phytochemical compounds. Thus, the effect of gallic acid-capped AuNPs (GA-AuNPs) on MMP-9 expression in EGF-treated TNBC MDA-MB-231 cells was analyzed in the present study. The so-called green synthesis of AuNPs by means of gallic acid was performed at pH10, and the resulting GA-AuNPs had spherical shape with an average diameter of approximately 50nm. GA-AuNPs notably suppressed migration and invasion of EGF-treated cells, and inhibited EGF-induced MMP-9 up-regulation. GA-AuNPs abrogated EGF-induced Akt/p65 and ERK/c-Jun phosphorylation, leading to down-regulation of MMP-9 mRNA and protein expression in EGF-treated cells. Meanwhile, EGF-induced p300 stabilization was found to be involved in MMP-9 expression, whereas GA-AuNPs inhibited the EGF-promoted stability of the p300 protein. Although GA-AuNPs and gallic acid suppressed EGF-induced MMP-9 up-regulation via the same signaling pathway, the effective concentration of gallic acid was approximately 100-fold higher than that of GA-AuNPs for inhibition of MMP-9 expression in EGF-treated cells to a similar extent. Collectively, our data indicate that, in comparison with gallic acid, GA-AuNPs have a superior ability to inhibit EGF/EGFR-mediated MMP-9 expression in TNBC MDA-MB-231 cells. Our findings also point to a way to improve the anti-tumor activity of gallic acid. Copyright © 2016 Elsevier Inc. All rights reserved.

Peptide-coated gold nanoparticles for modulation of angiogenesis in vivo.

PubMed

Roma-Rodrigues, Catarina; Heuer-Jungemann, Amelie; Fernandes, Alexandra R; Kanaras, Antonios G; Baptista, Pedro V

2016-01-01

In this work, peptides designed to selectively interact with cellular receptors involved in the regulation of angiogenesis were anchored to oligo-ethylene glycol-capped gold nanoparticles (AuNPs) and used to evaluate the modulation of vascular development using an ex ovo chick chorioallantoic membrane assay. These nanoparticles alter the balance between naturally secreted pro- and antiangiogenic factors, under various biological conditions, without causing toxicity. Exposure of chorioallantoic membranes to AuNP-peptide activators of angiogenesis accelerated the formation of new arterioles when compared to scrambled peptide-coated nanoparticles. On the other hand, antiangiogenic AuNP-peptide conjugates were able to selectively inhibit angiogenesis in vivo. We demonstrated that AuNP vectorization is crucial for enhancing the effect of active peptides. Our data showed for the first time the effective control of activation or inhibition of blood vessel formation in chick embryo via AuNP-based formulations suitable for the selective modulation of angiogenesis, which is of paramount importance in applications where promotion of vascular growth is desirable (eg, wound healing) or ought to be contravened, as in cancer development.

Highly active Au/δ-MoC and Au/β-Mo 2C catalysts for the low-temperature water gas shift reaction: effects of the carbide metal/carbon ratio on the catalyst performance

DOE PAGES

Posada-Pérez, Sergio; Gutiérrez, Ramón A.; Zuo, Zhijun; ...

2017-05-08

In this paper, the water gas shift (WGS) reaction catalyzed by orthorhombic β-Mo 2C and cubic δ-MoC surfaces with and without Au clusters supported thereon has been studied by means of a combination of sophisticated experiments and state-of-the-art computational modeling. Experiments evidence the importance of the metal/carbon ratio on the performance of these systems, where Au/δ-MoC is presented as a suitable catalyst for WGS at low temperatures owing to its high activity, selectivity (only CO 2 and H 2 are detected), and stability (oxycarbides are not observed). Periodic density functional theory-based calculations show that the supported Au clusters and themore » Au/δ-MoC interface do not take part directly in water dissociation but their presence is crucial to switch the reaction mechanism, drastically decreasing the effect of the reverse WGS reaction and favoring the WGS products desorption, thus leading to an increase in CO 2 and H 2 production. Finally, the present results clearly display the importance of the Mo/C ratio and the synergy with the admetal clusters in tuning the activity and selectivity of the carbide substrate.« less

Molecular oxygen adsorption and dissociation on Au12M clusters with M = Cu, Ag or Ir

NASA Astrophysics Data System (ADS)

Jiménez-Díaz, Laura M.; Pérez, Luis A.

2018-03-01

In this work, we present a density functional theory study of the structural and electronic properties of isolated neutral clusters of the type Au12M, with M = Cu, Ag, or Ir. On the other hand, there is experimental evidence that gold-silver, gold-copper and gold-iridium nanoparticles have an enhanced catalytic activity for the CO oxidation reaction. In order to address these phenomena, we also performed density functional calculations of the adsorption and dissociation of O2 on these nanoparticles. Moreover, to understand the effects of Cu, Ag, and Ir impurity atoms on the dissociation of O2, we also analyze this reaction in the corresponding pure gold cluster. The results indicate that the substitution of one gold atom in a Au13 cluster by Ag, Cu or Ir diminishes the activation energy barrier for the O2 dissociation by nearly 1 eV. This energy barrier is similar for Au12Ag and Au12Cu, whereas for Au12Ir is even lower. These results suggest that the addition of other transition metal atoms to gold nanoclusters can enhance their catalytic activity towards the CO oxidation reaction, independently of the effect that the substrate could have on supported nanoclusters.

Highly efficient and porous TiO2-coated Ag@Fe3O4@C-Au microspheres for degradation of organic pollutants

NASA Astrophysics Data System (ADS)

Shen, Mao; Chen, Suqing; Jia, Wenping; Fan, Guodong; Jin, Yanxian; Liang, Huading

2016-12-01

In this paper, we reported a novel hierarchical porous Ag@Fe3O4@C-Au@TiO2 core@shell microspheres with a highly photocatalytic activity and magnetically separable properties. The synthesis method is included of a Fe3O4 magnetic embedded Ag core (Ag@Fe3O4), an interlayer of carbon modified by PEI to form sufficient amounts of amine functional groups (Ag@Fe3O4@C-PEI), the grafting of Au nanoparticles on the surface of Ag@Fe3O4@C-PEI (Ag@Fe3O4@C-Au), and an ordered porous TiO2 structured shell. As an example of the applications, the photocatalytic activities of the samples were investigated by the reduction of Rhodamine B (RhB) under visible-light irradiation. The results show that the porous Ag@Fe3O4@C-Au@TiO2 core@shell microspheres display higher adsorption and photocatalytic activities compared to the pure porous TiO2 and Ag@Fe3O4@C@TiO2 microspheres, which are attributed to the local surface plasmon resonance (LSPR) by the Ag and Au nanoparticles and the high specific surface area.

Highly active Au/δ-MoC and Au/β-Mo 2C catalysts for the low-temperature water gas shift reaction: effects of the carbide metal/carbon ratio on the catalyst performance

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

Posada-Pérez, Sergio; Gutiérrez, Ramón A.; Zuo, Zhijun

In this paper, the water gas shift (WGS) reaction catalyzed by orthorhombic β-Mo 2C and cubic δ-MoC surfaces with and without Au clusters supported thereon has been studied by means of a combination of sophisticated experiments and state-of-the-art computational modeling. Experiments evidence the importance of the metal/carbon ratio on the performance of these systems, where Au/δ-MoC is presented as a suitable catalyst for WGS at low temperatures owing to its high activity, selectivity (only CO 2 and H 2 are detected), and stability (oxycarbides are not observed). Periodic density functional theory-based calculations show that the supported Au clusters and themore » Au/δ-MoC interface do not take part directly in water dissociation but their presence is crucial to switch the reaction mechanism, drastically decreasing the effect of the reverse WGS reaction and favoring the WGS products desorption, thus leading to an increase in CO 2 and H 2 production. Finally, the present results clearly display the importance of the Mo/C ratio and the synergy with the admetal clusters in tuning the activity and selectivity of the carbide substrate.« less

Investigation of oxygen reduction and methanol oxidation reaction activity of PtAu nano-alloy on surface modified porous hybrid nanocarbon supports

NASA Astrophysics Data System (ADS)

Parambath Vinayan, Bhaghavathi; Nagar, Rupali; Ramaprabhu, Sundara

2016-09-01

We investigate the electrocatalytic activity of PtAu alloy nanoparticles supported on various chemically modified carbon morphologies towards oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). The surface-modification of graphene nanosheets (f-G), multi-walled carbon nanotubes (f-MWNTs) and (graphene nanosheets-carbon nanotubes) hybrid support (f-G-MWNTs) were carried out by soft functionalization method using a cationic polyelectrolyte poly-(diallyldimethyl ammonium chloride). The Pt and PtAu alloy nanoparticles were dispersed over chemically modified carbon supports by sodium-borohydride assisted modified polyol reduction method. The electrochemical performance of all electrocatalysts were studied by half- and full-cell proton exchange membrane fuel cell (PEMFC) measurements and PtAu/f-G-MWNTs catalyst comparatively yielded the best catalytic performance. PEMFC full cell measurements of PtAu/f-G-MWNTs cathode electrocatalyst yield a maximum power density of 319 mW cm-2 at 60 °C without any back pressure,which is 2.1 times higher than that of cathode electrocatalyst Pt on graphene support. The high ORR and MOR activity of PtAu/f-G-MWNTs electrocatalyst is due to the alloying effect and inherent beneficial properties of porous hybrid nanocarbon support.

Sandwiched ZnO@Au@CdS nanorod arrays with enhanced visible-light-driven photocatalytical performance

NASA Astrophysics Data System (ADS)

Ren, Shoutian; Wang, Yingying; Fan, Guanghua; Gao, Renxi; Liu, Wenjun

2017-11-01

The development of high-performance photocatalysts is central to efforts focused on taking advantage of solar energy to overcome environmental and energy crises. Integrating different functional materials artfully into nanostructures can deliver more efficient photocatalytic activity. Here, sandwiched ZnO@Au@CdS nanorod films were synthesized via successive ZnO nanorod electrodeposition, Au sputtering and CdS electrodeposition. The as-synthesized composites were characterized by UV-vis spectrophotometer, x-ray diffractometer, scanning and transmission electron microscopy. Their photocatalytic activity was assessed by degrading Rhodamine B solution under visible light irradiation. ZnO@Au@CdS exhibited better photocatalytic performance than ZnO@CdS throughout the visible light region, and the corresponding enhancement factor of Au nanoparticles was measured as a function of CdS loading amount, and it could reach 190% with CdS deposition for 1 min. The normalized rate constant could reach 0.387 h-1 for ZnO@Au@CdS-1min, which was equivalent to or better than results in reference photocatalysts. The enhancement mechanism of Au nanoparticles was estimated by comparing the monochromatic photocatalytic action spectra with the absorption spectrum of ZnO@Au@CdS, and it was mainly determined by incident photon energy. With selective excitation of Au nanoparticles by incident photons, the excited hot electrons in Au NPs are transferred to the conduction band of ZnO to boost photocatalytic reaction. With selective excitation of CdS, the enhanced interband absorption of CdS and relay station effect of Au nanoparticles should be responsible for the enhanced photocatalytic performance. Our work not only opens the door to the design of efficient supported photocatalysts, but also helps to understand the enhancement mechanism of LSPR effect on the photoelectric conversion of semiconductors.

Light controllable catalytic activity of Au clusters decorated with photochromic molecules.

PubMed

Guo, Na; Yam, Kah Meng; Zhang, Chun

2018-06-15

By ab initio calculations, we show that when decorated with a photochromic molecule, the catalytic activity of an Au nanocluster can be reversibly controlled by light. The combination of a photochromic thiol-pentacarbonyl azobenzene (TPA) molecule and an Au 8 cluster is chosen as a model catalyst. The TPA molecule has two configurations (trans and cis) that can be reversibly converted to each other upon photo-excitation. Our calculations show that when the TPA takes the trans configuration, the combined system (trans-Au 8 ) is an excellent catalyst for CO oxidation. The reaction barrier of the catalyzed CO oxidation is less than 0.4 eV. While, the reaction barrier of CO oxidation catalyzed by cis-Au 8 is very high (>2.7 eV), indicating that the catalyst is inactive. These results pave the way for a new class of light controllable nanoscale catalysts.

Light controllable catalytic activity of Au clusters decorated with photochromic molecules

NASA Astrophysics Data System (ADS)

Guo, Na; Meng Yam, Kah; Zhang, Chun

2018-06-01

By ab initio calculations, we show that when decorated with a photochromic molecule, the catalytic activity of an Au nanocluster can be reversibly controlled by light. The combination of a photochromic thiol-pentacarbonyl azobenzene (TPA) molecule and an Au8 cluster is chosen as a model catalyst. The TPA molecule has two configurations (trans and cis) that can be reversibly converted to each other upon photo-excitation. Our calculations show that when the TPA takes the trans configuration, the combined system (trans-Au8) is an excellent catalyst for CO oxidation. The reaction barrier of the catalyzed CO oxidation is less than 0.4 eV. While, the reaction barrier of CO oxidation catalyzed by cis-Au8 is very high (>2.7 eV), indicating that the catalyst is inactive. These results pave the way for a new class of light controllable nanoscale catalysts.

Green synthesis of Nerium oleander-conjugated gold nanoparticles and study of its in vitro anticancer activity on MCF-7 cell lines and catalytic activity

NASA Astrophysics Data System (ADS)

Barai, Abir Chandan; Paul, Koushik; Dey, Aditi; Manna, Subhankar; Roy, Somenath; Bag, Braja Gopal; Mukhopadhyay, Chiradeep

2018-04-01

The phytochemicals present in the stem bark extract of Nerium oleander (commonly known as Karabi) have been utilized for the green synthesis of stable gold-conjugated nanoparticles at room temperature under very mild conditions. The green synthesized gold-conjugated nanoparticles were characterized by surface plasmon resonance spectroscopy, High resolution transmission electron microscopy, X-ray diffraction studies and dynamic light scattering. A mechanism for the synthesis and stabilization of gold-conjugated nanoparticles (AuNPs) has been proposed. Anticancer activity of the stabilized AuNPs studied against MCF-7 breast cancer cell line revealed that the stabilized AuNPs were highly effective for the apoptosis of cancer cells selectively. The antioxidant activity of the stem bark extract of Nerium oleander has also been studied against a long lived 2,2-diphenylpicrylhydrazyl radical at room temperature. Moreover, the utilization of the stabilized AuNPs as a catalyst has also been demonstrated. [Figure not available: see fulltext.

Biogenic synthesis of Ag-Au-In decorated on rGO nanosheet and its antioxidant and biological activities

NASA Astrophysics Data System (ADS)

Hazarika, Moushumi; Sonowal, Shashanka; Saikia, Indranirekha; Boruah, Purna K.; Das, Manash R.; Tamuly, Chandan

2017-09-01

Au-Ag-In-rGO nanocomposite was synthesized using fruit extract of Zanthoxylum rhetsa which is an eco-friendly, simple and green method. It was characterized by UV-visible, FT-IR, XRD, XPS, EDX, TEM technique. The antioxidant capacity of the nanocomposite was evaluated in presence of AgNO3, HAuCl4 and InCl3 solution respectively at 25 °C. The results showed significant antioxidant activity in presence of 1  ×  10-5 mM AgNO3 solution. The antibacterial activity of Au-Ag-In-rGO nanoparticles was carried out against the gram  -ve bacteria Pseudomonas aeruginosa, Escherichia coli and gram  +ve bacteria Staphylococcus aureus and Bacillus cereus. The bacterial growth kinetics was studied. The bacterial strain E. coli and S. aureus showed complete inhibition at concentration 100 µg ml-1. The activity is more effective in case of Au-Ag-In-rGO compared to GO.

Operando investigation of Au-MnO x thin films with improved activity for the oxygen evolution reaction

DOE PAGES

Frydendal, Rasmus; Seitz, Linsey C.; Sokaras, Dimosthenis; ...

2017-01-20

The electrochemical splitting of water holds great potential as a method for producing clean fuels by storing electricity from intermittent energy sources. The efficiency of such a process would be greatly facilitated by incorporating more active catalysts based on abundant materials for the oxygen evolution reaction. Manganese oxides are promising as catalysts for this reaction. Recent reports show that their activity can be drastically enhanced when modified with gold. Herein, we investigate highly active mixed Au-MnO x thin films for the oxygen evolution reaction, which exhibit more than five times improvement over pure MnO x. These films are characterized withmore » operando X-ray Absorption Spectroscopy, which reveal that Mn assumes a higher oxidation state under reaction conditions when Au is present. As a result, the magnitude of the enhancement is correlated to the size of the Au domains, where larger domains are the more beneficial.« less

Green synthesis of Nerium oleander-conjugated gold nanoparticles and study of its in vitro anticancer activity on MCF-7 cell lines and catalytic activity.

PubMed

Barai, Abir Chandan; Paul, Koushik; Dey, Aditi; Manna, Subhankar; Roy, Somenath; Bag, Braja Gopal; Mukhopadhyay, Chiradeep

2018-01-01

The phytochemicals present in the stem bark extract of Nerium oleander (commonly known as Karabi) have been utilized for the green synthesis of stable gold-conjugated nanoparticles at room temperature under very mild conditions. The green synthesized gold-conjugated nanoparticles were characterized by surface plasmon resonance spectroscopy, High resolution transmission electron microscopy, X-ray diffraction studies and dynamic light scattering. A mechanism for the synthesis and stabilization of gold-conjugated nanoparticles (AuNPs) has been proposed. Anticancer activity of the stabilized AuNPs studied against MCF-7 breast cancer cell line revealed that the stabilized AuNPs were highly effective for the apoptosis of cancer cells selectively. The antioxidant activity of the stem bark extract of Nerium oleander has also been studied against a long lived 2,2-diphenylpicrylhydrazyl radical at room temperature. Moreover, the utilization of the stabilized AuNPs as a catalyst has also been demonstrated.

One pot environmental friendly synthesis of gold nanoparticles using Punica Granatum Juice: A novel antioxidant agent for future dermatological and cosmetic applications.

PubMed

Gubitosa, Jennifer; Rizzi, Vito; Lopedota, Angela; Fini, Paola; Laurenzana, Anna; Fibbi, Gabriella; Fanelli, Fiorenza; Petrella, Andrea; Laquintana, Valentino; Denora, Nunzio; Comparelli, Roberto; Cosma, Pinalysa

2018-07-01

The interesting properties of Gold Nanoparticles (AuNPs) make them attractive for different application fields such as cosmetology, medicine and clinical nanotechnologies. In this work a fast, easy and eco-friendly method for the AuNPs synthesis is proposed by using the Punica Granatum Juice (PGJ) with potential dermatological and cosmetic applications. The AuNPs antioxidant activity, due to the presence of phenols from the juice, and their use as booster for improving the Sun Protection Factor (SPF) in commercial sunscreen formulations, are thus expounded. By using appropriate amounts of PGJ and HAuCl 4 , under mild work conditions, AuNPs with a mean size of 100 ± 40 nm are observed and carefully characterized. Solution pH, temperature, and volume were also changed for optimizing the AuNPs formation and features. The antioxidant activity was studied, by evaluating the AuNP ability of scavenging the radical 2,2-diphenyl-1-picrylhydrazylhydrate (DPPH). This finding was confirmed performing special experiments focused on the reaction between AuNPs and H 2 O 2 , by using suitable probes, such as 4-thiothymidine (S 4 TdR) and Cytochrome-c (Cyt-c). The SPF value was also calculated. The synthetized AuNPs showed a surface plasmon in visible range at 577 nm and resulted stable for long time in aqueous medium, also changing the pH values in the range 2-12. The studied antioxidant activity, confirmed also by performing special experiments with suitable probes, demonstrated the high performance of AuNPs. The AuNP photostability under sun irradiation is also shown. The calculated SPF values were in the range 3-18, related to AuNPs concentration in the range 1.80 × 10 -12 -1.00 × 10 -11  M. The same AuNPs concentrations were used for cellular experiments. Indeed, since the AuNPs-PGJ mediated will be potentially introduced by dermal contact, dermal fibroblasts (Human Dermal Fibroblasts, HDF) and Human Microvascular Endothelial Cells (HMVEC) were used to evaluate the possible effects of these nanoparticles as a preliminary step. The results indicated that an AuNP concentrations in the range 1.80 × 10 -12 -3.60 × 10 -12  M could be adopted since they do not appeared cyctotoxic. Copyright © 2018 Elsevier Inc. All rights reserved.

Au/MxOy/TiO2 catalysts for CO oxidation: promotional effect of main-group, transition, and rare-earth metal oxide additives.

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

Ma, Zhen; Overbury, Steven; Dai, Sheng

Au/TiO2 catalysts are active for CO oxidation, but they suffer from high-temperature sintering of the gold particles, and few attempts have been made to promote or stabilize Au/TiO2. Our recent communication addressed these issues by loading gold onto Al2O3/TiO2 prepared via surface-sol-gel processing of Al(sec-OC4H9)3 on TiO2. In our current full paper, Au/Al2O3/TiO2 catalysts were prepared alternatively by thermal decomposition of Al(NO3)3 on TiO2 followed by loading gold, and the influences of the decomposition temperature and Al2O3 content were systematically surveyed. This facile method was subsequently extended to the preparation of a battery of metal oxide-modified Au/TiO2 catalysts virtually notmore » reported. It was found that Au/TiO2 modified by CaO, NiO, ZnO, Ga2O3, Y2O3, ZrO2, La2O3, Pr2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Dy2O3, Ho2O3, Er2O3, or Yb2O3 could retain significant activity at ambient temperature even after aging in O2-He at 500 C, whereas unmodified Au/TiO2 lost its activity. Moreover, some 200 C-calcined promoted catalysts showed high activity even at about -100 C. The deactivation and regeneration of some of these new catalysts were studied. This work furnished novel catalysts for further fundamental and applied research.« less

Universal Multifunctional Nanoplatform Based on Target-Induced in Situ Promoting Au Seeds Growth to Quench Fluorescence of Upconversion Nanoparticles.

PubMed

Wu, Qiongqiong; Chen, Hongyu; Fang, Aijin; Wu, Xinyang; Liu, Meiling; Li, Haitao; Zhang, Youyu; Yao, Shouzhuo

2017-12-22

Construction of a new multifunctional chemo/biosensing platform for small biomolecules and tumor markers is of great importance in analytical chemistry. Herein, a novel universal multifunctional nanoplatform for biomolecules and enzyme activity detection was proposed based on fluorescence resonance energy transfer (FRET) between upconversion nanoparticles (UCNPs) and target-inducing enlarged gold nanoparticles (AuNPs). The reductive molecule such as H 2 O 2 can act as the reductant to reduce HAuCl 4 , which will make the Au seeds grow. The enlarged AuNPs can effectively quench the fluorescence of UCNPs owing to the good spectral overlap between the absorption band of the AuNPs and the emission band of the UCNPs. Utilizing the FRET between the UCNPs and enlarged AuNPs, good linear relationship between the fluorescence of UCNPs and the concentration of H 2 O 2 can be found. Based on this strategy, H 2 O 2 related molecules such as l-lactate, glucose, and uric acid can also be quantified. On the basis of UCNPs and PVP/HAuCl 4 , a general strategy for other reductants such as ascorbic acid (AA), dopamine (DA), or enzyme activity can be established. Therefore, the universal multifunctional nanoplatform based on UCNPs and the target-inducing in situ enlarged Au NPs will show its potential as a simple method for the detection of some life related reductive molecules, enzyme substrates, as well as enzyme activity.

Architecture effects of glucose oxidase/Au nanoparticle composite Langmuir-Blodgett films on glucose sensing performance

NASA Astrophysics Data System (ADS)

Wang, Ke-Hsuan; Wu, Jau-Yann; Chen, Liang-Huei; Lee, Yuh-Lang

2016-03-01

The Langmuir-Blodgett (LB) deposition technique is employed to prepare nano-composite films consisting of glucose oxidase (GOx) and gold nanoparticles (AuNPs) for glucose sensing applications. The GOx and AuNPs are co-adsorbed from an aqueous solution onto an air/liquid interface in the presence of an octadecylamine (ODA) template monolayer, forming a mixed (GOx-AuNP) monolayer. Alternatively, a composite film with a cascade architecture (AuNP/GOx) is also prepared by sequentially depositing monolayers of AuNPs and GOx. The architecture effects of the composite LB films on the glucose sensing are studied. The results show that the presence of AuNPs in the co-adsorption system does not affect the adsorption amount and preferred conformation (α-helix) of GOx. Furthermore, the incorporation of AuNPs in both composite films can significantly improve the sensing performance. However, the enhancement effects of the AuNPs in the two architectures are distinct. The major effect of the AuNPs is on the facilitation of charge-transfer in the (GOx-AuNP) film, but on the increase of catalytic activity in the (AuNP/GOx) one. Therefore, the sensing performance can be greatly improved by utilizing a film combining both architectures (AuNP/GOx-AuNP).

Extracellular facile biosynthesis, characterization and stability of gold nanoparticles by Bacillus licheniformis.

PubMed

Singh, Sneha; Vidyarthi, Ambarish Sharan; Nigam, Vinod Kumar; Dev, Abhimanyu

2014-02-01

The development of a reliable, eco-friendly process for synthesis of gold nanoparticles (AuNPs) has gained impetus in recent years to counter the drawbacks of chemical and physical methods. This study illustrates simple, green synthesis of AuNPs in vitro using cell lysate supernatant (CLS) of non-pathogenic bacteria and to investigate its potential antimicrobial activity. Gold nanoparticles were synthesized by the reduction of precursor AuCl4- ions using the CLS of Bacillus licheniformis at 37°C upon 24 h of incubation. The nanoparticles were characterized for their morphology, particle size, optical absorption, zeta potential, and stability. Further the antimicrobial activity was assayed using cup-plate method. The process of biosynthesis was extracellular and the gold ions were reduced to stable nanogold of average size 38 nm. However, upon storage of AuNPs for longer duration at room temperature stability was influenced in terms of increase in particle size and decrease in zeta potential with respect to as synthesized nanoparticles. SEM micrographs revealed the spherical shape of AuNPs and EDX analysis confirmed the presence of gold in the sample. Also clear zone of inhibition was observed against Bacilllus subtilis MTCC 8364, Pseudomonas aeruginosa MTCC 7925, and Escherichia coli MTCC 1698 confirming the antimicrobial activity of AuNPs. The bioprocess under study was simple and less time consuming as compared to other methods as the need for harvesting AuNPs from within the microbial cells via downstream process will be eliminated. Nanoparticles exhibited good stability even in absence of external stabilizing agents. AuNPs showed good antimicrobial activity against several Gram-negative and Gram-positive pathogenic bacteria. The extracellular biosynthesis from CLS may serve as a suitable alternative for large scale synthesis of gold nanoparticles in vitro. The synthesis from lysed bacterial cell strongly suggests that exposure of microbial whole cells to the gold solution for nanoparticle formation is not necessary and that microorganism even in lysed state retained its bioreduction potential. Further the potential of biologically synthesized AuNPs as antimicrobial agents will be of great commercial importance.

Biorecovery of gold as nanoparticles and its catalytic activities for p-nitrophenol degradation.

PubMed

Zhu, Nengwu; Cao, Yanlan; Shi, Chaohong; Wu, Pingxiao; Ma, Haiqin

2016-04-01

Recovery of gold from aqueous solution using simple and economical methodologies is highly desirable. In this work, recovery of gold as gold nanoparticles (AuNPs) by Shewanella haliotis with sodium lactate as electron donor was explored. The results showed that the process was affected by the concentration of biomass, sodium lactate, and initial gold ions as well as pH value. Specifically, the presence of sodium lactate determines the formation of nanoparticles, biomass, and AuCl4 (-) concentration mainly affected the size and dispersity of the products, reaction pH greatly affected the recovery efficiency, and morphology of the products in the recovery process. Under appropriate conditions (5.25 g/L biomass, 40 mM sodium lactate, 0.5 mM AuCl4 (-), and pH of 5), the recovery efficiency was almost 99 %, and the recovered AuNPs were mainly spherical with size range of 10-30 nm (~85 %). Meanwhile, Fourier transforms infrared spectroscopy and X-ray photoelectron spectroscopy demonstrated that carboxyl and amine groups might play an important role in the process. In addition, the catalytic activity of the AuNPs recovered under various conditions was testified by analyzing the reduction rate of p-nitrophenol by borohydride. The biorecovered AuNPs exhibited interesting size and shape-dependent catalytic activity, of which the spherical particle with smaller size showed the highest catalytic reduction activity with rate constant of 0.665 min(-1).

Hydrogen production by Tuning the Photonic Band Gap with the Electronic Band Gap of TiO2

NASA Astrophysics Data System (ADS)

Waterhouse, G. I. N.; Wahab, A. K.; Al-Oufi, M.; Jovic, V.; Anjum, D. H.; Sun-Waterhouse, D.; Llorca, J.; Idriss, H.

2013-10-01

Tuning the photonic band gap (PBG) to the electronic band gap (EBG) of Au/TiO2 catalysts resulted in considerable enhancement of the photocatalytic water splitting to hydrogen under direct sunlight. Au/TiO2 (PBG-357 nm) photocatalyst exhibited superior photocatalytic performance under both UV and sunlight compared to the Au/TiO2 (PBG-585 nm) photocatalyst and both are higher than Au/TiO2 without the 3 dimensionally ordered macro-porous structure materials. The very high photocatalytic activity is attributed to suppression of a fraction of electron-hole recombination route due to the co-incidence of the PBG with the EBG of TiO2 These materials that maintain their activity with very small amount of sacrificial agents (down to 0.5 vol.% of ethanol) are poised to find direct applications because of their high activity, low cost of the process, simplicity and stability.

Drug conjugated nanoparticles activated by cancer cell specific mRNA.

PubMed

Gossai, Nathan P; Naumann, Jordan A; Li, Nan-Sheng; Zamora, Edward A; Gordon, David J; Piccirilli, Joseph A; Gordon, Peter M

2016-06-21

We describe a customizable approach to cancer therapy in which a gold nanoparticle (Au-NP) delivers a drug that is selectively activated within the cancer cell by the presence of an mRNA unique to the cancer cell. Fundamental to this approach is the observation that the amount of drug released from the Au-NP is proportional to both the presence and abundance of the cancer cell specific mRNA in a cell. As proof-of-principle, we demonstrate both the efficient delivery and selective release of the multi-kinase inhibitor dasatinib from Au-NPs in leukemia cells with resulting efficacy in vitro and in vivo. Furthermore, these Au-NPs reduce toxicity against hematopoietic stem cells and T-cells. This approach has the potential to improve the therapeutic efficacy of a drug and minimize toxicity while being highly customizable with respect to both the cancer cell specific mRNAs targeted and drugs activated.

Three-dimensional nanoporous MoS2 framework decorated with Au nanoparticles for surface-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Sheng, Yingqiang; Jiang, Shouzhen; Yang, Cheng; Liu, Mei; Liu, Aihua; Zhang, Chao; Li, Zhen; Huo, Yanyan; Wang, Minghong; Man, Baoyuan

2017-08-01

The three-dimensional (3D) MoS2 decorated with Au nanoparticles (Au NPs) hybrids (3D MoS2-Au NPs) for surface-enhanced Raman scattering (SERS) sensing was demonstrated in this paper. SEM, Raman spectroscopy, TEM, SAED, EDX and XRD were performed to characterize 3D MoS2-Au NPs hybrids. Rhodamine 6G (R6G), fluorescein and gallic acid molecules were used as the probe for the SERS detection of the 3D MoS2-Au NPs hybrids. In addition, we modeled the enhancement of the electric field of MoS2-Au NPs hybrids using Finite-difference time-domain (FDTD) analysis, which can further give assistance to the mechanism understanding of the SERS activity.

Thermo-Responsive Amphiphilic Block Copolymers Stablilized Gold Nanoparticles: Synthesis and High Catalytic Properties.

PubMed

Lü, Jianhua; Yang, Yu; Gao, Junfang; Duan, Haichao; Lü, Changli

2018-06-19

A series of novel well-defined 8-hydroxyquinoline (HQ)-containing thermo-responsive amphiphilic diblock copolymers poly(styrene-co-5-(2-methacryloylethyloxy- methyl)-8-quinolinol)-b-poly(N-isopropylacrylamide) P(St-co-MQ)-b-PNIPAm (P1,2), P(NIPAm- co-MQ)-b-PSt (P3,4) and triblock copolymer poly(N-isopropylacrylamide)-b-poly(methyl- methacrylate-co-5-(2-methacryloylethyloxymethyl)-8-quinolinol)-b-polystyrene PNIPAm-b- P(MMA-co-MQ)-b-PSt (P5) were prepared by reversible addition fragmentation chain transfer (RAFT) polymerization, and their self-assembly behaviors were studied. The block copolymers P1-P5 stabilized gold nanoparticles (Au@P1-Au@P5) with small size and narrow distribution were obtained through in situ reduction of gold precursors in aqueous solution of polymer micelles with HQ as the coordination groups. The resulting Au@P nanohybrids possessed excellent catalytic activities for the reduction of nitrophenols using NaBH4. The size, morphology and surface chemistry of Au NPs could be controlled by adjusting the structure of block polymers with HQ in different block positions, which plays an important role in the catalytic properties. It was found that longer chain length of hydrophilic or hydrophobic segments of block copolymers were beneficial to elevate the catalytic activity of Au NPs for the reduction of nitrophenols, and the spherical nanoparticles (Au@P5) stabilized with triblock copolymer exhibit higher catalytic performance. Surprisingly, the gold nanowires (Au@P4) produced with P4 have a highest catalytic activity due to large abundance of grain boundaries. Excellent thermo-responsive behaviors for catalytic reaction make the as-prepared Au@P hybrids become an environmentally responsive nano-catalytic materials.

Au-nanoparticles grafted on plasma treated PE

NASA Astrophysics Data System (ADS)

Švorčík, V.; Chaloupka, A.; Řezanka, P.; Slepička, P.; Kolská, Z.; Kasálková, N.; Hubáček, T.; Siegel, J.

2010-03-01

Polyethylene (PE) surface was treated with Ar plasma. Activated surface was grafted from methanol solution of 1,2-ethanedithiol. Then the sample was immersed into freshly prepared colloid solution of Au-nanoparticles. Finally Au layer was sputtered on the samples. Properties of the modified PE were studied using various methods: AFM, EPR, RBS and nanoindentation. It was shown that the plasma treatment results in degradation of polymer chain (AFM) and creation of free radicals by EPR. After grafting with dithiol, the concentration of free radicals declines. The presence of Au and S in the surface layer after the coating with Au-nanoparticles was proved by RBS. Plasma treatment changes PE surface morphology and increases surface roughness, too. Another significant change in surface morphology and roughness was observed after deposition of Au-nanoparticles. Nanoindentation measurements show that the grafting with Au-nanoparticles increases adhesion of subsequently sputtered Au layer.

Physiographic and land cover attributes of the Puget Lowland and the active streamflow gaging network, Puget Sound Basin

USGS Publications Warehouse

Konrad, Christopher; Sevier, Maria

2014-01-01

Geospatial information for the active streamflow gaging network in the Puget Sound Basin was compiled to support regional monitoring of stormwater effects to small streams. The compilation includes drainage area boundaries and physiographic and land use attributes that affect hydrologic processes. Three types of boundaries were used to tabulate attributes: Puget Sound Watershed Characterization analysis units (AU); the drainage area of active streamflow gages; and the catchments of Regional Stream Monitoring Program (RSMP) sites. The active streamflow gaging network generally includes sites that represent the ranges of attributes for lowland AUs, although there are few sites with low elevations (less than 60 meters), low precipitation (less than 1 meter year), or high stream density (greater than 5 kilometers per square kilometers). The active streamflow gaging network can serve to provide streamflow information in some AUs and RSMP sites, particularly where the streamflow gage measures streamflow generated from a part of the AU or that drains to the RSMP site, and that part of the AU or RSMP site is a significant fraction of the drainage area of the streamgage. The maximum fraction of each AU or RSMP catchment upstream of a streamflow gage and the maximum fraction of any one gaged basin in an AU or RSMP along with corresponding codes are provided in the attribute tables.

BODIPY-Au(I): A Photosensitizer for Singlet Oxygen Generation and Photodynamic Therapy.

PubMed

Üçüncü, Muhammed; Karakuş, Erman; Kurulgan Demirci, Eylem; Sayar, Melike; Dartar, Suay; Emrullahoğlu, Mustafa

2017-05-19

Upon complexation with Au(I), a photoinactive BODIPY derivative was transformed into a highly photoactive triplet sensitizer. Along with high efficiency in singlet oxygen generation (Φ Δ = 0.84), the new BODIPY-Au(I) skeleton showed excellent photocytotoxic activity against cancer cell lines (EC 50 = 2.5 nM).

Spontaneous synthesis of gold nanoparticles on gum arabic-modified iron oxide nanoparticles as a magnetically recoverable nanocatalyst.

PubMed

Wu, Chien-Chen; Chen, Dong-Hwang

2012-06-19

A novel magnetically recoverable Au nanocatalyst was fabricated by spontaneous green synthesis of Au nanoparticles on the surface of gum arabic-modified Fe3O4 nanoparticles. A layer of Au nanoparticles with thickness of about 2 nm was deposited on the surface of gum arabic-modified Fe3O4 nanoparticles, because gum arabic acted as a reducing agent and a stabilizing agent simultaneously. The resultant magnetically recoverable Au nanocatalyst exhibited good catalytic activity for the reduction of 4-nitrophenol with sodium borohydride. The rate constants evaluated in terms of pseudo-first-order kinetic model increased with increase in the amount of Au nanocatalyst or decrease in the initial concentration of 4-nitrophenol. The kinetic data suggested that this catalytic reaction was diffusion-controlled, owing to the presence of gum arabic layer. In addition, this nanocatalyst exhibited good stability. Its activity had no significant decrease after five recycles. This work is useful for the development and application of magnetically recoverable Au nanocatalyst on the basis of green chemistry principles.

Spontaneous synthesis of gold nanoparticles on gum arabic-modified iron oxide nanoparticles as a magnetically recoverable nanocatalyst

PubMed Central

2012-01-01

A novel magnetically recoverable Au nanocatalyst was fabricated by spontaneous green synthesis of Au nanoparticles on the surface of gum arabic-modified Fe3O4 nanoparticles. A layer of Au nanoparticles with thickness of about 2 nm was deposited on the surface of gum arabic-modified Fe3O4 nanoparticles, because gum arabic acted as a reducing agent and a stabilizing agent simultaneously. The resultant magnetically recoverable Au nanocatalyst exhibited good catalytic activity for the reduction of 4-nitrophenol with sodium borohydride. The rate constants evaluated in terms of pseudo-first-order kinetic model increased with increase in the amount of Au nanocatalyst or decrease in the initial concentration of 4-nitrophenol. The kinetic data suggested that this catalytic reaction was diffusion-controlled, owing to the presence of gum arabic layer. In addition, this nanocatalyst exhibited good stability. Its activity had no significant decrease after five recycles. This work is useful for the development and application of magnetically recoverable Au nanocatalyst on the basis of green chemistry principles. PMID:22713480

Gamma radiation mediated green synthesis of gold nanoparticles using fermented soybean-garlic aqueous extract and their antimicrobial activity.

PubMed

El-Batal, Ahmed Ibrahim; Hashem, Abd-Algawad M; Abdelbaky, Noha M

2013-12-01

Aspergillus oryzae was used to enhance the mobilization of antioxidants of soybean matrix along with garlic as a co-substrate by modulating polyphenolic substances during solid-state fermentation. Mobilized polyphenols were used as a green tool for synthesis and stabilization of gold nanoparticles (AuNPs). The radiation-induced AuNPs synthesis is a simple, clean and inexpensive process which involves radiolysis of aqueous solution that provides an efficient method to reduce metal ions. Gamma irradiated aqueous extract of fermented soybean and garlic was used for rapid preparation of AuNPs combining both effects of radiolytic reactions by radiation and stabilization by bioactive components of fermented extract. The synthesized AuNPs were confirmed by UV-Visible spectrophotometry, dynamic light scattering (DLS), Fourier Transform infra red (FT-IR) spectrophotometry, and transmission electron microscope (TEM) analysis which revealed morphology of spherical AuNPs with size ranging from 7-12 nm. The synthesized AuNPs exhibited antimicrobial activity against both Gram positive and Gram negative bacteria, as measured by well diffusion assay.

Biomolecular Specificity Regulated Synthesis of Nanocatalysts and Heterointegration of Photosynthesis Nanodevices

DTIC Science & Technology

2016-01-01

TiO2-Au/Pd nanocomposite composed of P25 TiO2 nanoparticles and Au/Pd nanowheels is applied in benzimidazole synthesis as plasmon-enhanced...activity and selectivity. In this work, TiO2-Au/Pd nanocomposite composed of P25 TiO2 nanoparticles and Au/Pd nanowheels is applied in benzimidazole ...Pd Nanocomposite Photocatalyst for Tandem Synthesis of Benzimidazole 2.1 Approaches: Wet-chemical synthetic routes are explored to create

Improvement of oxygen reduction reaction and methanol tolerance characteristics for PdCo electrocatalysts by Au alloying and CO treatment.

PubMed

Wei, Yu-Chen; Liu, Chen-Wei; Wang, Kuan-Wen

2011-11-21

The mass ORR activity of CO heat-treated PdCoAu/C catalysts, compared to Pd/C, is enhanced approximately 6-fold, and even 25-fold in a methanol containing environment due to the formation of delicate PdCo and PdAu alloys enriched in the core and PdAu alloy species enriched on the shell structure. This journal is © The Royal Society of Chemistry 2011

Electrocatalytic activity of spots of electrodeposited noble-metal catalysts on carbon nanotubes modified glassy carbon.

PubMed

Chen, Xingxing; Eckhard, Kathrin; Zhou, Min; Bron, Michael; Schuhmann, Wolfgang

2009-09-15

A strategy for the screening of the electrocatalytic activity of electrocatalysts for possible application in fuel cells and other devices is presented. In this approach, metal nanoclusters (Pt, Au, Ru, and Rh and their codeposits) were prepared using a capillary-based droplet-cell by pulsed electrodeposition in a diffusion-restricted viscous solution. A glassy carbon surface was modified with carbon nanotubes (CNTs) by electrophoretic accumulation and was used as substrate for metal nanoparticle deposition. The formed catalyst spots on the CNT-modified glassy carbon surface were investigated toward their catalytic activity for oxygen reduction as a test reaction employing the redox competition mode of scanning electrochemical microscopy (RC-SECM). Qualitative information on the electrocatalytic activity of the catalysts was obtained by varying the potential applied to the substrate; semiquantitative evaluation was based on the determination of the electrochemically deposited catalyst loading by means of the charge transferred during the metal nanoparticle deposition. Qualitatively, Au showed the highest electrocatalytic activity toward the oxygen reduction reaction (ORR) in phosphate buffer among all investigated single metal catalysts which was attributed to the much higher loading of Au achieved during electrodeposition. Coelectrodeposited Au-Pt catalysts showed a more positive onset potential (-150 mV in RC-SECM experiments) of the ORR in phosphate buffer at pH 6.7. After normalizing the SECM image by the charge during the metal nanocluster deposition which represents the mass loading of the catalyst, Ru showed a higher electrocatalytic activity toward the ORR than Au.

Inhibition of discoidin domain receptor 2-mediated lung cancer cells progression by gold nanoparticle-aptamer-assisted delivery of peptides containing transmembrane-juxtamembrane 1/2 domain

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

Kim, Daehwan; Yeom, Ji-Hyun; Lee, Boeun

The delivery of biologically functional peptides into mammalian cells can be a direct and effective method for cancer therapy and treatment of other diseases. Discoidin domain receptor 2 (DDR2) is a collagen-induced receptor tyrosine kinase recently identified as a novel therapeutic target in lung cancer. In this study, we report that peptides containing the functional domain of DDR2 can be efficiently delivered into lung malignant cancer cells via a gold nanoparticle-DNA aptamer conjugate (AuNP-Apt)-based system. Peptide delivery resulted in the abrogation of DDR2 activation triggered by collagen. Moreover, the peptide delivered by the AuNP-Apt system inhibited cancer cell proliferation andmore » invasion mediated by DDR2 activation. Thus, these results suggest that peptide loaded onto AuNP-Apt conjugates can be used for the development of peptide-based biomedical applications for the treatment of DDR2-positive cancer. - Highlights: • TM-JM1/2 peptides are efficiently delivered into cells by AuNP-Apt-conjugates. • TM-JM1/2 peptides loaded onto AuNP-Apt conjugates inhibit DDR2 activation. • Inhibition of DDR2 activation by TM-JM1/2 peptides decreases tumor progression.« less

Phototodynamic activity of zinc monocarboxyphenoxy phthalocyane (ZnMCPPc) conjugated to gold silver (AuAg) nanoparticles in melanoma cancer cells

NASA Astrophysics Data System (ADS)

Manoto, Sello L.; Oluwole, David O.; Malabi, Rudzani; Maphanga, Charles; Ombinda-Lemboumba, Saturnin; Nyokong, Tebello; Mthunzi-Kufa, Patience

2017-02-01

Photodynamic therapy (PDT) is a minimally invasive therapeutic modality for the treatment of neoplastic and non-neoplastic diseases. In PDT of cancer, irradiation with light of a specific wavelength leads to activation of a photosensitizer which results in generation of reactive oxygen species (ROS) which induces cell death. Many phthalocyanine photosensitizers are hydrophobic and insoluble in water, which limits their therapeutic efficiency. Consequently, advanced delivery systems and strategies are needed to improve the effectiveness of these photosensitizers. Nanoparticles have shown promising results in increasing aqueous solubility, bioavailability, stability and delivery of photosensitizers to their target. This study investigated the photodynamic activity of zinc monocarboxyphenoxy phthalocyanine (ZnMCPPc) conjugated to gold silver (AuAg) nanoparticles in melanoma cancer cells. The photodynamic activity of ZnMCPPc conjugated to AuAg nanoparticles were evaluated using cellular morphology, viability, proliferation and cytotoxicity. Untreated cells showed no changes in cellular morphology, proliferation and cytotoxicity. However, photoactivated ZnMCPPc conjugated to AuAg nanoparticles showed changes in cell morphology and a dose dependent decrease in cellular viability, proliferation and an increase in cell membrane damage. The ZnMCPPc conjugated to AuAg nanoparticles used in this study was highly effective in inducing cell death of melanoma cancer cells.

Influence of Cu, Au and Ag on structural and surface properties of bioactive coatings based on titanium.

PubMed

Wojcieszak, D; Mazur, M; Kalisz, M; Grobelny, M

2017-02-01

In this work influence of copper, silver and gold additives on structural and surface properties of biologically active thin films based on titanium have been described. Coatings were prepared by magnetron sputtering method. During each process metallic discs (targets) - Ti and the additive (Cu, Ag or Au) were co-sputtered in argon atmosphere. Structural investigation of as-deposited coatings was performed with the aid of XRD and SEM/EDS method. It was found that all prepared thin films were homogenous. Addition of Cu, Ag and Au resulted in nanocrystalline structure. Moreover, influence of these additives on hardness and antibacterial activity of titanium coatings was also studied. Ti-Cu, Ti-Ag and Ti-Au films had lower hardness as-compared to Ti. According to AAS results the difference of their activity was related to the ion migration process. It was found that Ti-Ag and Ti-Au coatings had biocidal effect related to direct contact of their surface with microorganisms. In the case of Ti-Cu antimicrobial activity had direct and indirect nature due to efficient ion migration process from the film surface to the surrounding environment. Functional features of coatings such as wettability and corrosion resistance were also examined and included in the comprehensive analysis. Copyright © 2016 Elsevier B.V. All rights reserved.

Correlation between Gas Bubble Formation and Hydrogen Evolution Reaction Kinetics at Nanoelectrodes.

PubMed

Chen, Qianjin; Luo, Long

2018-04-17

We report the correlation between H 2 gas bubble formation potential and hydrogen evolution reaction (HER) activity for Au and Pt nanodisk electrodes (NEs). Microkinetic models were formulated to obtain the HER kinetic information for individual Au and Pt NEs. We found that the rate-determining steps for the HER at Au and Pt NEs were the Volmer step and the Heyrovsky step, respectively. More interestingly, the standard rate constant ( k 0 ) of the rate-determining step was found to vary over 2 orders of magnitude for the same type of NEs. The observed variations indicate the HER activity heterogeneity at the nanoscale. Furthermore, we discovered a linear relationship between bubble formation potential ( E bubble ) and log( k 0 ) with a slope of 125 mV/decade for both Au and Pt NEs. As log ( k 0 ) increases, E bubble shifts linearly to more positive potentials, meaning NEs with higher HER activities form H 2 bubbles at less negative potentials. Our theoretical model suggests that such linear relationship is caused by the similar critical bubble formation condition for Au and Pt NEs with varied sizes. Our results have potential implications for using gas bubble formation to evaluate the HER activity distribution of nanoparticles in an ensemble.

Molecularly stabilised ultrasmall gold nanoparticles: synthesis, characterization and bioactivity

NASA Astrophysics Data System (ADS)

Leifert, Annika; Pan-Bartnek, Yu; Simon, Ulrich; Jahnen-Dechent, Willi

2013-06-01

Gold nanoparticles (AuNPs) are widely used as contrast agents in electron microscopy as well as for diagnostic tests. Due to their unique optical and electrical properties and their small size, there is also a growing field of potential applications in medical fields of imaging and therapy, for example as drug carriers or as active compounds in thermotherapy. Besides their intrinsic optical properties, facile surface decoration with (bio)functional ligands renders AuNPs ideally suited for many industrial and medical applications. However, novel AuNPs may have toxicological profiles differing from bulk and therefore a thorough analysis of the quantitative structure-activity relationship (QSAR) is required. Several mechanisms are proposed that cause adverse effects of nanoparticles in biological systems. Catalytic generation of reactive species due to the large and chemically active surface area of nanomaterials is well established. Because nanoparticles approach the size of biological molecules and subcellular structures, they may overcome natural barriers by active or passive uptake. Ultrasmall AuNPs with sizes of 2 nm or less may even behave as molecular ligands. These types of potential interactions would imply a size and ligand-dependent behaviour of any nanomaterial towards biological systems. Thus, to fully understand their QSAR, AuNPs bioactivity should be analysed in biological systems of increasing complexity ranging from cell culture to whole animal studies.

Exploring the activity of a novel Au/TiC(001) model catalyst towards CO and CO 2 hydrogenation

DOE PAGES

Asara, Gian Giacomo; Ricart, Josep M.; Rodriguez, Jose A.; ...

2015-02-02

Small metallic nanoparticles supported on transition metal carbides exhibit an unexpected high activity towards a series of chemical reactions. In particular, the Au/TiC system has proven to be an excellent catalyst for SO 2 decomposition, thiophene hydrodesulfurization, O 2 and H 2 dissociation and the water gas shift reaction. Recent studies have shown that Au/TiC is a very good catalyst for the reverse water–gas shift (CO 2 + H 2 → CO + H 2O) and CO 2 hydrogenation to methanol. The present work further expands the range of applicability of this novel type of systems by exploring the catalyticmore » activity of Au/TiC towards the hydrogenation of CO or CO 2 with periodic density functional theory (DFT) calculations on model systems. Hydrogen dissociates easily on Au/TiC but direct hydrogenation of CO to methanol is hindered by very high activation barriers implying that, on this model catalyst, methanol production from CO 2 involves the hydrogenation of a HOCO-like intermediate. Thus, when dealing with mixtures of syngas (CO/CO 2/H 2/H 2O), CO could be transformed into CO 2 through the water gas shift reaction with subsequent hydrogenation of CO 2 to methanol.« less

Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts

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

Wang, Lu-Cun; Friend, C. M.; Fushimi, Rebecca

The activation of molecular O 2as well as the reactivity of adsorbed oxygen species is of central importance in aerobic selective oxidation chemistry on Au-based catalysts. Herein, we address the issue of O 2activation on unsupported nanoporous gold (npAu) catalysts by applying a transient pressure technique, a temporal analysis of products (TAP) reactor, to measure the saturation coverage of atomic oxygen, its collisional dissociation probability, the activation barrier for O 2dissociation, and the facility with which adsorbed O species activate methanol, the initial step in the catalytic cycle of esterification. The results from these experiments indicate that molecular O 2dissociationmore » is associated with surface silver, that the density of reactive sites is quite low, that adsorbed oxygen atoms do not spill over from the sites of activation onto the surrounding surface, and that methanol reacts quite facilely with the adsorbed oxygen atoms. In addition, the O species from O 2dissociation exhibits reactivity for the selective oxidation of methanol but not for CO. The TAP experiments also revealed that the surface of the npAu catalyst is saturated with adsorbed O under steady state reaction conditions, at least for the pulse reaction.« less

Active site densities, oxygen activation and adsorbed reactive oxygen in alcohol activation on npAu catalysts

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

Wang, Lu-Cun; Friend, C. M.; Fushimi, Rebecca

2016-01-01

The activation of molecular O 2as well as the reactivity of adsorbed oxygen species is of central importance in aerobic selective oxidation chemistry on Au-based catalysts. Herein, we address the issue of O 2activation on unsupported nanoporous gold (npAu) catalysts by applying a transient pressure technique, a temporal analysis of products (TAP) reactor, to measure the saturation coverage of atomic oxygen, its collisional dissociation probability, the activation barrier for O 2dissociation, and the facility with which adsorbed O species activate methanol, the initial step in the catalytic cycle of esterification. The results from these experiments indicate that molecular O 2dissociationmore » is associated with surface silver, that the density of reactive sites is quite low, that adsorbed oxygen atoms do not spill over from the sites of activation onto the surrounding surface, and that methanol reacts quite facilely with the adsorbed oxygen atoms. In addition, the O species from O 2dissociation exhibits reactivity for the selective oxidation of methanol but not for CO. The TAP experiments also revealed that the surface of the npAu catalyst is saturated with adsorbed O under steady state reaction conditions, at least for the pulse reaction.« less

Advances in Gold Catalysis and Understanding the Catalytic Mechanism.

PubMed

Ishida, Tamao; Koga, Hiroaki; Okumura, Mitsutaka; Haruta, Masatake

2016-10-01

When gold is deposited as nanoparticles (NPs) with mean diameters of 2-5 nm or clusters with mean diameters below 2 nm onto a variety of supports such as metal oxides, carbons, polymers, etc., the supported Au NPs exhibit unique catalytic properties, while bulk Au is almost inert as a catalyst. A lot of research works indicate that the key factors of the catalysis by supported Au NPs are the selection of the supports, the control of the Au NP size, the shape of the Au NPs, and the strong junction between Au NPs and the supports, because the perimeter zone around Au NPs acts as the active site for many reactions. In order to elucidate the origin of catalysis by supported Au NPs, the interplay between physicochemical analysis, computational studies, and rational experiments for catalysis by supported Au NPs is becoming more and more important. This article summarizes our experiences and progress in such interplay. © 2016 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The role of aqueous leaf extract of Tinospora crispa as reducing and capping agents for synthesis of gold nanoparticles

NASA Astrophysics Data System (ADS)

Apriandanu, D. O. B.; Yulizar, Y.

2017-04-01

Environmentally friendly method for green synthesis of Au nanoparticles (AuNP) using aqueous leaf extract of Tinospora crispa (TLE) was reported. TLE has the ability for reducing and capping AuNP. Identification of active compounds in aqueous leaf extract was obtained by phytochemical analysis and Fourier transform infrared spectroscopy (FTIR). The AuNP-TLE growth was characterized using UV-Vis spectrophotometer. The particle size and the distribution of AuNP were confirmed by particle size analyzer (PSA). AuNP-TLE formation was optimized by varying the extract concentration and time of the synthesis process. UV-Vis absorption spectrum of optimum AuNP formation displayed by the surface plasmon resonance at maximum wavelength of λmax 536 nm. The PSA result showed that AuNP has size distribution of 80.60 nm and stable up to 21 days. TEM images showed that the size of the AuNP is ± 25 nm.

Bimetallic Au-Pd nanoparticles on 2D supported graphitic carbon nitride and reduced graphene oxide sheets: A comparative photocatalytic degradation study of organic pollutants in water.

PubMed

Darabdhara, Gitashree; Das, Manash R

2018-04-01

Novel and sustainable bimetallic nanoparticles of Au-Pd on 2D graphitic carbon nitride (g-C 3 N 4 ) and reduced graphene oxide (rGO) sheets was designed adopting an eco-friendly chemical route to obtain Au-Pd/g-C 3 N 4 and Au-Pd/rGO, respectively. Elimination of hazardous pollutants, particularly phenol from water is urgent for environment remediation due to its significant carcinogenicity. Considering this aspect, the Au-Pd/g-C 3 N 4 and Au-Pd/rGO nanocomposites are used as photocatalyst towards degradation of toxic phenol, 2-chlorophenol (2-CP) and 2-nitrophenol (2-NP) under natural sunlight and UV light irradiation. Au-Pd/g-C 3 N 4 nanocomposite exhibited higher activity then Au/g-C 3 N 4 , Pd/g-C 3 N 4 and Au-Pd/rGO nanocomposites with more than 95% degradation in 180 min under sunlight. The obtained degradation efficiency of our materials is better than many other reported photocatalysts. Incorporation of nitrogen atoms in the carbon skeleton of g-C 3 N 4 provides much better properties to Au-Pd/g-C 3 N 4 nanocomposite than carbon based Au-Pd/rGO leading to its higher degradation efficiency. Due to the presence of these nitrogen atoms and some defects, g-C 3 N 4 possesses appealing electrical, chemical and functional properties. Photoluminescence results further revealed the efficient charge separation and delayed recombination of photo-induced electron-hole pairs in the Au-Pd/g-C 3 N 4 nanocomposite. Generation of reactive oxygen species during photocatalysis is well explained through photoluminescence study and the sustainability of these photocatalyst was ascertained through reusability study up to eight and five consecutive cycles for Au-Pd/g-C 3 N 4 and Au-Pd/rGO nanocomposites, respectively without substantial loss in its activity. Characterization of the photocatalysts after reaction signified the stability of the nanocomposites and added advantage to our developed photocatalytic system. Copyright © 2018 Elsevier Ltd. All rights reserved.

Bi-functional Au/FeS (Au/Co3O4) composite for in situ SERS monitoring and degradation of organic pollutants

NASA Astrophysics Data System (ADS)

Ma, Shuzhen; Cai, Qian; Lu, Kailing; Liao, Fan; Shao, Mingwang

2016-01-01

The bi-functional Au/FeS (Au/Co3O4) composite was fabricated by in situ reducing Au nanoparticles onto the surface of FeS (Co3O4). The as-prepared FeS possessed a multi-structure composed of plenty of nanoplates, which were coated by Au nanoparticles with an average size of 47.5 nm. While the Co3O4 showed a thin hexagonal sheet containing Au nanoparticles on its surface with an average size of 79.0 nm. Both the as-prepared Au/FeS and Au/Co3O4 composites exhibited excellent SERS performance, capable of enhancing the Raman signals of R6G molecules with the enhancement factor up to 1.81 × 106 and 7.60 × 104, respectively. Moreover, Au/FeS (Au/Co3O4) composite also has been verified to have intrinsic peroxidase-like activity, which could decompose H2O2 into hydroxyl radicals and then degrade organic pollutants into small molecules. Therefore, SERS can be used to real-time and in situ monitoring the degradation process of R6G molecules, employing the Au/FeS (Au/Co3O4) composite both as SERS substrate and catalyst.

Novel Au-TiC Catalysts for CO Oxidation and Desulfurization Processes

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

Rodriguez, J.A.; Liu, P.; Takahashi, Y.

2011-05-30

Recent articles dealing with the physical and chemical properties of novel Au-TiC catalysts are reviewed. High-resolution photoemission, scanning tunneling microscopy and first-principles periodic density-functional calculations were used to study the deposition of gold on a TiC(0 0 1) surface. Gold grows forming two-dimensional (very low coverage) and three-dimensional (medium and large coverage) islands on the carbide substrate. A positive shift in the binding energy of the C 1s core level is observed after the deposition of Au on TiC(0 0 1). The results of the density-functional calculations corroborate the formation of Au-C bonds. In general, the bond between Au andmore » the TiC(0 0 1) surface exhibits very little ionic character, but there is a substantial polarization of electrons around Au that facilitates bonding of the adatoms with electron-acceptor molecules (CO, O{sub 2}, C{sub 2}H{sub 4}, SO{sub 2}, thiophene, etc.). Experimental measurements indicate that Au/TiC(0 0 1) is a very good catalysts for the oxidation of CO, the destruction of SO{sub 2} and the hydrodesulfurization of thiophene. At temperatures below 200 K, Au/TiC(0 0 1) is able to perform the 2CO + O{sub 2} {yields} 2CO{sub 2} reaction and the full decomposition of SO{sub 2}. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(0 0 1) or Au(1 1 1), a Au/TiC(0 0 1) surface displays a hydrodesulfurization activity higher than that of conventional Ni/MoS{sub x} catalysts. Metal carbides are excellent supports for enhancing the chemical reactivity of gold. The Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces.« less

Novel Au-TiC Catalysts for CO Oxidation and Desulfurization Processes

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

J Rodriguez; P Liu; Y Takahashi

2011-12-31

Recent articles dealing with the physical and chemical properties of novel Au-TiC catalysts are reviewed. High-resolution photoemission, scanning tunneling microscopy and first-principles periodic density-functional calculations were used to study the deposition of gold on a TiC(0 0 1) surface. Gold grows forming two-dimensional (very low coverage) and three-dimensional (medium and large coverage) islands on the carbide substrate. A positive shift in the binding energy of the C 1s core level is observed after the deposition of Au on TiC(0 0 1). The results of the density-functional calculations corroborate the formation of Au-C bonds. In general, the bond between Au andmore » the TiC(0 0 1) surface exhibits very little ionic character, but there is a substantial polarization of electrons around Au that facilitates bonding of the adatoms with electron-acceptor molecules (CO, O{sub 2}, C{sub 2}H{sub 4}, SO{sub 2}, thiophene, etc.). Experimental measurements indicate that Au/TiC(0 0 1) is a very good catalysts for the oxidation of CO, the destruction of SO{sub 2} and the hydrodesulfurization of thiophene. At temperatures below 200 K, Au/TiC(0 0 1) is able to perform the 2CO + O{sub 2} {yields} 2CO{sub 2} reaction and the full decomposition of SO{sub 2}. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(0 0 1) or Au(1 1 1), a Au/TiC(0 0 1) surface displays a hydrodesulfurization activity higher than that of conventional Ni/MoS{sub x} catalysts. Metal carbides are excellent supports for enhancing the chemical reactivity of gold. The Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces.« less

Thermo-responsive PNIPAM-metal hybrids: An efficient nanocatalyst for the reduction of 4-nitrophenol

NASA Astrophysics Data System (ADS)

Satapathy, Smith Sagar; Bhol, Prachi; Chakkarambath, Aswathy; Mohanta, Jagdeep; Samantaray, Kunal; Bhat, Suresh K.; Panda, Subhendu K.; Mohanty, Priti S.; Si, Satyabrata

2017-10-01

Micron size thermoresponsive cross-linked polymeric microgels of poly(N-isopropylacrylamide) (PNIPAM) are used as "microreactor" for embedding metal nanoparticles of different shapes. Using a simple and robust method, we have synthesized various polymer-metal hybrid nanostructures incorporated with Au nanorods (AuNR), Au nanospheres (AuNS) and Ag nanospheres (AgNS). These hybrid nanostructures have been characterized by transmission electron microscope (TEM), UV-vis spectroscopy, dynamic light scattering (DLS) and static light scattering (SLS) followed by their catalytic activity. TEM studies directly confirmed the mondispersity of synthesized hybrid microgels and stability of the embedded metal nanoparticles within the microgels. Optical studies confirmed the presence of respective absorption bands that correspond to AuNS, AgNS and AuNR respectively. Extensive DLS studies demonstrated that although these hybrid microgels preserve their thermoresponsive properties, i.e their hydrodynamic radius decreased with increasing temperature, their thermosensitivity were comparatively lesser than pure PNIPAM microgels. Combining with studies using static light scattering, we further found that AuNS and AgNS were inhomogeneously distributed within microgels where the majority of the nanoparticles present within the loosely cross-linked shell. On the other hand AuNR were distributed more homogeneously within the microgels. Catalytic performance of various nanostructures loaded onto PNIPAM microgel beads were evaluated by studying the catalytic reduction of 4-nitrophenol. Complete catalytic conversion using AgNS occurred in ∼30 min with a first-order rate constant of 0.159 min-1 having a 7 min induction period. On the other hand no induction period was observed for AuNS and AuNR and the reaction completed in 3-4 min with a first-order rate constant of 1.607 min-1 and 1.627 min-1 respectively. Further, PNIPAM-AuNS and PNIPAM-AuNR possess better catalytic activity as well as recyclability compared to that of PNIPAM-AgNS.

Kinetics of transformation of deformation processed gold-matrix composite

NASA Astrophysics Data System (ADS)

Wongpreedee, Kageeporn

Gold matrix Ḏeformation-processed M&barbelow;etal M&barbelow;etal C&barbelow;omposites (DMMC) have been developed that have better strength and conductivity than conventional gold alloys. However, DMMC possess metastable two-phase microstructures, and their strength and conductivity decrease after prolonged exposure to elevated temperatures. The kinetics of the transformation from the metastable two-phase microstructure to the equilibrium single-phase solid solution is of interest. This document describes a study of the elevated temperature stability of Au DMMC's and the relationship between microstructure and resistivity of three compositions: Au-7 vol %Ag, Au-14 vol %Ag, and Au-vol 7%Pt. DMMC samples were prepared by a powder metallurgy technique and mechanical processes. The smallest final diameter of these wires was 120 mum. Avrami and Arrhenius relations were used to evaluate the kinetic transformation. The extensive deformation used to produce these composites reshaped the initially equi-axed powder particles into a nanofilamentary composite. Electrical resistivity measurements were used to determine the degree of transformation from the initial metastable nano-filamentary composite to the equilibrium solid solution condition. These measurements indicated that this transformation in Au-14 at%Ag, Au-7 at %Ag Au and Au-7 at %Pt DMMC wires proceeded with activation energies of 141, 156, and 167 kJ/mol, respectively. It is thought that these empirically determined activation energies differ from those determined in single crystal, planar interface Au-Ag and Au-Pt diffusion couples due to chemical potential, surface curvature, and strain effects. The DMMC systems reach the equilibrium solid solution condition faster than single crystal, planar interface systems for two reasons: (1) far more defects (dislocations, grain boundaries, vacancies from non-conservative dislocation motion, etc.) are present in the Au-Ag and Au-Pt DMMC composites, and (2) the small radius of curvature of the Ag and Pt filaments increases the chemical potential for diffusion in the DMMC.

Gold nanocluster-based vaccines for dual-delivery of antigens and immunostimulatory oligonucleotides

NASA Astrophysics Data System (ADS)

Tao, Yu; Zhang, Yan; Ju, Enguo; Ren, Hui; Ren, Jinsong

2015-07-01

We here report a facile one-pot synthesis of fluorescent gold nanoclusters (AuNCs) via the peptide biomineralization method, which can elicit specific immunological responses. The as-prepared peptide-protected AuNCs (peptide-AuNCs) display strong red fluorescence, and more importantly, as compared to the peptide alone, the immune stimulatory ability of the resulting peptide-AuNCs can not only be retained, but can also be efficaciously enhanced. Moreover, through a dual-delivery of antigen peptides and cytosine-phosphate-guanine (CpG) oligodeoxynucleotides (ODNs), the as-prepared peptide-AuNC-CpG conjugates can also act as smart self-vaccines to assist in the generation of high immunostimulatory activity, and be applied as a probe for intracellular imaging. Both in vitro and in vivo studies provide strong evidence that the AuNC-based vaccines may be utilized as safe and efficient immunostimulatory agents that are able to prevent and/or treat a variety of ailments.We here report a facile one-pot synthesis of fluorescent gold nanoclusters (AuNCs) via the peptide biomineralization method, which can elicit specific immunological responses. The as-prepared peptide-protected AuNCs (peptide-AuNCs) display strong red fluorescence, and more importantly, as compared to the peptide alone, the immune stimulatory ability of the resulting peptide-AuNCs can not only be retained, but can also be efficaciously enhanced. Moreover, through a dual-delivery of antigen peptides and cytosine-phosphate-guanine (CpG) oligodeoxynucleotides (ODNs), the as-prepared peptide-AuNC-CpG conjugates can also act as smart self-vaccines to assist in the generation of high immunostimulatory activity, and be applied as a probe for intracellular imaging. Both in vitro and in vivo studies provide strong evidence that the AuNC-based vaccines may be utilized as safe and efficient immunostimulatory agents that are able to prevent and/or treat a variety of ailments. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02240a

Smart app-based on-field colorimetric quantification of mercury via analyte-induced enhancement of the photocatalytic activity of TiO2-Au nanospheres.

PubMed

Ravindranath, Rini; Periasamy, Arun Prakash; Roy, Prathik; Chen, Yu-Wen; Chang, Huan-Tsung

2018-06-04

We have devised a unique strategy for highly sensitive, selective, and colorimetric detection of mercury based on analyte-induced enhancement of the photocatalytic activity of TiO 2 -Au nanospheres (TiO 2 -Au NSs) toward degradation of methylene blue (MB). Through electrostatic interactions, Au nanoparticles are attached to poly-(sodium 4-styreneulfonate)/poly(diallyldimethylammonium chloride) modified TiO 2 nanoparticles, which then form an Au shell on each TiO 2 core through reduction of Au 3+ with ascorbic acid. Notably, the deposition of Hg species (Hg 2+ /CH 3 Hg + ) onto TiO 2 -Au NSs through strong Au-Hg aurophilic interactions speeds up catalytic degradation of MB. The first-order degradation rates of MB by TiO 2 -Au NSs and TiO 2 -Au-Hg NSs are 1.4 × 10 -2  min -1 and 2.1 × 10 -2  min -1 , respectively. Using a commercial absorption spectrometer, the TiO 2 -Au NSs/MB approach provides linearity (R 2  = 0.98) for Hg 2+ over a concentration range of 10.0 to 100.0 nM, with a limit of detection (LOD) of 1.5 nM. On the other hand, using a low-cost smartphone app that records the color changes (ΔRGB) of MB solution based on the red-blue-green (RGB) component values, the TiO 2 -Au NSs/MB approach provides an LOD of 2.0 nM for Hg 2+ and 5.0 nM for CH 3 Hg + , respectively. Furthermore, the smartphone app sensing system has been validated for the analyses of various samples, including tap water, lake water, soil, and Dorm II, showing its great potential for on-line analysis of environmental and biological samples. Graphical Abstract ᅟ.

Gold core/Ceria shell-based redox active nanozyme mimicking the biological multienzyme complex phenomenon

DOE PAGES

Bhagat, Stuti; Srikanth Vallabani, NV; Shutthanandan, Vaithiyalingam; ...

2017-12-02

Catalytically active individual gold (Au) and cerium oxide (CeO 2) nanoparticles (NPs) are well known to exhibit specific enzyme-like activities, such as natural catalase, oxidase, superoxide dismutase, and peroxidase enzymes. Our activities have been maneuvered to design several biological applications such as immunoassays, glucose detection, radiation and free radical protection and tissue engineering. In biological systems, multienzyme complexes are involved in catalyzing important reactions of essential metabolic processes such as respiration, biomolecule synthesis, and photosynthesis. It is well known that metabolic processes linked with multienzyme complexes offer several advantages over reactions catalyzed by individual enzymes. A functional nanozyme depicting multienzymemore » like properties has eluded the researchers in the nanoscience community for the past few decades. Here, we have designed a functional multienzyme in the form of Gold (core)-CeO 2 (shell) nanoparticles (Au/CeO 2 CSNPs) exhibiting excellent peroxidase, catalase, and superoxide dismutase enzyme-like activities that are controlled simply by tuning the pH. The reaction kinetic parameters reveal that the peroxidase-like activity of this core-shell nanozyme is comparable to natural horseradish peroxidase (HRP) enzyme. Unlike peroxidase-like activity exhibited by other nanomaterials, Au/CeO 2 CSNPs showed a decrease in hydroxyl radical formation, suggesting that the biocatalytic reactions are performed by efficient electron transfers. A significant enzyme-like activity of this core-shell nanoparticle was conserved at extreme pH (2 – 11) and temperatures (up to 90 °C), clearly suggesting the superiority over natural enzymes. Further, the utility of peroxidase-like activity of this core-shell nanoparticles was extended for the detection of glucose, which showed a linear range of detection between (100 µM – 1 mM). It is hypothesized that the proximity of the redox potentials of Au+/Au and Ce (III)/Ce (IV) may result in a redox couple promoting the multienzyme activity of core-shell nanoparticles. Au/CeO 2 CSNPs may open new directions for development of single platform sensors in multiple biosensing applications.« less

Gold core/Ceria shell-based redox active nanozyme mimicking the biological multienzyme complex phenomenon

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

Bhagat, Stuti; Srikanth Vallabani, NV; Shutthanandan, Vaithiyalingam

Catalytically active individual gold (Au) and cerium oxide (CeO 2) nanoparticles (NPs) are well known to exhibit specific enzyme-like activities, such as natural catalase, oxidase, superoxide dismutase, and peroxidase enzymes. Our activities have been maneuvered to design several biological applications such as immunoassays, glucose detection, radiation and free radical protection and tissue engineering. In biological systems, multienzyme complexes are involved in catalyzing important reactions of essential metabolic processes such as respiration, biomolecule synthesis, and photosynthesis. It is well known that metabolic processes linked with multienzyme complexes offer several advantages over reactions catalyzed by individual enzymes. A functional nanozyme depicting multienzymemore » like properties has eluded the researchers in the nanoscience community for the past few decades. Here, we have designed a functional multienzyme in the form of Gold (core)-CeO 2 (shell) nanoparticles (Au/CeO 2 CSNPs) exhibiting excellent peroxidase, catalase, and superoxide dismutase enzyme-like activities that are controlled simply by tuning the pH. The reaction kinetic parameters reveal that the peroxidase-like activity of this core-shell nanozyme is comparable to natural horseradish peroxidase (HRP) enzyme. Unlike peroxidase-like activity exhibited by other nanomaterials, Au/CeO 2 CSNPs showed a decrease in hydroxyl radical formation, suggesting that the biocatalytic reactions are performed by efficient electron transfers. A significant enzyme-like activity of this core-shell nanoparticle was conserved at extreme pH (2 – 11) and temperatures (up to 90 °C), clearly suggesting the superiority over natural enzymes. Further, the utility of peroxidase-like activity of this core-shell nanoparticles was extended for the detection of glucose, which showed a linear range of detection between (100 µM – 1 mM). It is hypothesized that the proximity of the redox potentials of Au+/Au and Ce (III)/Ce (IV) may result in a redox couple promoting the multienzyme activity of core-shell nanoparticles. Au/CeO 2 CSNPs may open new directions for development of single platform sensors in multiple biosensing applications.« less

Talin does not associate exclusively with alpha 2b beta 3 integrin in activated human platelets.

PubMed

Escolar, G; Diaz-Ricart, M; White, J G

1995-05-01

Talin is a high-molecular-weight protein that may stabilize connections between cytoplasmic actin and the submembrane portion of glycoprotein IIb-IIIa (GPIIb-IIIa) (alpha 2b beta 3 integrin) in thrombin-stimulated human platelets. Using morphologic and electrophoretic techniques, we have examined the association of talin with the cytoskeleton of platelets activated by thrombin in the presence of fibrinogen-coated gold particles (Fgn/Au). Ultrastructural studies confirmed the presence of Fgn/Au firmly bound to the outside membranes of detergent-extracted platelets. Immunoblots of protein bands showed GPIIIa, but not talin, associated with cytoskeletons of activated platelets. Immunogold cytochemical techniques were performed on ultrathin cryosections of whole platelets to localize talin at the ultrastructural level. Studies were performed on normal platelets and platelets defective in GPIIb-IIIa (Glanzmann's thrombasthenia) and GPIb (Bernard-Soulier syndrome). Talin was randomly distributed in the cytoplasm of resting platelets. Activation resulted in binding of Fgn/Au to the surface membrane and redistribution of talin to the submembrane region. However, no definitive colocalization between the two markers was noted. Activated thrombasthenic platelets failed to bind Fgn/Au, but talin was localized to the submembrane location. After activation, talin was confined to the submembrane zone of Bernard-Soulier syndrome platelets. No definitive colocalization was observed between large clusters of Fgn/Au-occupied receptors and talin distributed in the submembrane region. GPIb and GPIIb-IIIa are not necessary for talin to localize in the submembrane region of activated cells. Talin does not redistribute exclusively with GPIIb-IIIa, and it may stabilize connections with other glycoproteins.

In-vitro free radical scavenging activity of biosynthesized gold and silver nanoparticles using Prunus armeniaca (apricot) fruit extract

NASA Astrophysics Data System (ADS)

Dauthal, Preeti; Mukhopadhyay, Mausumi

2013-01-01

In-vitro free radical scavenging activity of biosynthesized gold (Au-NPs) and silver (Ag-NPs) nanoparticles was investigated in the present study. Natural precursor Prunus armeniaca (apricot) fruit extract was used as a reducing agent for the nanoparticle synthesis. The free radical scavenging activity of the nanoparticles were observed by modified 1,1'-diphynyl-2-picrylhydrazyl, DPPH and 2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonic acid), ABTS assay. The synthesized nanoparticles were characterized by UV-Visible spectroscopy, dynamic light scattering, transmission electron microscopy (TEM), X-ray diffraction (XRD), energy dispersive spectroscopy, and fourier transform infrared spectroscopy (FTIR). Appearance of optical absorption peak at 537 nm (2.20 keV) and 435 nm (3 keV) within 0.08 and 0.5 h of reaction time was confirmed the presence of metallic Au and Ag nanoclusters, respectively. Nearly spherical nanoparticles with majority of particle below 20 nm (TEM) for both Au-NPs and Ag-NPs were synthesized. XRD pattern confirmed the existence of pure nanocrystalline Au-NPs while few additional peaks in the vicinity of fcc silver-speculated crystallization of metalloproteins of fruit extract on the surface of the Ag-NPs and vice versa. FTIR spectra was supported the role of amino acids of protein/enzymes of fruit extract for synthesis and stabilization of nanoparticles. Dose-dependent scavenging activity was observed for Au-NPs and Ag-NPs in both DPPH and ABTS in-vitro assay. 50 % scavenging activity for DPPH were 11.27 and 16.18 mg and for ABTS 3.40 and 7.12 mg with Au-NPs and Ag-NPs, respectively.

Investigation of the Origin of Catalytic Activity in Oxide-Supported Nanoparticle Gold

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

Harrison, Ian

Since Haruta’s discovery in 1987 of the surprising catalytic activity of supported Au nanoparticles, we have seen a very large number of experimental and theoretical efforts to explain this activity and to fully understand the nature of the behavior of the responsible active sites. In 2011, we discovered that a dual catalytic site at the perimeter of ~3nm diameter Au particles supported on TiO 2 is responsible for oxidative catalytic activity. O 2 molecules bind with Au atoms and Ti4+ ions in the TiO 2 support and the weakened O-O bond dissociates at low temperatures, proceeding to produce O atomsmore » which act as oxidizing agents for the test molecule, CO. The papers supported by DOE have built on this finding and have been concerned with two aspects of the behavior of Au/TiO 2 catalysts: (1). Mechanistic behavior of dual catalytic sites in the oxidation of organic molecules such as ethylene and acetic acid; (2). Studies of the electronic properties of the TiO 2 (110) single crystal in relation to its participation in charge transfer at the occupied dual catalytic site. A total of 20 papers have been produced through DOE support of this work. The papers combine IR spectroscopic investigations of Au/TiO 2 catalysts with surface science on the TiO 2(110) and TiO 2 nanoparticle surfaces with modern density functional modeling. The primary goals of the work were to investigate the behavior of the dual Au/Ti 4+ site for the partial oxidation of alcohols to acids, the hydrogenation of aldehydes and ketones to alcohols, and the condensation of oxygenate intermediates- all processes related to the utilization of biomass in the production of useful chemical energy sources.« less

Antibacterial, antibiofilm and cytotoxic effects of Nigella sativa essential oil coated gold nanoparticles.

PubMed

Manju, Sivalingam; Malaikozhundan, Balasubramanian; Vijayakumar, Sekar; Shanthi, Sathappan; Jaishabanu, Ameeramja; Ekambaram, Perumal; Vaseeharan, Baskaralingam

2016-02-01

This study reports the biological synthesis of gold nanoparticles using essential oil of Nigella sativa (NsEO-AuNPs). The synthesized NsEO-AuNPs were characterized by UV-visible spectra, X-ray diffraction (XRD), FTIR and Transmission electron microscopy (TEM). UV-vis spectra of NsEO-AuNPs showed strong absorption peak at 540 nm. The X-ray diffraction analysis revealed crystalline nature of nanoparticle with distinctive facets (111, 200, 220 and 311 planes) of NsEO-AuNPs. The FTIR spectra recorded peaks at 3388, 2842, 1685, 1607, 1391 and 1018 cm(-1). TEM studies showed the spherical shape of nanoparticles and the particle size ranges between 15.6 and 28.4 nm. The antibacterial activity of NsEO-AuNPs was greater against Gram positive Staphylococcus aureus MTCC 9542 (16 mm) than Gram negative Vibrio harveyi MTCC 7771 (5 mm) at the concentration of 10 μg ml(-1). NsEO-AuNPs effectively inhibited the biofilm formation of S. aureus and V. harveyi by decreasing the hydrophobicity index (78% and 46% respectively). The in-vitro anti-lung cancer activity confirmed by MTT assay on the cell line of A549 carcinoma cells showed IC50 values of bulk Au at 87.2 μg ml(-1), N. sativa essential oil at 64.15 μg ml(-1) and NsEO-AuNPs at 28.37 μg ml(-1). The IC50 value showed that NsEO-AuNPs was highly effective in inhibiting the A549 lung cancer cells compared to bulk Au and N. sativa essential oil. Copyright © 2015 Elsevier Ltd. All rights reserved.

A novel antimicrobial therapy for the control of Aeromonas hydrophila infection in aquaculture using marine polysaccharide coated gold nanoparticle.

PubMed

Vijayakumar, Sekar; Vaseeharan, Baskaralingam; Malaikozhundan, Balasubramanian; Gobi, Narayanan; Ravichandran, Samuthirapandian; Karthi, Sellamuthu; Ashokkumar, Balasubramaniem; Sivakumar, Natesan

2017-09-01

In the present study, we prepared fucoidan coated Au-NPs (Fu-AuNPs), and examined its antimicrobial activity against Aeromonas hydrophila. The green synthesized Fu-AuNPs were bio-physically characterized by Ultraviolet-visible (UV-Vis) spectroscopy, X-ray Diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR), Higher Transmission Electron Microscopy (HR-TEM), Zeta potential analysis and Energy Dispersive X-ray spectroscopy (EDX). Fu-AuNPs were crystalline in nature, spherical to triangular in shape, with particle size ranging within 10-100 nm. The synthesized Fu-AuNPs at 100 μg mL -1 showed inhibition zone against A. hydrophila (23.2 mm) which is much higher than that of commercial antibiotic chloramphenicol (17.3 mm). The biofilm inhibitory activity of Fu-AuNPs against Gram negative (Aeromonas hydrophila) was higher. Light and confocal laser scanning microscopic observations showed that the Fu-AuNPs at 100 μg mL -1 inhibited the biofilm of A. hydrophila. The cytotoxicity study indicated that Fu-AuNPs were effective in inhibiting the viability of human cervical cancer cells (HeLa) at 100 μg mL -1 . In another experiment, the antibacterial effect of Fu-AuNPs on tilapia, Oreochromis mossambicus were evaluated in vivo. The mortality rate of O. mossambicus infected by A. hydrophila was much higher (90%), whereas, the mortality of O. mossambicus that received Fu-AuNPs followed by challenge with A. hydrophia was reduced to 30%. This study concludes that Fu-AUNPs are effective in the control of A. hydrophila infections in O. mossambicus. Copyright © 2017 Elsevier Ltd. All rights reserved.

Multi-walled carbon nanotube structural instability with/without metal nanoparticles under electron beam irradiation

NASA Astrophysics Data System (ADS)

Khan, Imran; Huang, Shengli; Wu, Chenxu

2017-12-01

The structural transformation of multi-walled carbon nanotubes (MWCNT) under electron beam (e-beam) irradiation at room temperature is studied, with respect to a novel passivation effect due to gold nanoparticles (Au NPs). MWCNT structural evolution induced by energetic e-beam irradiation leads to faster shrinkage, as revealed via in situ transmission electron microscopy, while MWCNT surface modification with Au NPs (Au-MWCNT) slows down the shrinkage by impeding the structural evolution process for a prolonged time under the same irradiation conditions. The new relationship between MWCNT and Au-MWCNT shrinking radii and irradiation time illustrates that the MWCNT shrinkage rate is faster than either theoretical predictions or the same process in Au-MWCNTs. As compared with the outer surface energy (positive curvature), the inner surface energy (negative curvature) of the MWCNT contributes more to the athermal evaporation of tube wall atoms, leading to structural instability and shrinkage under e-beam irradiation. Conversely, Au NPs possess only outer surface energy (positive curvature) compared with the MWCNT. Their presence on MWCNT surfaces retards the dynamics of MWCNT structural evolution by slowing down the evaporation process of carbon atoms, thus restricting Au-MWCNT shrinkage. Au NP interaction and growth evolves athermally on MWCNT surfaces, exhibits increase in their size, and indicates the association of this mechanism with the coalescence induced by e-beam activated electronic excitations. Despite their growth, Au NPs show extreme structural stability, and remain crystalline under prolonged irradiation. It is proposed that the surface energy of MWCNTs and Au NPs, together with e-beam activated soft modes or lattice instability effects, predominantly govern all the above varieties of structural evolution.

Photothermal effects from Au-Cu2O core-shell nanocubes, octahedra, and nanobars with broad near-infrared absorption tunability

NASA Astrophysics Data System (ADS)

Wang, Hsiang-Ju; Yang, Kung-Hsun; Hsu, Shih-Chen; Huang, Michael H.

2015-12-01

Other than the display of purely optical phenomenon, the recently-discovered facet-dependent optical properties of metal-Cu2O nanocrystals have become useful by illuminating Au-Cu2O nanocubes and octahedra having a surface plasmon resonance (SPR) absorption band in the near-infrared (NIR) region from octahedral Au cores with 808 nm light for heat generation. After 5 min of light irradiation, a solution of Au-Cu2O nanocubes can reach 65 °C with their Au SPR band matching the illuminating light wavelength. Photothermal efficiency has been found to be facet-dependent. In addition, short gold nanorods were employed to synthesize {100}-bound rectangular Au-Cu2O nanobars with a tunable longitudinal Au SPR absorption band covering a broad NIR range from ~1050 to 1400 nm. Because the Au SPR bands can become fixed with relatively thin Cu2O shells of less than 15 nm, ultrasmall nanobars having a size of 61 nm directly red-shift the Au SPR band to 1047 nm. And 73 nm nanobars can give a Au SPR band at 1390 nm. Truncated nanobars exposing {100}, {110}, and {111} facets give a very blue-shifted Au SPR band. The nanobars also exhibit photothermal activity when illuminated by 1064 nm light. These small Au-Cu2O nanocrystals represent the simplest nanostructure design to absorb light covering the entire NIR wavelengths.Other than the display of purely optical phenomenon, the recently-discovered facet-dependent optical properties of metal-Cu2O nanocrystals have become useful by illuminating Au-Cu2O nanocubes and octahedra having a surface plasmon resonance (SPR) absorption band in the near-infrared (NIR) region from octahedral Au cores with 808 nm light for heat generation. After 5 min of light irradiation, a solution of Au-Cu2O nanocubes can reach 65 °C with their Au SPR band matching the illuminating light wavelength. Photothermal efficiency has been found to be facet-dependent. In addition, short gold nanorods were employed to synthesize {100}-bound rectangular Au-Cu2O nanobars with a tunable longitudinal Au SPR absorption band covering a broad NIR range from ~1050 to 1400 nm. Because the Au SPR bands can become fixed with relatively thin Cu2O shells of less than 15 nm, ultrasmall nanobars having a size of 61 nm directly red-shift the Au SPR band to 1047 nm. And 73 nm nanobars can give a Au SPR band at 1390 nm. Truncated nanobars exposing {100}, {110}, and {111} facets give a very blue-shifted Au SPR band. The nanobars also exhibit photothermal activity when illuminated by 1064 nm light. These small Au-Cu2O nanocrystals represent the simplest nanostructure design to absorb light covering the entire NIR wavelengths. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06847a

SERS spectral study of HAuCl4-cysteine nanocatalytic reaction and its application for detection of heparin sodium with label-free VB4r molecular probe

NASA Astrophysics Data System (ADS)

Wang, Xiaoliang; Jiang, Caina; Qin, Yanna; Peng, Yutao; Wen, Guiqing; Liang, Aihui; Jiang, Zhiliang

2017-04-01

In the presence of nanocatalyst, L-cysteine reduce HAuCl4 rapidly to form gold nanoparticles (AuNP), and a quick nanocatalytic preparation procedure was established for Au/AuNP sol with highly active surface enhanced Raman scattering (SERS) effect and good stability. The nanoreaction was also studied by absorption, resonance Rayleigh scattering (RRS), transmission electron microscopy (TEM) and energy spectra. In the selected conditions, the analyte heparin sodium (HS) could react with victoria blue 4 R (VB4r) to form associated complexes which have very weak SERS effect to make the SERS signals decrease. The SERS signals at 1617 cm-1 reduced linearly with HS concentration increasing. Upon addition of FeCl3, it hydrolyzed to form stable Fe(OH)3 sol platform that carried SERS active Au/AuNPs to enhance the sensitivity. Accordingly, we established a SERS quantitative analysis method in the sol substrate of Fe(OH)3-Au/AuNPs, with a linear range of 0.5-75 ng/mL HS and a detection limit of 0.2 ng/mL. HS in real samples was determined, with a relative standard deviation of 2.65-7.63% and a recovery of 99.3-101%.

Inhibition of gold nanoparticles (AuNPs) on pathogenic biofilm formation and invasion to host cells.

PubMed

Yu, Qilin; Li, Jianrong; Zhang, Yueqi; Wang, Yufan; Liu, Lu; Li, Mingchun

2016-05-25

Owing to the growing infectious diseases caused by eukaryotic and prokaryotic pathogens, it is urgent to develop novel antimicrobial agents against clinical pathogenic infections. Biofilm formation and invasion into the host cells are vital processes during pathogenic colonization and infection. In this study, we tested the inhibitory effect of Au nanoparticles (AuNPs) on pathogenic growth, biofilm formation and invasion. Interestingly, although the synthesized AuNPs had no significant toxicity to the tested pathogens, Candida albicans and Pseudomonas aeruginosa, the nanoparticles strongly inhibited pathogenic biofilm formation and invasion to dental pulp stem cells (DPSCs). Further investigations revealed that AuNPs abundantly bound to the pathogen cells, which likely contributed to their inhibitory effect on biofilm formation and invasion. Moreover, treatment of AuNPs led to activation of immune response-related genes in DPSCs, which may enhance the activity of host immune system against the pathogens. Zeta potential analysis and polyethylene glycol (PEG)/polyethyleneimine (PEI) coating tests further showed that the interaction between pathogen cells and AuNPs is associated with electrostatic attractions. Our findings shed novel light on the application of nanomaterials in fighting against clinical pathogens, and imply that the traditional growth inhibition test is not the only way to evaluate the drug effect during the screening of antimicrobial agents.

Implantation of Fe3O4 Nanoparticles in Shells of Au@m-SiO2 Yolk@Shell Nanocatalysts with Both Improved Recyclability and Catalytic Activity.

PubMed

Li, Yanan; Jin, Chenjing; Yuan, Ganyin; Han, Jie; Wang, Minggui; Guo, Rong

2017-08-01

Multifunctional nanocatalysts of Au@Fe 3 O 4 /m-SiO 2 yolk@shell hybrids had been developed through a template-assisted synthesis, where Fe 3 O 4 nanoparticles (∼12 nm) and m-SiO 2 shells were sequentially assembled on surfaces of Au/SiO 2 core/shell templates, followed by selective etching of the inner SiO 2 cores, leading to the formation of Au@Fe 3 O 4 /m-SiO 2 yolk@shell hybrids. The Fe 3 O 4 nanoparticles were implanted in the inner surfaces of m-SiO 2 shells with partially exposed surfaces to the inner cavity. The novel design not only ensures a high surface area (540.0 m 2 /g) and saturation magnetization (48.6 emu/g) of the hybrids but also enables interaction between Au and Fe 3 O 4 nanoparticles. Catalytic tests toward the reduction of 4-nitrophenol in the presence of NaBH 4 indicated that Au@Fe 3 O 4 /m-SiO 2 yolk@shell nanocatalysts not only showed high stability and recyclability but also maintained improved catalytic activity as a result of the synergetic effect resulting from Au and Fe 3 O 4 interactions.

SERS study of surface plasmon resonance induced carrier movement in Au@Cu2O core-shell nanoparticles

NASA Astrophysics Data System (ADS)

Chen, Lei; Zhang, Fan; Deng, Xin-Yu; Xue, Xiangxin; Wang, Li; Sun, Yantao; Feng, Jing-Dong; Zhang, Yongjun; Wang, Yaxin; Jung, Young Mee

2018-01-01

A plasmon induced carrier movement enhanced mechanism of surface-enhanced Raman scattering (SERS) was investigated using a charge-transfer (CT) enhancement mechanism. Here, we designed a strategy to study SERS in Au@Cu2O nanoshell nanoparticles with different shell thicknesses. Among the plasmonically coupled nanostructures, Au spheres with Cu2O shells have been of special interest due to their ultrastrong electromagnetic fields and controllable carrier transfer properties, which are useful for SERS. Au@Cu2O nanoshell nanoparticles (NPs) with shell thicknesses of 48-56 nm are synthesized that exhibit high SERS activity. This high activity originates from plasmonic-induced carrier transfer from Au@Cu2O to 4-mercaptobenzoic acid (MBA). The CT transition from the valence band (VB) of Cu2O to the second excited π-π* transition of MBA, and is of b2 electronic symmetry, which was enhanced significantly. The Herzberg-Teller selection rules were employed to predict the observed enhanced b2 symmetry modes. The system constructed in this study combines the long-range electromagnetic effect of Au NPs, localized surface plasmon resonance (LSPR) of the Au@Cu2O nanoshell, and the CT contribution to assist in understanding the SERS mechanism based on LSPR-induced carrier movement in metal/semiconductor nanocomposites.

Monolayer-enriched production of Au-decorated WS 2 Nanosheets via Defect Engineering

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

Dunklin, Jeremy R.; Lafargue, Paul; Higgins, Thomas M.

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 (WS 2) undergoes a spontaneous redox reaction with gold (III) chloride (AuCl 3). Au nanoparticles (NPs) predominantly nucleate at nanosheet edges with tuneable NP size and density. AuCl 3 is preferentially reduced on multi-layer WS 2 and resulting large Au aggregates are easily separatedmore » 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 AuCl 3 to Au 0 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.« less

Monolayer-enriched production of Au-decorated WS 2 Nanosheets via Defect Engineering

DOE PAGES

Dunklin, Jeremy R.; Lafargue, Paul; Higgins, Thomas M.; ...

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 (WS 2) undergoes a spontaneous redox reaction with gold (III) chloride (AuCl 3). Au nanoparticles (NPs) predominantly nucleate at nanosheet edges with tuneable NP size and density. AuCl 3 is preferentially reduced on multi-layer WS 2 and resulting large Au aggregates are easily separatedmore » 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 AuCl 3 to Au 0 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.« less

Polyethylenimine-assisted seed-mediated synthesis of gold nanoparticles for surface-enhanced Raman scattering studies

NASA Astrophysics Data System (ADS)

Philip, Anish; Ankudze, Bright; Pakkanen, Tuula T.

2018-06-01

Large-sized gold nanoparticles (AuNPs) were synthesized with a new polyethylenimine - assisted seed - mediated method for surface-enhanced Raman scattering (SERS) studies. The size and polydispersity of gold nanoparticles are controlled in the growth step with the amounts of polyethylenimine (PEI) and seeds. Influence of three silicon oxide supports having different surface morphologies, namely halloysite (Hal) nanotubes, glass plates and inverse opal films of SiO2, on the performance of gold nanoparticles in Raman scattering of a 4-aminothiophenol (4-ATP) analyte was investigated. Electrostatic interaction between positively charged polyethylenimine-capped AuNPs and negatively charged surfaces of silicon oxide supports was utilized in fabrication of the SERS substrates using deposition and infiltration methods. The Au-photonic crystal of the three SERS substrate groups is the most active one as it showed the highest analytical enhancement factor (AEF) and the lowest detection limit of 1x10-8 M for 4-ATP. Coupling of the optical properties of photonic crystals with the plasmonic properties of AuNPs provided Au-photonic crystals with the high SERS activity. The AuNPs clusters formed both in the photonic crystal and on the glass plate are capable of forming more hot spots as compared to sparsely distributed AuNPs on Hal nanotubes and thereby increasing the SERS enhancement.

Kondo effect in single cobalt phthalocyanine molecules adsorbed on Au(111) monoatomic steps

NASA Astrophysics Data System (ADS)

Zhao, Aidi; Hu, Zhenpeng; Wang, Bing; Xiao, Xudong; Yang, Jinlong; Hou, J. G.

2008-06-01

The Kondo effect in single dehydrogenated cobalt phthalocyanine (CoPc) molecules adsorbed on Au(111) monoatomic steps was studied with a low temperature scanning tunneling microscope. The CoPc molecules adsorbed on Au(111) monoatomic steps show two typical configurations, which can be dehydrogenated to reveal Kondo effect. Moreover, the Kondo temperatures (TK) measured for different molecules vary in a large range from ~150 to ~550 K, increasing monotonically with decreasing Co-Au distance. A simple model consisting of a single Co 3dz2 orbital and a Au 6s orbital is considered and gives a qualitative explanation to the dependence. The large variation of TK is attributed to the variation of the interaction between the magnetic-active cobalt ion and the Au substrate resulted from different Co-Au distances.

One-dimensional TiO2 nanomaterials: preparation and catalytic applications.

PubMed

Wu, Yu; Yu, Jie; Liu, Hong-Mei; Xu, Bo-Qing

2010-10-01

This work reports on the syntheses of one-dimensional (1D) H2Ti3O7 materials (nanotubes, nanowires and their mixtures) by autoclaving anatase titania (Raw-TiO2) in NaOH-containing ethanol-water solutions, followed by washing with acid solution. The synthesized nanosized materials were characterized using XRD, TEM/HRTEM, BET and TG techniques. The autoclaving temperature (120-180 degrees C) and ethanol-to-water ratio (V(EtOH)/V(H2O) = 0/60 approximately 30/30) were shown to be critical to the morphology of H2Ti3O7 product. The obtained H2Ti3O7 nanostructures were calcined at 400-900 degrees C to prepare 1D-TiO2 nanomaterials. H2Ti3O7 nanotubes were converted to anatase nanorods while H2Ti3O7 nanowires to TiO2(B) nanowires after the calcination at 400 degrees C. The calcination at higher temperatures led to gradual decomposition of the wires to rods and phase transformation from TiO2(B) to anatase then to rutile. Photocatalytic degradation of methyl orange was conducted to compare the photocatalytic activity of these 1D materials. These 1D materials were used as new support to prepare Au/TiO2 catalysts for CO oxidation at 0 degrees C and 1,3-butadiene hydrogenation at 120 degrees C. For the CO oxidation reaction, Au particles supported on anatase nanorods derived from the H2Ti3O7 nanotubes (Au/W-180-400) were 1.6 times active that in Au/P25-TiO2, 4 times that in Au/Raw-TiO2, and 8 times that on TiO2(B) nanowires derived from the H2Ti3O7 nanotubes (Au/M-180-400). For the hydrogenation of 1,3-butadiene, however, the activity of Au particles in Au/M-180-400 was 3 times higher than those in Au/W-180-400 but similar to those in Au/P25-TiO2. These results demonstrate that the potential of 1D-TiO2 nanomaterials in catalysis is versatile.

Comparative study on the effect of H2 pre-adsorption on CO oxidation in O2-poor atmosphere over Au/TiO2 and TiO2: Temperature programmed surface reaction by a multiplexed mass spectrometer testing

NASA Astrophysics Data System (ADS)

Si, Ruiru; Liu, Junfeng; Zhang, Yujuan; Chen, Xun; Dai, Wenxin; Fu, Xianzhi

2016-11-01

The behaviors of H2 pre-adsorption on CO oxidation in an O2-poor stream containing a trace H2O over Au/TiO2 and TiO2 have been investigated by a temperature programmed surface reaction testing, respectively. It was found that the H2 pre-adsorption could keep CO oxidation without H2O consumption over Au/TiO2, but suppress CO oxidation over TiO2. The chemisorption testing showed that the H2 adsorption at Au/TiO2 could benefit to the formation of Ti-bonded hydroxyl species (Ti4+-OH), while the H2 adsorption at TiO2 would consume the Ti-bonded hydroxyl species and form the bridge hydroxyl species (Ti4+-OH-Ti4+). These results show that only the Ti-bonded hydroxyl species (not all kinds of hydroxyl species) could act as the active species of oxidizing CO. Furthermore, it is suggested that the dissociative hydrogen adsorbed at Au sites could activate the lattice oxygen of TiO2 to form the active Ti-bonded hydroxyl species (hydrogen spillover from Au to TiO2), which exhibit a strong reducibility than the H directly adsorbed at TiO2.

Green synthesis of gold nanoparticles using Citrus maxima peel extract and their catalytic/antibacterial activities.

PubMed

Yuan, Chun-Gang; Huo, Can; Gui, Bing; Cao, Wei-Ping

2017-08-01

The peel of Citrus maxima ( C. maxima ) is the primary byproducts during the process of fruit or juice in food industries, and it was always considered as biomass waste for further treatments. In this study, the authors reported a simple and eco-friendly method to synthesise gold nanoparticles (AuNPs) using C. maxima peel extract as reducing and capping agents. The synthesised AuNPs were characterised by UV-visible spectrum, X-ray diffraction (XRD), transmission electron microscope (TEM) and Fourier-transform infrared spectroscopy (FTIR). The UV-visible spectrum of the AuNPs colloid showed a characteristic peak at 540 nm. The peaks of XRD analysis at (2 θ ) 38.30°, 44.28°, 64.62°, 77.57° and 81.75° were assigned to (111), (200), (220), (311) and (222) planes of the face-centered cubic (fcc) lattice of gold. The TEM images showed that AuNPs were nearly spherical in shape with the size of 8-25 nm. The FTIR spectrum revealed that some bioactive compounds capped the surface of synthesised AuNPs. The biosynthesised AuNPs performed strong catalytic activity in degradation of 4-nitrophenol to 4-aminophenol and good antibacterial activity against both gram negative ( Escherichia coli ) and gram positive ( Staphylococcus aureus ) bacterium. The synthesis procedure was proved simple, cost effective and environment friendly.

The evolving activity of the dynamically young comet C/2009 P1 (Garradd)

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

Bodewits, D.; Farnham, T. L.; A'Hearn, M. F.

2014-05-01

We used the Ultraviolet-Optical Telescope on board Swift to observe the dynamically young comet C/2009 P1 (Garradd) from a heliocentric distance of 3.5 AU pre-perihelion until 4.0 AU outbound. At 3.5 AU pre-perihelion, comet Garradd had one of the highest dust-to-gas ratios ever observed, matched only by comet Hale-Bopp. The evolving morphology of the dust in its coma suggests an outburst that ended around 2.2 AU pre-perihelion. Comparing slit-based measurements and observations acquired with larger fields of view indicated that between 3 AU and 2 AU pre-perihelion a significant extended source started producing water in the coma. We demonstrate thatmore » this source, which could be due to icy grains, disappeared quickly around perihelion. Water production by the nucleus may be attributed to a constantly active source of at least 75 km{sup 2}, estimated to be >20% of the surface. Based on our measurements, the comet lost 4 × 10{sup 11} kg of ice and dust during this apparition, corresponding to at most a few meters of its surface. Even though this was likely not the comet's first passage through the inner solar system, the activity of Garradd was complex and changed significantly during the time it was observed.« less

Gold nanoparticles production using reactor and cyclotron based methods in assessment of (196,198)Au production yields by (197)Au neutron absorption for therapeutic purposes.

PubMed

Khorshidi, Abdollah

2016-11-01

Medical nano-gold radioisotopes is produced regularly using high-flux nuclear reactors, and an accelerator-driven neutron activator can turn out higher yield of (197)Au(n,γ)(196,198)Au reactions. Here, nano-gold production via radiative/neutron capture was investigated using irradiated Tehran Research Reactor flux and also simulated proton beam of Karaj cyclotron in Iran. (197)Au nano-solution, including 20nm shaped spherical gold and water, was irradiated under Tehran reactor flux at 2.5E+13n/cm(2)/s for (196,198)Au activity and production yield estimations. Meanwhile, the yield was examined using 30MeV proton beam of Karaj cyclotron via simulated new neutron activator containing beryllium target, bismuth moderator around the target, and also PbF2 reflector enclosed the moderator region. Transmutation in (197)Au nano-solution samples were explored at 15 and 25cm distances from the target. The neutron flux behavior inside the water and bismuth moderators was investigated for nano-gold particles transmutation. The transport of fast neutrons inside bismuth material as heavy nuclei with a lesser lethargy can be contributed in enhanced nano-gold transmutation with long duration time than the water moderator in reactor-based method. Cyclotron-driven production of βeta-emitting radioisotopes for brachytherapy applications can complete the nano-gold production technology as a safer approach as compared to the reactor-based method. Copyright © 2016 Elsevier B.V. All rights reserved.

Selective Enhancement of Nucleases by Polyvalent DNA-Functionalized Gold Nanoparticles

PubMed Central

Prigodich, Andrew E.; Alhasan, Ali H.

2011-01-01

We demonstrate that polyvalent DNA-functionalized gold nanoparticles (DNA-Au NPs) selectively enhance Ribonuclease H (RNase H) activity, while inhibiting most biologically relevant nucleases. This combination of properties is particularly interesting in the context of gene regulation, since high RNase H activity results in rapid mRNA degradation and general nuclease inhibition results in high biological stability. We investigate the mechanism of selective RNase H activation and find that the high DNA density of DNA-Au NPs is responsible for this unusual behavior. This work adds to our understanding of polyvalent DNA-Au NPs as gene regulation agents, and suggests a new model for selectively controlling protein-nanoparticle interactions. PMID:21268581

Photocatalytic reduction of organic pollutant under visible light by green route synthesized gold nanoparticles.

PubMed

Choudhary, Bharat C; Paul, Debajyoti; Gupta, Tarun; Tetgure, Sandesh R; Garole, Vaman J; Borse, Amulrao U; Garole, Dipak J

2017-05-01

We report a rapid method of green chemistry approach for synthesis of gold nanoparticles (AuNPs) using Lagerstroemia speciosa leaf extract (LSE). L. speciosa plant extract is known for its effective treatment of diabetes and kidney related problems. The green synthesis of AuNPs was complete within 30min at 25°C. The same could also be achieved within 2min at a higher reaction temperature (80°C). Both UV-visible spectroscopy and transmission electron microscopy results suggest that the morphology and size distribution of AuNPs are dependent on the pH of gold solution, gold concentration, volume of LSE, and reaction time and temperature. Comparison between Fourier transform infrared spectroscopy (FT-IR) spectra of LSE and the synthesized AuNPs indicate an active role of polyphenolic functional groups (from gallotannins, lagerstroemin, and corosolic acid) in the green synthesis and capping of AuNPs. The green route synthesized AuNPs show strong photocatalytic activity in the reduction of dyes viz., methylene blue, methyl orange, bromophenol blue and bromocresol green, and 4-nitrophenol under visible light in the presence of NaBH 4 . The non-toxic and cost effective LSE mediated AuNPs synthesis proposed in this study is extremely rapid compared to the other reported methods that require hours to days for complete synthesis of AuNPs using various plant extracts. Strong and stable photocatalytic behavior makes AuNPs attractive in environmental applications, particularly in the reduction of organic pollutants in wastewater. Copyright © 2016. Published by Elsevier B.V.

Facile fabrication of network film electrodes with ultrathin Au nanowires for nonenzymatic glucose sensing and glucose/O2 fuel cell.

PubMed

Yang, Lu; Zhang, Yijia; Chu, Mi; Deng, Wenfang; Tan, Yueming; Ma, Ming; Su, Xiaoli; Xie, Qingji; Yao, Shuozhuo

2014-02-15

We report here on the facile fabrication of network film electrodes with ultrathin Au nanowires (AuNWs) and their electrochemical applications for high-performance nonenzymatic glucose sensing and glucose/O2 fuel cell under physiological conditions (pH 7.4, containing 0.15M Cl(-)). AuNWs with an average diameter of ~7 or 2 nm were prepared and can self-assemble into robust network films on common electrodes. The network film electrode fabricated with 2-nm AuNWs exhibits high sensitivity (56.0 μA cm(-2)mM(-1)), low detection limit (20 μM), short response time (within 10s), excellent selectivity, and good storage stability for nonenzymatic glucose sensing. Glucose/O2 fuel cells were constructed using network film electrodes as the anode and commercial Pt/C catalyst modified glassy carbon electrode as cathode. The glucose/O2 fuel cell using 2-nm AuNWs as anode catalyst output a maximum power density of is 126 μW cm(-2), an open-circuit cell voltage of 0.425 V, and a short-circuit current density of 1.34 mA cm(-2), respectively. Due to the higher specific electroactive surface area of 2-nm AuNWs, the network film electrode fabricated with 2-nm AuNWs exhibited higher electrocatalytic activity toward glucose oxidation than the network film electrode fabricated with 7-nm AuNWs. The network film electrode exhibits high electrocatalytic activity toward glucose oxidation under physiological conditions, which is helpful for constructing implantable electronic devices. © 2013 Elsevier B.V. All rights reserved.

Durable electrocatalytic-activity of Pt-Au/C cathode in PEMFCs.

PubMed

Selvaganesh, S Vinod; Selvarani, G; Sridhar, P; Pitchumani, S; Shukla, A K

2011-07-21

Longevity remains as one of the central issues in the successful commercialization of polymer electrolyte membrane fuel cells (PEMFCs) and primarily hinges on the durability of the cathode. Incorporation of gold (Au) to platinum (Pt) is known to ameliorate both the electrocatalytic activity and stability of cathode in relation to pristine Pt-cathodes that are currently being used in PEMFCs. In this study, an accelerated stress test (AST) is conducted to simulate prolonged fuel-cell operating conditions by potential cycling the carbon-supported Pt-Au (Pt-Au/C) cathode. The loss in performance of PEMFC with Pt-Au/C cathode is found to be ∼10% after 7000 accelerated potential-cycles as against ∼60% for Pt/C cathode under similar conditions. These data are in conformity with the electrochemical surface-area values. PEMFC with Pt-Au/C cathode can withstand >10,000 potential cycles with very little effect on its performance. X-ray diffraction and transmission electron microscopy studies on the catalyst before and after AST suggest that incorporating Au with Pt helps mitigate aggregation of Pt particles during prolonged fuel-cell operations while X-ray photoelectron spectroscopy reflects that the metallic nature of Pt is retained in the Pt-Au catalyst during AST in comparison to Pt/C that shows a major portion of Pt to be present as oxidic platinum. Field-emission scanning electron microscopy conducted on the membrane electrode assembly before and after AST suggests that incorporating Au with Pt helps mitigating deformations in the catalyst layer. This journal is © the Owner Societies 2011

The Role of Mg(OH)2 in the So-Called "Base-Free" Oxidation of Glycerol with AuPd Catalysts.

PubMed

Fu, Jile; He, Qian; Miedziak, Peter J; Brett, Gemma L; Huang, Xiaoyang; Pattisson, Samuel; Douthwaite, Mark; Hutchings, Graham J

2018-02-16

Mg(OH) 2 - and Mg(OH) 2 -containing materials can provide excellent performance as supports for AuPd nanoparticles for the oxidation of glycerol in the absence of base, which is considered to be a result of additional basic sites on the surface of the support. However, its influence on the reaction solution is not generally discussed. In this paper, we examine the relationship between the basic Mg(OH) 2 support and AuPd nanoparticles in detail using four types of catalyst. For these reactions, the physical interaction between Mg(OH) 2 and AuPd was adjusted. It was found that the activity of the AuPd nanoparticles increased with the amount of Mg(OH) 2 added under base-free conditions, regardless of its interaction with the noble metals. In order to investigate how Mg(OH) 2 affected the glycerol oxidation, detailed information about the performance of AuPd/Mg(OH) 2 , physically mixed (AuPd/C+Mg(OH) 2 ) and (AuPd/C+NaHCO 3 ) was obtained and compared. Furthermore, NaOH and Mg(OH) 2 were added during the reaction using AuPd/C. All these results indicate that the distinctive and outstanding performance of Mg(OH) 2 supported catalysts in base-free condition is in fact directly related to its ability to affect the pH during the reaction and as such, assists with the initial activation of the primary alcohol, which is considered to be the rate determining step in the reaction. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interaction of SO2 with Cu/TiC(0 0 1) and Au/TiC(0 0 1): Toward a New Family of DeSOx Catalysts

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

L Feria; J Rodriguez; T Jirsak

2011-12-31

Experiments carried out under well-controlled conditions and density functional theory (DFT)-based calculations evidence that Cu and Au nanoparticles supported on a TiC(0 0 1) surface are quite active for the dissociation of the SO{sub 2} molecule. The Cu/TiC(0 0 1) and Au/TiC(0 0 1) systems cleave both S-O bonds of SO{sub 2} at a temperature of 150 K, displaying a reactivity much larger than that of TiC(0 0 1) or extended surfaces of bulk copper and gold. The origin of the high activity of the Cu/TiC(0 0 1) and Au/TiC(0 0 1) systems lies on the interaction between the Cmore » atoms of the substrate and the metal atoms of the supported particle, which results in a large polarization of its electron density. Experiments and theory consistently indicate that the Cu/TiC system is more active toward SO{sub 2} dissociation than the Au/TiC system. This type of systems may provide alternative and efficient DeSO{sub x} catalysts.« less

Interaction of SO2 with Cu/TiC(001) and Au/TiC(001): Towards a New Family of DeSOx Catalysts

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

Rodriguez, J.A.; Feria, L.; Jirsak, T.

2011-04-25

Experiments carried out under well-controlled conditions and density functional theory (DFT)-based calculations evidence that Cu and Au nanoparticles supported on a TiC(0 0 1) surface are quite active for the dissociation of the SO{sub 2} molecule. The Cu/TiC(0 0 1) and Au/TiC(0 0 1) systems cleave both S-O bonds of SO{sub 2} at a temperature of 150 K, displaying a reactivity much larger than that of TiC(0 0 1) or extended surfaces of bulk copper and gold. The origin of the high activity of the Cu/TiC(0 0 1) and Au/TiC(0 0 1) systems lies on the interaction between the Cmore » atoms of the substrate and the metal atoms of the supported particle, which results in a large polarization of its electron density. Experiments and theory consistently indicate that the Cu/TiC system is more active toward SO{sub 2} dissociation than the Au/TiC system. This type of systems may provide alternative and efficient DeSO{sub x} catalysts.« less

Tumor necrosis factor interaction with gold nanoparticles

NASA Astrophysics Data System (ADS)

Tsai, De-Hao; Elzey, Sherrie; Delrio, Frank W.; Keene, Athena M.; Tyner, Katherine M.; Clogston, Jeffrey D.; Maccuspie, Robert I.; Guha, Suvajyoti; Zachariah, Michael R.; Hackley, Vincent A.

2012-05-01

We report on a systematic investigation of molecular conjugation of tumor necrosis factor-α (TNF) protein onto gold nanoparticles (AuNPs) and the subsequent binding behavior to its antibody (anti-TNF). We employ a combination of physical and spectroscopic characterization methods, including electrospray-differential mobility analysis, dynamic light scattering, polyacrylamide gel electrophoresis, attenuated total reflectance-Fourier transform infrared spectroscopy, fluorescence assay, and enzyme-linked immunosorbent assay. The native TNF used in this study exists in the active homotrimer configuration prior to conjugation. After binding to AuNPs, the maximum surface density of TNF is (0.09 +/- 0.02) nm-2 with a binding constant of 3 × 106 (mol L-1)-1. Dodecyl sulfate ions induce desorption of monomeric TNF from the AuNP surface, indicating a relatively weak intermolecular binding within the AuNP-bound TNF trimers. Anti-TNF binds to both TNF-conjugated and citrate-stabilized AuNPs, showing that non-specific binding is significant. Based on the number of anti-TNF molecules adsorbed, a substantially higher binding affinity was observed for the TNF-conjugated surface. The inclusion of thiolated polyethylene glycol (SH-PEG) on the AuNPs inhibits the binding of anti-TNF, and the amount of inhibition is related to the number ratio of surface bound SH-PEG to TNF and the way in which the ligands are introduced. This study highlights the challenges in quantitatively characterizing complex hybrid nanoscale conjugates, and provides insight on TNF-AuNP formation and activity.We report on a systematic investigation of molecular conjugation of tumor necrosis factor-α (TNF) protein onto gold nanoparticles (AuNPs) and the subsequent binding behavior to its antibody (anti-TNF). We employ a combination of physical and spectroscopic characterization methods, including electrospray-differential mobility analysis, dynamic light scattering, polyacrylamide gel electrophoresis, attenuated total reflectance-Fourier transform infrared spectroscopy, fluorescence assay, and enzyme-linked immunosorbent assay. The native TNF used in this study exists in the active homotrimer configuration prior to conjugation. After binding to AuNPs, the maximum surface density of TNF is (0.09 +/- 0.02) nm-2 with a binding constant of 3 × 106 (mol L-1)-1. Dodecyl sulfate ions induce desorption of monomeric TNF from the AuNP surface, indicating a relatively weak intermolecular binding within the AuNP-bound TNF trimers. Anti-TNF binds to both TNF-conjugated and citrate-stabilized AuNPs, showing that non-specific binding is significant. Based on the number of anti-TNF molecules adsorbed, a substantially higher binding affinity was observed for the TNF-conjugated surface. The inclusion of thiolated polyethylene glycol (SH-PEG) on the AuNPs inhibits the binding of anti-TNF, and the amount of inhibition is related to the number ratio of surface bound SH-PEG to TNF and the way in which the ligands are introduced. This study highlights the challenges in quantitatively characterizing complex hybrid nanoscale conjugates, and provides insight on TNF-AuNP formation and activity. Electronic supplementary information (ESI) available: Experimental procedures, instrumentation, materials and calculations. See DOI: 10.1039/c2nr30415e

DFT calculations for Au adsorption onto a reduced TiO2 (110) surface with the coexistence of Cl

NASA Astrophysics Data System (ADS)

Tada, Kohei; Sakata, Kohei; Yamada, Satoru; Okazaki, Kazuyuki; Kitagawa, Yasutaka; Kawakami, Takashi; Yamanaka, Shusuke; Okumura, Mitsutaka

2014-02-01

Residual chlorines, which originate from HAuCl4, enhance the aggregation of gold (Au) nanoparticles and clusters, preventing the generation of highly active supported Au catalysts. However, the detailed mechanism of residual-chlorine-promoted aggregation of Au is unknown. Herein to investigate this mechanism, density functional theory (DFT) calculations of Au and Cl adsorption onto a reduced rutile TiO2 (110) surface were performed using a generalised gradient approximation Perdew, Burke, and Ernzerhof formula (GGA-PBE) functional and plane-wave basis. Although both Au and Cl atoms prefer to mono-absorb onto oxygen defect sites, Cl atoms have a stronger absorption onto a reduced TiO2 (110) surface, abbreviated as rTiO2 (110) in the following, than Au atoms. Additionally, co-adsorption of a Cl atom and a Au atom or Au nanorod onto a rTiO2 surface was investigated; Cl adsorption onto an oxygen defect site weakens the interaction between a Au atom or Au nanorod and rTiO2 (110) surface. The calculation results suggest that the depletion of interaction between Au and rTiO2 surface is due to strong interaction between Cl atoms at oxygen defect sites and neighbouring bridging oxygen (OB) atoms.

Synthesis of gold nanoparticles using renewable Punica granatum juice and study of its catalytic activity

NASA Astrophysics Data System (ADS)

Dash, Shib Shankar; Bag, Braja Gopal

2014-01-01

Punica granatum juice, a delicious multivitamin drink of great medicinal significance, is rich in different types of phytochemicals, such as terpenoids, alkaloids, sterols, polyphenols, sugars, fatty acids, aromatic compounds, amino acids, tocopherols, etc. We have demonstrated the use of the juice for the synthesis of gold nanoparticles (AuNPs) at room temperature under very mild conditions. The synthesis of the AuNPs was complete in few minutes and no extra stabilizing or capping agents were necessary. The size of the nanoparticles could be controlled by varying the concentration of the fruit extract. The AuNPs were characterized by surface plasmon resonance spectroscopy, high resolution transmission electron microscopy, fourier transform infrared spectroscopy and X-ray diffraction studies. Catalytic activity of the synthesized colloidal AuNPs has also been demonstrated.

Fabrication of bimetallic Cu/Au nanotubes and their sensitive, selective, reproducible and reusable electrochemical sensing of glucose

NASA Astrophysics Data System (ADS)

Tee, Si Yin; Ye, Enyi; Pan, Pei Hua; Lee, Coryl Jing Jun; Hui, Hui Kim; Zhang, Shuang-Yuan; Koh, Leng Duei; Dong, Zhili; Han, Ming-Yong

2015-06-01

Herein, we report a facile two-step approach to produce gold-incorporated copper (Cu/Au) nanostructures through controlled disproportionation of the Cu+-oleylamine complex at 220 °C to form copper nanowires and the subsequent reaction with Au3+ at different temperatures of 140, 220 and 300 °C. In comparison with copper nanowires, these bimetallic Cu/Au nanostructures exhibit their synergistic effect to greatly enhance glucose oxidation. Among them, the shape-controlled Cu/Au nanotubes prepared at 140 °C show the highest electrocatalytic activity for non-enzymatic glucose sensing in alkaline solution. In addition to high sensitivity and fast response, the Cu/Au nanotubes possess high selectivity against interferences from other potential interfering species and excellent reproducibility with long-term stability. By introducing gold into copper nanostructures at a low level of 3, 1 and 0.1 mol% relative to the initial copper precursor, a significant electrocatalytic enhancement of the resulting bimetallic Cu/Au nanostructures starts to occur at 1 mol%. Overall, the present fabrication of stable Cu/Au nanostructures offers a promising low-cost platform for sensitive, selective, reproducible and reusable electrochemical sensing of glucose.Herein, we report a facile two-step approach to produce gold-incorporated copper (Cu/Au) nanostructures through controlled disproportionation of the Cu+-oleylamine complex at 220 °C to form copper nanowires and the subsequent reaction with Au3+ at different temperatures of 140, 220 and 300 °C. In comparison with copper nanowires, these bimetallic Cu/Au nanostructures exhibit their synergistic effect to greatly enhance glucose oxidation. Among them, the shape-controlled Cu/Au nanotubes prepared at 140 °C show the highest electrocatalytic activity for non-enzymatic glucose sensing in alkaline solution. In addition to high sensitivity and fast response, the Cu/Au nanotubes possess high selectivity against interferences from other potential interfering species and excellent reproducibility with long-term stability. By introducing gold into copper nanostructures at a low level of 3, 1 and 0.1 mol% relative to the initial copper precursor, a significant electrocatalytic enhancement of the resulting bimetallic Cu/Au nanostructures starts to occur at 1 mol%. Overall, the present fabrication of stable Cu/Au nanostructures offers a promising low-cost platform for sensitive, selective, reproducible and reusable electrochemical sensing of glucose. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02399h

Monodispersed porous flowerlike PtAu nanocrystals as effective electrocatalysts for ethanol oxidation

NASA Astrophysics Data System (ADS)

Li, Shumin; Xu, Hui; Xiong, Zhiping; Zhang, Ke; Wang, Caiqin; Yan, Bo; Guo, Jun; Du, Yukou

2017-11-01

Designing and tuning the bimetallic nanoparticles with desirable morphology and structure can embody them with greatly enhanced electrocatalytic activity and stability towards liquid fuel oxidation. We herein reported a facile one-pot method for the controlled synthesis of monodispersed binary PtAu nanoflowers with abundant exposed surface area. Owing to its fantastic structure, synergistic and electronic effect, such as-prepared PtAu nanoflowers exhibited outstandingly high electrocatalytic activity with the mass activity of 6482 mA mg-1 towards ethanol oxidation, which is 28.3 times higher than that of commercial Pt/C (227 mA mg-1). More interesting, the present PtAu nanoflower catalysts are more stable for the ethanol oxidation reaction in the alkaline with lower current density decay and retained a much higher current density after successive CVs of 500 cycles than that of commercial Pt/C. This work may open a new way for maximizing the catalytic performance of electrocatalysts towards ethanol oxidation by synthesizing shape-controlled alloy nanoparticles with more surface active sites to enhance the performances of direct fuel cells reaction, chemical conversion, and beyond.

Undecylprodigiosin conjugated monodisperse gold nanoparticles efficiently cause apoptosis in colon cancer cells in vitro

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

Nikodinovic-Runic, Jasmina; Mojic, Marija; Kang, Yijin

2014-01-01

Bacterial pigment undecylprodigiosin (UP) was produced using Streptomyces sp. JS520 and conjugated to monodisperse gold nanoparticles (UP-Au). Both UP and UP-Au showed cytocidal activity towards melanoma (A375), lung carcinoma (A549), breast cancer (MCF-7) and colon cancer (HCT-116) cells, inducing apoptosis with IC50 values ranging from 0.4 to 4 mu g ml(-1). Unconjugated UP had a tendency to lose its activity over time and to change biophysical characteristics over pH. The loss of the pigment potency was overcome by conjugation with gold nanoparticles. UP-Au exhibited high stability over pH 3.8 to 7.4 and its activity remained unaffected in time. Nano-packing changedmore » the mechanism of UP toxicity by converting the intracellular signals from a mitochondrial dependent to a mitochondrial independent apoptotic process. The availability of nonpyrogenic UP in high amounts, together with specific anticancer activity and improved stability in the complex with gold nanoparticles, presents a novel platform for further development of UP-Au complexes as an anticancer drug suitable for clinical applications.« less

Au coated PS nanopillars as a highly ordered and reproducible SERS substrate

NASA Astrophysics Data System (ADS)

Kim, Yong-Tae; Schilling, Joerg; Schweizer, Stefan L.; Sauer, Guido; Wehrspohn, Ralf B.

2017-07-01

Noble metal nanostructures with nanometer gap size provide strong surface-enhanced Raman scattering (SERS) which can be used to detect trace amounts of chemical and biological molecules. Although several approaches were reported to obtain active SERS substrates, it still remains a challenge to fabricate SERS substrates with high sensitivity and reproducibility using low-cost techniques. In this article, we report on the fabrication of Au sputtered PS nanopillars based on a template synthetic method as highly ordered and reproducible SERS substrates. The SERS substrates are fabricated by anodic aluminum oxide (AAO) template-assisted infiltration of polystyrene (PS) resulting in hemispherical structures, and a following Au sputtering process. The optimum gap size between adjacent PS nanopillars and thickness of the Au layers for high SERS sensitivity are investigated. Using the Au sputtered PS nanopillars as an active SERS substrate, the Raman signal of 4-methylbenzenethiol (4-MBT) with a concentration down to 10-9 M is identified with good signal reproducibility, showing great potential as promising tool for SERS-based detection.

Importance of Plasmonic Heating on Visible Light Driven Photocatalysis of Gold Nanoparticle Decorated Zinc Oxide Nanorods

PubMed Central

Bora, Tanujjal; Zoepfl, David; Dutta, Joydeep

2016-01-01

Herein we explore the role of localized plasmonic heat generated by resonantly excited gold (Au) NPs on visible light driven photocatalysis process. Au NPs are deposited on the surface of vertically aligned zinc oxide nanorods (ZnO NRs). The localized heat generated by Au NPs under 532 nm continuous laser excitation (SPR excitation) was experimentally probed using Raman spectroscopy by following the phonon modes of ZnO. Under the resonant excitation the temperature at the surface of the Au-ZnO NRs reaches up to about 300 °C, resulting in almost 6 times higher apparent quantum yield (AQY) for photocatalytic degradation of methylene blue (MB) compared to the bare ZnO NRs. Under solar light irradiation the Au-ZnO NRs demonstrated visible light photocatalytic activity twice that of what was achieved with bare ZnO NRs, while significantly reduced the activation energy required for the photocatalytic reactions allowing the reactions to occur at a faster rate. PMID:27242172

Fast and Simple Microwave Synthesis of TiO2/Au Nanoparticles for Gas-Phase Photocatalytic Hydrogen Generation.

PubMed

May-Masnou, Anna; Soler, Lluís; Torras, Miquel; Salles, Pol; Llorca, Jordi; Roig, Anna

2018-01-01

The fabrication of small anatase titanium dioxide (TiO 2 ) nanoparticles (NPs) attached to larger anisotropic gold (Au) morphologies by a very fast and simple two-step microwave-assisted synthesis is presented. The TiO 2 /Au NPs are synthesized using polyvinylpyrrolidone (PVP) as reducing, capping and stabilizing agent through a polyol approach. To optimize the contact between the titania and the gold and facilitate electron transfer, the PVP is removed by calcination at mild temperatures. The nanocatalysts activity is then evaluated in the photocatalytic production of hydrogen from water/ethanol mixtures in gas-phase at ambient temperature. A maximum value of 5.3 mmol·[Formula: see text]h -1 (7.4 mmol·[Formula: see text]h -1 ) of hydrogen is recorded for the system with larger gold particles at an optimum calcination temperature of 450°C. Herein we demonstrate that TiO 2 -based photocatalysts with high Au loading and large Au particle size (≈50 nm) NPs have photocatalytic activity.

Complete Au@ZnO core-shell nanoparticles with enhanced plasmonic absorption enabling significantly improved photocatalysis

NASA Astrophysics Data System (ADS)

Sun, Yiqiang; Sun, Yugang; Zhang, Tao; Chen, Guozhu; Zhang, Fengshou; Liu, Dilong; Cai, Weiping; Li, Yue; Yang, Xianfeng; Li, Cuncheng

2016-05-01

Nanostructured ZnO exhibits high chemical stability and unique optical properties, representing a promising candidate among photocatalysts in the field of environmental remediation and solar energy conversion. However, ZnO only absorbs the UV light, which accounts for less than 5% of total solar irradiation, significantly limiting its applications. In this article, we report a facile and efficient approach to overcome the poor wettability between ZnO and Au by carefully modulating the surface charge density on Au nanoparticles (NPs), enabling rapid synthesis of Au@ZnO core-shell NPs at room temperature. The resulting Au@ZnO core-shell NPs exhibit a significantly enhanced plasmonic absorption in the visible range due to the Au NP cores. They also show a significantly improved photocatalytic performance in comparison with their single-component counterparts, i.e., the Au NPs and ZnO NPs. Moreover, the high catalytic activity of the as-synthesized Au@ZnO core-shell NPs can be maintained even after many cycles of photocatalytic reaction. Our results shed light on the fact that the Au@ZnO core-shell NPs represent a promising class of candidates for applications in plasmonics, surface-enhanced spectroscopy, light harvest devices, solar energy conversion, and degradation of organic pollutants.Nanostructured ZnO exhibits high chemical stability and unique optical properties, representing a promising candidate among photocatalysts in the field of environmental remediation and solar energy conversion. However, ZnO only absorbs the UV light, which accounts for less than 5% of total solar irradiation, significantly limiting its applications. In this article, we report a facile and efficient approach to overcome the poor wettability between ZnO and Au by carefully modulating the surface charge density on Au nanoparticles (NPs), enabling rapid synthesis of Au@ZnO core-shell NPs at room temperature. The resulting Au@ZnO core-shell NPs exhibit a significantly enhanced plasmonic absorption in the visible range due to the Au NP cores. They also show a significantly improved photocatalytic performance in comparison with their single-component counterparts, i.e., the Au NPs and ZnO NPs. Moreover, the high catalytic activity of the as-synthesized Au@ZnO core-shell NPs can be maintained even after many cycles of photocatalytic reaction. Our results shed light on the fact that the Au@ZnO core-shell NPs represent a promising class of candidates for applications in plasmonics, surface-enhanced spectroscopy, light harvest devices, solar energy conversion, and degradation of organic pollutants. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00933f

Kinetically controlled synthesis of Au102(SPh)44 nanoclusters and catalytic application

NASA Astrophysics Data System (ADS)

Chen, Yongdong; Wang, Jin; Liu, Chao; Li, Zhimin; Li, Gao

2016-05-01

We here explore a kinetically controlled synthetic protocol for preparing solvent-solvable Au102(SPh)44 nanoclusters which are isolated from polydispersed gold nanoclusters by solvent extraction and size exclusion chromatography (SEC). The as-obtained Au102(SPh)44 nanoclusters are determined by matrix-assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) mass spectrometry, in conjunction with UV-vis spectroscopy and thermogravimetric analysis (TGA). However, Au99(SPh)42, instead of Au102(SPh)44, is yielded when the polydispersed gold nanoclusters are etched in the presence of excess thiophenol under thermal conditions (e.g., 80 °C). Interestingly, the Au102(SPh)44 nanoclusters also can convert to Au99(SPh)42 with equivalent thiophenol ligands, evidenced by the analyses of UV-vis and MALDI mass spectrometry. Finally, the TiO2-supported Au102(SPh)44 nanocluster catalyst is investigated in the selective oxidation of sulfides into sulfoxides by the PhIO oxidant and gives rise to high catalytic activity (e.g., 80-99% conversion of R-S-R' sulfides with 96-99% selectivity for R-S(&z.dbd;O)-R' sulfoxides). The Au102(SPh)44/TiO2 catalyst also shows excellent recyclability in the sulfoxidation process.We here explore a kinetically controlled synthetic protocol for preparing solvent-solvable Au102(SPh)44 nanoclusters which are isolated from polydispersed gold nanoclusters by solvent extraction and size exclusion chromatography (SEC). The as-obtained Au102(SPh)44 nanoclusters are determined by matrix-assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) mass spectrometry, in conjunction with UV-vis spectroscopy and thermogravimetric analysis (TGA). However, Au99(SPh)42, instead of Au102(SPh)44, is yielded when the polydispersed gold nanoclusters are etched in the presence of excess thiophenol under thermal conditions (e.g., 80 °C). Interestingly, the Au102(SPh)44 nanoclusters also can convert to Au99(SPh)42 with equivalent thiophenol ligands, evidenced by the analyses of UV-vis and MALDI mass spectrometry. Finally, the TiO2-supported Au102(SPh)44 nanocluster catalyst is investigated in the selective oxidation of sulfides into sulfoxides by the PhIO oxidant and gives rise to high catalytic activity (e.g., 80-99% conversion of R-S-R' sulfides with 96-99% selectivity for R-S(&z.dbd;O)-R' sulfoxides). The Au102(SPh)44/TiO2 catalyst also shows excellent recyclability in the sulfoxidation process. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08338a

Bifunctional Ag@SiO 2 /Au Nanoparticles for Probing Sequential Catalytic Reactions by Surface-Enhanced Raman Spectroscopy

DOE PAGES

Wu, Yiren; Su, Dong; Qin, Dong

2017-02-22

Here, we report the synthesis of bifunctional Ag@SiO 2/Au nanoparticles with an “islands in the sea” configuration by titrating HAuCl 4 solution into an aqueous suspension of Ag@SiO 2 core–shell nanocubes in the presence of NaOH, ascorbic acid, and poly(vinyl pyrrolidone) at pH 11.9. The NaOH plays an essential role in generating small pores in the SiO 2 shell in situ, followed by the epitaxial deposition of Au from the Ag surface through the pores, leading to the formation of Au islands (6–12 nm in size) immersed in a SiO 2 sea. Furthermore, by controlling the amount of HAuCl 4more » titrated into the reaction system, the Au islands can be made to pass through and protrude from the SiO 2 shell, embracing catalytic activity toward the reduction of 4-nitrophenol to 4-aminophenol by NaBH4. And while the Ag in the core provides a strong surface-enhanced Raman scattering activity, the SiO 2 sea helps maintain the Au component as compact, isolated, and stabilized islands. The Ag@SiO 2/Au nanoparticles can serve as a bifunctional probe to monitor the stepwise Au-catalyzed reduction of 4-nitrothiophenol to 4-aminothiophenol by NaBH 4 and Ag-catalyzed oxidation of 4-aminothiophenol to trans-4,4'-dimercaptoazobenzene by the O 2 from air in the same reaction system.« less

Bifunctional Ag@SiO 2 /Au Nanoparticles for Probing Sequential Catalytic Reactions by Surface-Enhanced Raman Spectroscopy

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

Wu, Yiren; Su, Dong; Qin, Dong

Here, we report the synthesis of bifunctional Ag@SiO 2/Au nanoparticles with an “islands in the sea” configuration by titrating HAuCl 4 solution into an aqueous suspension of Ag@SiO 2 core–shell nanocubes in the presence of NaOH, ascorbic acid, and poly(vinyl pyrrolidone) at pH 11.9. The NaOH plays an essential role in generating small pores in the SiO 2 shell in situ, followed by the epitaxial deposition of Au from the Ag surface through the pores, leading to the formation of Au islands (6–12 nm in size) immersed in a SiO 2 sea. Furthermore, by controlling the amount of HAuCl 4more » titrated into the reaction system, the Au islands can be made to pass through and protrude from the SiO 2 shell, embracing catalytic activity toward the reduction of 4-nitrophenol to 4-aminophenol by NaBH4. And while the Ag in the core provides a strong surface-enhanced Raman scattering activity, the SiO 2 sea helps maintain the Au component as compact, isolated, and stabilized islands. The Ag@SiO 2/Au nanoparticles can serve as a bifunctional probe to monitor the stepwise Au-catalyzed reduction of 4-nitrothiophenol to 4-aminothiophenol by NaBH 4 and Ag-catalyzed oxidation of 4-aminothiophenol to trans-4,4'-dimercaptoazobenzene by the O 2 from air in the same reaction system.« less

Bioinspired Synthesis of Photocatalytic Nanocomposite Membranes Based on Synergy of Au-TiO2 and Polydopamine for Degradation of Tetracycline under Visible Light.

PubMed

Wang, Chen; Wu, Yilin; Lu, Jian; Zhao, Juan; Cui, Jiuyun; Wu, Xiuling; Yan, Yongsheng; Huo, Pengwei

2017-07-19

A bioinspired photocatalytic nanocomposite membrane was successfully prepared via polydopamine (pDA)-coated poly(vinylidene fluoride) (PVDF) membrane, as a secondary platform for vacuum-filtrated Au-TiO 2 nanocomposites, with enhanced photocatalytic activity. The degradation efficiency of Au-TiO 2 /pDA/PVDF membranes reached 92% when exposed to visible light for 120 min, and the degradation efficiency of Au-TiO 2 /pDA/PVDF membranes increased by 26% compared to that of Au-TiO 2 powder and increased by 51% compared to that of TiO 2 /pDA/PVDF nanocomposite membranes. The degradation efficiency remained about 90% after five cycle experiments, and the Au-TiO 2 /pDA/PVDF nanocomposite membranes showed good stability, regeneration performance, and easy recycling. The pDA coating not only served as a bioadhesion interface to improve the bonding force between the catalyst and the membrane substrate but also acted as a photosensitizer to broaden the wavelength response range of TiO 2 , and the structure of Au-TiO 2 /pDA/PVDF also improves the transfer rate of photogenerated electrons; the surface plasmon resonance effect of Au also played a positive role in improving the activity of the catalyst. Therefore, we believe that this study opens up a new strategy in preparing the bioinspired photocatalytic nanocomposite membrane for potential wastewater purification, catalysis, and as a membrane separation field.

Analyzing the electrooxidation of ethylene glycol and glucose over platinum-modified gold electrocatalysts in alkaline electrolyte using in-situ infrared spectroscopy

NASA Astrophysics Data System (ADS)

Mahoney, Elizabeth G.; Sheng, Wenchao; Cheng, Mei; Lee, Kevin X.; Yan, Yushan; Chen, Jingguang G.

2016-02-01

Platinum modified gold (Pt/Au) catalysts are evaluated for the electrooxidation of ethylene glycol (EG) and glucose (Glc). The Pt/Au catalysts are synthesized on an Au disk and supported Au/C particles through the galvanic displacement of a copper monolayer with Pt. The Pt/Au catalysts are compared to monometallic Pt and Au catalysts for the oxidation of EG and Glc in alkaline electrolyte. The Pt/Au disk has an onset potential for these reactions that is similar to Pt and is lower than Au. The supported catalysts are less active toward the electrooxidation of EG and Glc than the corresponding disk electrodes, but the Pt/Au/C also has an onset potential similar to Pt/C. In-situ FTIR is used to analyze the C-C bond scission in both reactions on the surfaces of Pt, Au, and Pt/Au disks. While the Pt/Au disk is found to have a low onset potential for the oxidation of EG, it does not produce as much CO2 as bulk Pt. On the other hand, the FTIR results show that CO2 is produced for the oxidation of Glc on the Pt/Au disk. These results show promise for the possibility of decreasing the amount of Pt needed for the electrooxidation of polyol molecules.

Facile preparation of surfactant-free Au NPs/RGO/Ni foam for degradation of 4-nitrophenol and detection of hydrogen peroxide.

PubMed

Liu, Y Y; Guo, X L; Zhao, L; Zhu, L; Chen, Z T; Chen, J; Zhang, Y; Sun, L T; Zhao, Y H

2018-06-08

The application of Au nanoparticles (Au NPs) often requires surface modification with chemical surfactants, which dramatically reduce the surface activity and increase the chemical contamination and cost of Au NPs. In this research, we have developed a novel Au NPs/reduced graphene oxide/Ni foam hybrid (Au NPs/RGO/NiF) by in situ reduction through ascorbic acid and replacement reaction. This method is green, facile and efficient. The Au NPs are free of chemical surfactants and are homogeneously distributed on the surface of the RGO/NiF. The as-prepared Au NPs/RGO/NiF hybrid is uniform, stable and exhibits not only a high reduction efficiency for the reduction of 4-nitrophenol with a catalytic kinetic constant of up to 0.46 min -1 (0.15 cm 3 catalysis) but also a sensitive and selective detection of H 2 O 2 with a detection limit of ∼1.60 μM.

Direct observation of interfacial Au atoms on TiO₂ in three dimensions.

PubMed

Gao, Wenpei; Sivaramakrishnan, Shankar; Wen, Jianguo; Zuo, Jian-Min

2015-04-08

Interfacial atoms, which result from interactions between the metal nanoparticles and support, have a large impact on the physical and chemical properties of nanoparticles. However, they are difficult to observe; the lack of knowledge has been a major obstacle toward unraveling their role in chemical transformations. Here we report conclusive evidence of interfacial Au atoms formed on the rutile (TiO2) (110) surfaces by activation using high-temperature (∼500 °C) annealing in air. Three-dimensional imaging was performed using depth-sectioning enabled by aberration-corrected scanning transmission electron microscopy. Results show that the interface between Au nanocrystals and TiO2 (110) surfaces consists of a single atomic layer with Au atoms embedded inside Ti-O. The number of interfacial Au atoms is estimated from ∼1-8 in an interfacial atomic column. Direct impact of interfacial Au atoms is observed on an enhanced Au-TiO2 interaction and the reduction of surface TiO2; both are critical to Au catalysis.

Stabilizing ultrasmall Au clusters for enhanced photoredox catalysis.

PubMed

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.

Construction of Au@Pt core—satellite nanoparticles based on in-situ reduction of polymeric ionic liquid protected gold nanoparticles

NASA Astrophysics Data System (ADS)

Wu, Wenlan; Li, Junbo; Zou, Sheng; Guo, Jinwu; Zhou, Huiyun

2017-03-01

A method of in-situ reduction to prepare Au@Pt core-satellite nanoparticles (NPs) is described by using Au NPs coating poly[1-methyl 3-(2-methacryloyloxy propylimidazolium bromine)] (PMMPImB-@-Au NPs) as the template. After electrostatic complex chloroplatinic acid with PMMPImB shell, the composite NP was directly reduced with N2H4 to produce Au@Pt core-satellite NPs. The characterization of composite and core-satellite NPs under different amounts of chloroplatinic acid were studied by DLS, UV-vis absorption spectrum and TEM. The satellite Pt NPs with a small size ( 2 nm) dotted around Au core, and the resulting Au@Pt core-satellite NPs showed a red-shift surface plasmon resonance (SPR) and a good dispersion due to effectively electrostatic repulsion providing by the polymeric ionic liquid (PIL) shell. Finally, Au@Pt core-satellite NPs exhibit an enhanced catalytic activity and cycled catalytic capability for the reduction of p-nitrophenol with NaBH4.

Facile preparation of surfactant-free Au NPs/RGO/Ni foam for degradation of 4-nitrophenol and detection of hydrogen peroxide

NASA Astrophysics Data System (ADS)

Liu, Y. Y.; Guo, X. L.; Zhao, L.; Zhu, L.; Chen, Z. T.; Chen, J.; Zhang, Y.; Sun, L. T.; Zhao, Y. H.

2018-06-01

The application of Au nanoparticles (Au NPs) often requires surface modification with chemical surfactants, which dramatically reduce the surface activity and increase the chemical contamination and cost of Au NPs. In this research, we have developed a novel Au NPs/reduced graphene oxide/Ni foam hybrid (Au NPs/RGO/NiF) by in situ reduction through ascorbic acid and replacement reaction. This method is green, facile and efficient. The Au NPs are free of chemical surfactants and are homogeneously distributed on the surface of the RGO/NiF. The as-prepared Au NPs/RGO/NiF hybrid is uniform, stable and exhibits not only a high reduction efficiency for the reduction of 4-nitrophenol with a catalytic kinetic constant of up to 0.46 min‑1 (0.15 cm3 catalysis) but also a sensitive and selective detection of H2O2 with a detection limit of ∼1.60 μM.

Interaction of size-selected gold nanoclusters with dopamine

NASA Astrophysics Data System (ADS)

Montone, Georgia R.; Hermann, Eric; Kandalam, Anil K.

2016-12-01

We present density functional theory based results on the interaction of size-selected gold nanoclusters, Au10 and Au20, with dopamine molecule. The gold clusters interact strongly with the nitrogen site of dopamine, thereby forming stable gold-dopamine complexes. Our calculations further show that there is no site specificity on the planar Au10 cluster with all the edge gold atoms equally preferred. On the other hand, in the pyramidal Au20 cluster, the vertex metal atom is the most active site. As the size increased from Au10 to Au20, the interaction strength has shown a declining trend. The effect of aqueous environment on the interaction strengths were also studied by solvation model. It is found that the presence of solvent water stabilizes the interaction between the metal cluster and dopamine molecule, even though for Au10 cluster the energy ordering of the isomers changed from that of the gas-phase.

Highly selective and sensitive method for Cu2 + detection based on chiroptical activity of L-Cysteine mediated Au nanorod assemblies

NASA Astrophysics Data System (ADS)

Abbasi, Shahryar; Khani, Hamzeh

2017-11-01

Herein, we demonstrated a simple and efficient method to detect Cu2 + based on amplified optical activity in the chiral nanoassemblies of gold nanorods (Au NRs). L-Cysteine can induce side-by-side or end-to-end assembly of Au NRs with an evident plasmonic circular dichroism (PCD) response due to coupling between surface plasmon resonances (SPR) of Au NRs and the chiral signal of L-Cys. Because of the obvious stronger plasmonic circular dichrosim (CD) response of the side-by-side assembly compared with the end-to-end assemblies, SS assembled Au NRs was selected as a sensitive platform and used for Cu2 + detection. In the presence of Cu2 +, Cu2 + can catalyze O2 oxidation of cysteine to cystine. With an increase in Cu2 + concentration, the L-Cysteine-mediated assembly of Au NRs decreased because of decrease in the free cysteine thiol groups, and the PCD signal decreased. Taking advantage of this method, Cu2 + could be detected in the concentration range of 20 pM-5 nM. Under optimal conditions, the calculated detection limit was found to be 7 pM.

Adsorption of carbon monoxide on smaller gold-cluster anions in an atmospheric-pressure flow-reactor: temperature and humidity dependence.

PubMed

Wallace, William T; Wyrwas, Richard B; Leavitt, Andrew J; Whetten, Robert L

2005-03-07

In the absence of moisture and at room temperature, the activity and saturation of CO on gold cluster anions, Au(N)-, are known to be highly dependent on the size of the cluster. Small Au(N)- clusters (N = 2,3) showed no adsorption activity, and the saturation CO adsorption values did not increase proportionately to cluster size or area. Here, we report on the effects of water vapor and temperature on the ability of Au(N)- clusters to adsorb CO in a high-pressure, fast-flow reactor. In contrast to all earlier reports, our results using this method show that smaller gold-cluster anions bind single and multiple CO groups at ambient temperature and above. In particular, species previously unseen at room temperature, corresponding to Au2(CO)-, Au3(CO) and Au4(CO)2, have been observed. Apparently, the presence of water vapor facilitates the adsorption of CO on the smaller clusters, possibly by aiding in the release of adsorption energy. As the number of studies concerning gold catalysis has continually increased over the past decade, these results provide important new information on the possible role of moisture in gold catalysis.

One-step synthesis of graphene/Au nanoparticle composite by epoxy resin: electrocatalytic detection of H2O2 and catalytic reduction of 4-nitrophenol

NASA Astrophysics Data System (ADS)

Zhang, Yonghang; Zhang, Qixian; Lü, Wei

2017-10-01

In the present work, graphene/gold nanoparticle (AuNP) composites were synthesized via a one-step and green method using modified epoxy resin E-44 (AB-EP-44)—a phenolic—as both stabilizer and reductant in aqueous solution. The as-prepared samples were further characterized by ultraviolet-visible (UV-Vis) absorption spectra, transmission electron microscopy (TEM) and x-ray photoelectron spectroscopy (XPS), proving the successful synthesis of graphene/AuNP composites, and that the small AuNPs with an average diameter of ~3 nm were uniformly dispersed on graphene sheets. The composites exhibited excellent electrochemical activity towards reduction of H2O2 with a good linear response from 0-130 µM and a high sensitivity of 0.283 µA µM-1 cm-2 in addition, a detection limit of ~0.45 µM (the signal/noise:3) was achieved by using a graphene/AuNP sensor. Furthermore, the graphene/AuNP composites showed highly catalytic activity toward 4-nitrophenol (4-NP) reduction. The present green and simple synthesis approach also could be used to prepare other metal/graphene nanomaterials.

Photocatalytic detoxification of Acid Red 18 by modified ZnO catalyst under sunlight irradiation

NASA Astrophysics Data System (ADS)

Senthilraja, A.; Subash, B.; Dhatshanamurthi, P.; Swaminathan, M.; Shanthi, M.

2015-03-01

In this work, hybrid structured Bi-Au-ZnO composite was prepared by precipitation-decomposition method. This method is mild, economical and efficient. Bi-Au-ZnO was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectrum (EDS), diffuse reflectance spectra (DRS), photoluminescence spectra (PL) and BET surface area measurements. Photocatalytic activity of Bi-Au-ZnO was evaluated by irradiating the Acid Red 18 (AR 18) dye solution under sun light. Heterostructured Bi-Au-ZnO photocatalyst showed higher photocatalytic activity than those of individual Bi-ZnO, Au-ZnO, bare ZnO, and TiO2-P25 at pH 11. The effects of operational parameters such as the amount of catalyst dosage, dye concentration, initial pH on photo mineralization of AR 18 dye have been analyzed. The mineralization of AR 18 has been confirmed by chemical oxygen demand (COD) measurements. A possible mechanism is proposed for the degradation of AR 18 under sun light. Finally, Bi-Au-ZnO heterojunction photocatalyst was more stable and could be easily recycled several times opening a new avenue for potential industrial applications.

Hydrogen production by Tuning the Photonic Band Gap with the Electronic Band Gap of TiO2

PubMed Central

Waterhouse, G. I. N.; Wahab, A. K.; Al-Oufi, M.; Jovic, V.; Anjum, D. H.; Sun-Waterhouse, D.; Llorca, J.; Idriss, H.

2013-01-01

Tuning the photonic band gap (PBG) to the electronic band gap (EBG) of Au/TiO2 catalysts resulted in considerable enhancement of the photocatalytic water splitting to hydrogen under direct sunlight. Au/TiO2 (PBG-357 nm) photocatalyst exhibited superior photocatalytic performance under both UV and sunlight compared to the Au/TiO2 (PBG-585 nm) photocatalyst and both are higher than Au/TiO2 without the 3 dimensionally ordered macro-porous structure materials. The very high photocatalytic activity is attributed to suppression of a fraction of electron-hole recombination route due to the co-incidence of the PBG with the EBG of TiO2 These materials that maintain their activity with very small amount of sacrificial agents (down to 0.5 vol.% of ethanol) are poised to find direct applications because of their high activity, low cost of the process, simplicity and stability. PMID:24108361

Rational design of binder-free noble metal/metal oxide arrays with nanocauliflower structure for wide linear range nonenzymatic glucose detection

PubMed Central

Li, Zhenzhen; Xin, Yanmei; Zhang, Zhonghai; Wu, Hongjun; Wang, Peng

2015-01-01

One-dimensional nanocomposites of metal-oxide and noble metal were expected to present superior performance for nonenzymatic glucose detection due to its good conductivity and high catalytic activity inherited from noble metal and metal oxide respectively. As a proof of concept, we synthesized gold and copper oxide (Au/CuO) composite with unique one-dimensional nanocauliflowers structure. Due to the nature of the synthesis method, no any foreign binder was needed in keeping either Au or CuO in place. To the best of our knowledge, this is the first attempt in combining metal oxide and noble metal in a binder-free style for fabricating nonenzymatic glucose sensor. The Au/CuO nanocauliflowers with large electrochemical active surface and high electrolyte contact area would promise a wide linear range and high sensitive detection of glucose with good stability and reproducibility due to its good electrical conductivity of Au and high electrocatalytic activity of CuO. PMID:26068705

Preparation of Pt Ag alloy nanoisland/graphene hybrid composites and its high stability and catalytic activity in methanol electro-oxidation

PubMed Central

2011-01-01

In this article, PtAg alloy nanoislands/graphene hybrid composites were prepared based on the self-organization of Au@PtAg nanorods on graphene sheets. Graphite oxides (GO) were prepared and separated to individual sheets using Hummer's method. Graphene nano-sheets were prepared by chemical reduction with hydrazine. The prepared PtAg alloy nanomaterial and the hybrid composites with graphene were characterized by SEM, TEM, and zeta potential measurements. It is confirmed that the prepared Au@PtAg alloy nanorods/graphene hybrid composites own good catalytic function for methanol electro-oxidation by cyclic voltammograms measurements, and exhibited higher catalytic activity and more stability than pure Au@Pt nanorods and Au@AgPt alloy nanorods. In conclusion, the prepared PtAg alloy nanoislands/graphene hybrid composites own high stability and catalytic activity in methanol electro-oxidation, so that it is one kind of high-performance catalyst, and has great potential in applications such as methanol fuel cells in near future. PMID:21982417

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

PubMed Central

Liu, Siqi; Xu, Yi-Jun

2016-01-01

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. PMID:26947754

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

NASA Astrophysics Data System (ADS)

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.

Gold nanoparticle-polydimethylsiloxane films reflect light internally by optical diffraction and Mie scattering

NASA Astrophysics Data System (ADS)

Dunklin, Jeremy R.; Forcherio, Gregory T.; Roper, D. Keith

2015-08-01

Optical properties of polymer films embedded with plasmonic nanoparticles (NPs) are important in many implementations. In this work, optical extinction by polydimethylsiloxane (PDMS) films containing gold (Au) NPs was enhanced at resonance compared to AuNPs in suspensions, Beer-Lambert law, or Mie theory by internal reflection due to optical diffraction in 16 nm AuNP-PDMS films and Mie scattering in 76 nm AuNP-PDMS films. Resonant extinction per AuNP for 16 nm AuNPs with negligible resonant Mie scattering was enhanced up to 1.5-fold at interparticle separation (i.e., Wigner-Seitz radii) comparable to incident wavelength. It was attributable to diffraction through apertures formed by overlapping electric fields of adjacent, resonantly excited AuNPs at Wigner-Seitz radii equal to or less than incident wavelengths. Resonant extinction per AuNP for strongly Mie scattering 76 nm AuNPs was enhanced up to 1.3-fold at Wigner-Seitz radii four or more times greater than incident wavelength. Enhanced light trapping from diffraction and/or scattering is relevant to optoelectronic, biomedical, and catalytic activity of substrates embedded with NPs.

Synthesis and catalytic activity of the metastable phase of gold phosphide

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

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

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

Antitumor Activity of Alloy and Core-Shell-Type Bimetallic AgAu Nanoparticles

NASA Astrophysics Data System (ADS)

Shmarakov, Igor; Mukha, Iuliia; Vityuk, Nadiia; Borschovetska, Vira; Zhyshchynska, Nelya; Grodzyuk, Galyna; Eremenko, Anna

2017-05-01

Nanoparticles (NPs) of noble metals, namely gold and silver, remain promising anticancer agents capable of enhancing current surgery- and chemotherapeutic-based approaches in cancer treatment. Bimetallic AgAu composition can be used as a more effective agent due to the synergetic effect. Among the physicochemical parameters affecting gold and silver nanoparticle biological activity, a primary concern relates to their size, shape, composition, charge, etc. However, the impact of metal components/composition as well as metal topological distribution within NPs is incompletely characterized and remains to be further elucidated and clarified. In the present work, we tested a series of colloidal solutions of AgAu NPs of alloy and core-shell type for an antitumor activity depending on metal molar ratios (Ag:Au = 1:1; 1:3; 3:1) and topological distribution of gold and silver within NPs (AucoreAgshell; AgcoreAushell). The efficacy at which an administration of the gold and silver NPs inhibits mouse Lewis lung carcinoma (LLC) growth in vivo was compared. The data suggest that in vivo antitumor activity of the studied NPs strongly depends on gold and silver interaction arising from their ordered topological distribution. NPs with Ag core covered by Au shell were the most effective among the NPs tested towards LLC tumor growth and metastasizing inhibition. Our data show that among the NPs tested in this study, AgcoreAushell NPs may serve as a suitable anticancerous prototype.

Coalescence of functional gold and monodisperse silver nanoparticles mediated by black Panax ginseng Meyer root extract

PubMed Central

Wang, Dandan; Markus, Josua; Kim, Yeon-Ju; Wang, Chao; Jiménez Pérez, Zuly Elizabeth; Ahn, Sungeun; Aceituno, Verónica Castro; Mathiyalagan, Ramya; Yang, Deok Chun

2016-01-01

A rapid biological synthesis of multifunctional gold nanoparticle (AuNp) and monodisperse silver nanoparticle (AgNp) was achieved by an aqueous extract of black Panax ginseng Meyer root. The physicochemical transformation into black ginseng (BG) greatly enhanced the pharmacological activities of white ginseng and its minor ginsenoside content. The optimal temperature conditions and kinetics of bioreduction were investigated. Formation of BG-AuNps and BG-AgNps was verified by ultraviolet–visible spectrophotometry at 548 and 412 nm, respectively. The biosynthesized BG-AgNps were spherical and monodisperse with narrow distribution, while BG-AuNps were icosahedral-shaped and moderately polydisperse. Synthesized nanoparticles exhibited long-term stability in buffers of pH 7.0–8.0 and biological media (5% bovine serum albumin) at an ambient temperature and at 37°C. BG-AgNps showed effective antibacterial activity against Escherichia coli and Staphylococcus aureus. BG-AuNps and BG-AgNps demonstrated increased scavenging activity against 2,2-diphenyl-1-picrylhydrazyl free radicals. In addition, BG-AuNps and BG-AgNps were nontoxic to HaCaT and MCF-7 cells; the latter showed no cytotoxicity at concentrations lower than 10 µg/mL. At higher concentrations, BG-AgNps exhibited apparent apoptotic activity in MCF-7 breast cancer cell line through reactive oxygen species generation and nuclear fragmentation. PMID:28008248

Activation product analysis in a mixed sample containing both fission and neutron activation products

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

Morrison, Samuel S.; Clark, Sue B.; Eggemeyer, Tere A.

Activation analysis of gold (Au) is used to estimate neutron fluence resulting from a criticality event; however, such analyses are complicated by simultaneous production of other gamma-emitting fission products. Confidence in neutron fluence estimates can be increased by quantifying additional activation products such as platinum (Pt), tantalum (Ta), and tungsten (W). This work describes a radiochemical separation procedure for the determination of these activation products. Anion exchange chromatography is used to separate anionic forms of these metals in a nitric acid matrix; thiourea is used to isolate the Au and Pt fraction, followed by removal of the Ta fraction usingmore » hydrogen peroxide. W, which is not retained on the first anion exchange column, is transposed to an HCl/HF matrix to enhance retention on a second anion exchange column and finally eluted using HNO3/HF. Chemical separations result in a reduction in the minimum detectable activity by a factor of 287, 207, 141, and 471 for 182Ta, 187W, 197Pt, and 198Au respectively, with greater than 90% recovery for all elements. These results represent the highest recoveries and lowest minimum detectable activities for 182Ta, 187W, 197Pt, and 198Au from mixed fission-activation product samples to date, enabling considerable refinement in the measurement uncertainties for neutron fluences in highly complex sample matrices.« less

Chromogenic Detection of Dipeptidyl Peptidase IV (DPP-IV) Activity using Peptide-Functionalized Gold Nanoparticles

NASA Astrophysics Data System (ADS)

Abul-Huda, Yasin Mohammad

Metal nanoparticles offer a useful platform for a wide range of biological applications especially for biosensing, bioimaging and drug delivery. This thesis presents a body of original research describing the synthesis, characterisation and development of a novel and convenient biosensing assay for detection of dipeptidyl peptidase IV (DPP-IV) enzyme activity using peptide functionalized gold nanoparticles. The distinctive optical and physical properties of gold nanoparticles (Au NP) were harnessed for the development of a colorimetric assay for rapid sensing of DPP-IV activities and screening DPP-IV inhbitors. The citrate reduction method for Au NPs synthesis was optimised and several potential peptide substrates (GPDC, VP-EN-DC, C/G dipeptide, GPG-EN-PEG4-LA, GPDCALNNC) were designed to provide substrates that mimic the DPP-IV natural substrates. The performances of the substrate functionalized Au NPs were assessed for their appropriateness for the detection of the enzyme activity. Addition of DPP-IV to the solutions containing the functionalized Au NPs resulted in cleavage of the substrate and thus causing the aggregation of the Au NPs which in turn led to a shift of the surface plasmon peak toward longer wavelengths, and a change of the colour of the colloidal suspension from red to blue. Overall, real-time detection of DPP-IV activity over a broader range (0-40 U/L) with high selectivity and stability was obtained, thus providing a method that can be used to determine the levels of DPP-IV/CD26 in biological fluids such as serum and plasma. Further assay developments were conducted to overcome limitations encountered with the original Au NP assay, especially the narrow dynamic linear range and stability in high ionic strength solutions. Validation and comparison of the Au NP assay developed has revealed that this method is highly correlated to the gold standard chromogenic Gly-Pro-pNA method for detection of enzyme activity in biological samples. Very good recoveries (in the range 83.6 -114.9%) were obtained in spiked serum samples, which indicate that this assay could provide a suitable alternative for enzyme activity detection with the naked eye and without the need for sophisticated instruments. Investigations into the effects of incorporating different stabilizers in order to improve the stability of the peptide functionalized Au NP in high ionic strength solutions were also investigated. Gold nanoparticles have different shapes and structures and an alternative approach for detection of DPP-IV activity using gold nanorods due to their higher refractive index sensitivities was explored. As a conclusion, three out of five approaches, all utilising Au NP-ligand conjugates were demonstrated useful for the detection of the DPP-IV activity. The system developed here is portable and would permit on-site analysis of samples, which offers a real alternative approach from traditional assays and reduces the need for laboratory testing. The logical next step in this research would be the continuation of experiments to transform this test into a point of care testing device that could offer an early detection tool for disease management.

Thiol ligand-induced transformation of Au38(SC2H4Ph)24 to Au36(SPh-t-Bu)24.

PubMed

Zeng, Chenjie; Liu, Chunyan; Pei, Yong; Jin, Rongchao

2013-07-23

We report a disproportionation mechanism identified in the transformation of rod-like biicosahedral Au38(SCH2CH2Ph)24 to tetrahedral Au36(TBBT)24 nanoclusters. Time-dependent mass spectrometry and optical spectroscopy analyses unambiguously map out the detailed size-conversion pathway. The ligand exchange of Au38(SCH2CH2Ph)24 with bulkier 4-tert-butylbenzenethiol (TBBT) until a certain extent starts to trigger structural distortion of the initial biicosahedral Au38(SCH2CH2Ph)24 structure, leading to the release of two Au atoms and eventually the Au36(TBBT)24 nanocluster with a tetrahedral structure, in which process the number of ligands is interestingly preserved. The other product of the disproportionation process, i.e., Au40(TBBT)m+2(SCH2CH2Ph)24-m, was concurrently observed as an intermediate, which was the result of addition of two Au atoms and two TBBT ligands to Au38(TBBT)m(SCH2CH2Ph)24-m. The reaction kinetics on the Au38(SCH2CH2Ph)24 to Au36(TBBT)24 conversion process was also performed, and the activation energies of the structural distortion and disproportionation steps were estimated to be 76 and 94 kJ/mol, respectively. The optical absorption features of Au36(TBBT)24 are interpreted on the basis of density functional theory simulations.

New comprehensive studies of a gold(III) Dithiocarbamate complex with proven anticancer properties: Aqueous dissolution with cyclodextrins, pharmacokinetics and upstream inhibition of the ubiquitin-proteasome pathway.

PubMed

Tomasello, Marianna F; Nardon, Chiara; Lanza, Valeria; Di Natale, Giuseppe; Pettenuzzo, Nicolò; Salmaso, Stefano; Milardi, Danilo; Caliceti, Paolo; Pappalardo, Giuseppe; Fregona, Dolores

2017-09-29

The gold(III)-dithiocarbamate complex AuL12 (dibromo [ethyl-N-(dithiocarboxy-kS,kS')-N-methylglycinate] gold(III)), is endowed with promising in vitro/in vivo antitumor activity and toxicological profile. Here, we report our recent strategies to improve its water solubility and stability under physiological conditions along with our efforts for unravelling its tangled mechanism of action. We used three types of α-cyclodextrins (CDs), namely β-CD, Me-β-CD and HP-β-CD to prepare aqueous solutions of AuL12. The ability of these natural oligosaccharide carriers to enhance water solubility of hydrophobic compounds, allowed drug stability of AuL12 to be investigated. Moreover, pharmacokinetic experiments were first carried out for a gold(III) coordination compound, after i.v. injection of the nanoformulation AuL12/HP-β-CD to female mice. The gold content in the blood samples was detected at scheduled times by AAS (atomic absorption spectrometry) analysis, highlighting a fast biodistribution with a t β1/2 of few minutes and a slow escretion (t α1/2 of 14.3 h). The in vitro cytotoxic activity of AuL12 was compared with the AuL12/HP-β-CD mixture against a panel of three human tumor cell lines (i.e., HeLa, KB and MCF7). Concerning the mechanism of action, we previously reported the proteasome-inhibitory activity of some our gold(III)-based compounds. In this work, we moved from the proteasome target to upstream of the important ubiquitin-proteasome pathway, testing the effects of AuL12 on the polyubiquitination reactions involving the Ub-activating (E1) and -conjugating (E2) enzymes. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

Electrochemical synthesis of mesoporous Pt-Au binary alloys with tunable compositions for enhancement of electrochemical performance.

PubMed

Yamauchi, Yusuke; Tonegawa, Akihisa; Komatsu, Masaki; Wang, Hongjing; Wang, Liang; Nemoto, Yoshihiro; Suzuki, Norihiro; Kuroda, Kazuyuki

2012-03-21

Mesoporous Pt-Au binary alloys were electrochemically synthesized from lyotropic liquid crystals (LLCs) containing corresponding metal species. Two-dimensional exagonally ordered LLC templates were prepared on conductive substrates from diluted surfactant solutions including water, a nonionic surfactant, ethanol, and metal species by drop-coating. Electrochemical synthesis using such LLC templates enabled the preparation of ordered mesoporous Pt-Au binary alloys without phase segregation. The framework composition in the mesoporous Pt-Au alloy was controlled simply by changing the compositional ratios in the precursor solution. Mesoporous Pt-Au alloys with low Au content exhibited well-ordered 2D hexagonal mesostructures, reflecting those of the original templates. With increasing Au content, however, the mesostructural order gradually decreased, thereby reducing the electrochemically active surface area. Wide-angle X-ray diffraction profiles, X-ray photoelectron spectra, and elemental mapping showed that both Pt and Au were atomically distributed in the frameworks. The electrochemical stability of mesoporous Pt-Au alloys toward methanol oxidation was highly improved relative to that of nonporous Pt and mesoporous Pt films, suggesting that mesoporous Pt-Au alloy films are potentially applicable as electrocatalysts for direct methanol fuel cells. Also, mesoporous Pt-Au alloy electrodes showed a highly sensitive amperometric response for glucose molecules, which will be useful in next-generation enzyme-free glucose sensors.

Solvothermal synthesis of Au@Fe3O4 nanoparticles for antibacterial applications

NASA Astrophysics Data System (ADS)

Kelgenbaeva, Zhazgul; Abdullaeva, Zhypargul; Murzubraimov, Bektemir

2018-04-01

We present Au@Fe3O4 nanoparticles obtained from Fe nanoparticles and HAuCl4 using a simple solvothermal method. Trisodium citrate (C6H5Na3O7*2H2O) served as a reducing agent for Au. X-ray diffraction analysis, electronic microscopes and energy-dispersive X-ray spectroscopy revealed cubic structure, elemental composition (Au, Fe and O) and spherical shape of nanoparticles. Antibacterial activity of the sample was tested against E. coli bacteria and obtained results were discussed.

FAST TRACK COMMUNICATION: Novel mechanism for nanoscale catalysis

NASA Astrophysics Data System (ADS)

Msezane, Alfred Z.; Felfli, Zineb; Sokolovski, Dmitri

2010-10-01

The interplay between Regge resonances and Ramsauer-Townsend minima in the electron elastic total cross sections for Au and Pd atoms along with their large electron affinities is proposed as the fundamental atomic mechanism responsible for the observed exceptional catalytic properties of Au nanoparticles and to explain why the combination Au-Pd possesses an even higher catalytic activity than Au or Pd separately when catalyzing H2O2, consistent with recent experiments. The investigation uses the recent complex angular momentum description of electron scattering from neutral atoms and the proposed mechanism in general.

Toward the Design of a Hierarchical Perovskite Support: Ultra-Sintering-Resistant Gold Nanocatalysts for CO Oxidation

DOE PAGES

Tian, Chengcheng; Zhu, Xiang; Abney, Carter W.; ...

2017-04-12

An ultrastable Au nanocatalyst based on a heterostructured perovskite support with high surface area and uniform LaFeO3 nanocoatings was successfully synthesized and tested for CO oxidation. Strikingly, small Au nanoparticles (4-6 nm) are obtained after calcination in air at 700 °C and under reaction conditions. The designed Au catalyst not only possessed extreme sintering resistance but also showed high catalytic activity and stability because of the strong interfacial interaction between Au and the heterostructured perovskite support.

Cationic gemini surfactant-assisted synthesis of hollow Au nanostructures by stepwise reductions.

PubMed

Wang, Wentao; Han, Yuchun; Tian, Maozhang; Fan, Yaxun; Tang, Yongqiang; Gao, Mingyuan; Wang, Yilin

2013-06-26

A novel synthetic approach was developed for creating versatile hollow Au nanostructures by stepwise reductions of Au(III) upon the use of cationic gemini surfactant hexamethylene-1,6-bis(dodecyl dimethylammonium bromide) (C12C6C12Br2) as a template agent. It was observed that the Au(I) ions obtained from the reduction of Au(III) by ascorbic acid can assist the gemini surfactant to form vesicles, capsule-like, and tube-like aggregates that subsequently act as soft templates for hollow Au nanostructures upon further reduction of Au(I) to Au(0) by NaBH4. It was demonstrated that the combination of C12C6C12Br2 and Au(I) plays a key role in regulating the structure of the hollow precursors not only because C12C6C12Br2 has a stronger aggregation ability in comparison with its single chain counterpart but also because the electrostatic repulsion between head groups of C12C6C12Br2 is greatly weakened after Au(III) is converted to Au(I), which is in favor of the construction of vesicles, capsule-like, and tube-like aggregates. Compared with solid Au nanospheres, the resultant hollow nanostructures exhibit enhanced electrocatalytic activities in methanol oxidation, following the order of elongated nanocapsule > nanocapsule > nanosphere. Benefiting from balanced interactions between the gemini surfactant and Au(I), this soft-template method may present a facile and versatile approach for the controlled synthesis of Au nanostructures potentially useful for fuel cells and other Au nanodevices.

Tailoring oxide properties: An impact on adsorption characteristics of molecules and metals

NASA Astrophysics Data System (ADS)

Honkala, Karoliina

2014-12-01

Both density functional theory calculations and numerous experimental studies demonstrate a variety of unique features in metal supported oxide films and transition metal doped simple oxides, which are markedly different from their unmodified counterparts. This review highlights, from the computational perspective, recent literature on the properties of the above mentioned surfaces and how they adsorb and activate different species, support metal aggregates, and even catalyse reactions. The adsorption of Au atoms and clusters on metal-supported MgO films are reviewed together with the cluster's theoretically predicted ability to activate and dissociate O2 at the Au-MgO(100)/Ag(100) interface, as well as the impact of an interface vacancy to the binding of an Au atom. In contrast to a bulk MgO surface, an Au atom binds strongly on a metal-supported ultra-thin MgO film and becomes negatively charged. Similarly, Au clusters bind strongly on a supported MgO(100) film and are negatively charged favouring 2D planar structures. The adsorption of other metal atoms is briefly considered and compared to that of Au. Existing computational literature of adsorption and reactivity of simple molecules including O2, CO, NO2, and H2O on mainly metal-supported MgO(100) films is discussed. Chemical reactions such as CO oxidation and O2 dissociation are discussed on the bare thin MgO film and on selected Au clusters supported on MgO(100)/metal surfaces. The Au atoms at the perimeter of the cluster are responsible for catalytic activity and calculations predict that they facilitate dissociative adsorption of oxygen even at ambient conditions. The interaction of H2O with a flat and stepped Ag-supported MgO film is summarized and compared to bulk MgO. The computational results highlight spontaneous dissociation on MgO steps. Furthermore, the impact of water coverage on adsorption and dissociation is addressed. The modifications, such as oxygen vacancies and dopants, at the oxide-metal interface and their effect on the adsorption characteristics of water and Au are summarized. Finally, more limited computational literature on transition metal (TM) doped CaO(100) and MgO(100) surfaces is presented. Again, Au is used as a probe species. Similar to metal-supported MgO films, Au binds more strongly than on undoped CaO(100) and becomes negatively charged. The discussion focuses on rationalization of Au adsorption with the help of Born-Haber cycle, which reveals that the so-called redox energy including the electron transfer from the dopant to the Au atom together with the simultaneous structural relaxation of lattice atoms is responsible for enhanced binding. In addition, adsorption energy dependence on the position and type of the dopant is summarized.

Genome-wide analysis of short interspersed nuclear elements SINES revealed high sequence conservation, gene association and retrotranspositional activity in wheat

PubMed Central

Ben-David, Smadar; Yaakov, Beery; Kashkush, Khalil

2013-01-01

Short interspersed nuclear elements (SINEs) are non-autonomous non-LTR retroelements that are present in most eukaryotic species. While SINEs have been intensively investigated in humans and other animal systems, they are poorly studied in plants, especially in wheat (Triticum aestivum). We used quantitative PCR of various wheat species to determine the copy number of a wheat SINE family, termed Au SINE, combined with computer-assisted analyses of the publicly available 454 pyrosequencing database of T. aestivum. In addition, we utilized site-specific PCR on 57 Au SINE insertions, transposon methylation display and transposon display on newly formed wheat polyploids to assess retrotranspositional activity, epigenetic status and genetic rearrangements in Au SINE, respectively. We retrieved 3706 different insertions of Au SINE from the 454 pyrosequencing database of T. aestivum, and found that most of the elements are inserted in A/T-rich regions, while approximately 38% of the insertions are associated with transcribed regions, including known wheat genes. We observed typical retrotransposition of Au SINE in the second generation of a newly formed wheat allohexaploid, and massive hypermethylation in CCGG sites surrounding Au SINE in the third generation. Finally, we observed huge differences in the copy numbers in diploid Triticum and Aegilops species, and a significant increase in the copy numbers in natural wheat polyploids, but no significant increase in the copy number of Au SINE in the first four generations for two of three newly formed allopolyploid species used in this study. Our data indicate that SINEs may play a prominent role in the genomic evolution of wheat through stress-induced activation. PMID:23855320

Genome-wide analysis of short interspersed nuclear elements SINES revealed high sequence conservation, gene association and retrotranspositional activity in wheat.

PubMed

Ben-David, Smadar; Yaakov, Beery; Kashkush, Khalil

2013-10-01

Short interspersed nuclear elements (SINEs) are non-autonomous non-LTR retroelements that are present in most eukaryotic species. While SINEs have been intensively investigated in humans and other animal systems, they are poorly studied in plants, especially in wheat (Triticum aestivum). We used quantitative PCR of various wheat species to determine the copy number of a wheat SINE family, termed Au SINE, combined with computer-assisted analyses of the publicly available 454 pyrosequencing database of T. aestivum. In addition, we utilized site-specific PCR on 57 Au SINE insertions, transposon methylation display and transposon display on newly formed wheat polyploids to assess retrotranspositional activity, epigenetic status and genetic rearrangements in Au SINE, respectively. We retrieved 3706 different insertions of Au SINE from the 454 pyrosequencing database of T. aestivum, and found that most of the elements are inserted in A/T-rich regions, while approximately 38% of the insertions are associated with transcribed regions, including known wheat genes. We observed typical retrotransposition of Au SINE in the second generation of a newly formed wheat allohexaploid, and massive hypermethylation in CCGG sites surrounding Au SINE in the third generation. Finally, we observed huge differences in the copy numbers in diploid Triticum and Aegilops species, and a significant increase in the copy numbers in natural wheat polyploids, but no significant increase in the copy number of Au SINE in the first four generations for two of three newly formed allopolyploid species used in this study. Our data indicate that SINEs may play a prominent role in the genomic evolution of wheat through stress-induced activation. © 2013 Ben-Gurion University The Plant Journal © 2013 John Wiley & Sons Ltd.

Fabrication of novel ternary Au/CeO2@g-C3N4 nanocomposite: kinetics and mechanism investigation of 4-nitrophenol reduction, and benzyl alcohol oxidation

NASA Astrophysics Data System (ADS)

Kohantorabi, Mona; Gholami, Mohammad Reza

2018-06-01

Au nanoparticles supported on cerium oxide/graphitic carbon nitride (CeO2@g-C3N4) was synthesized and used as heterogeneous catalyst in redox reaction. The catalyst was characterized by different techniques such as FT-IR, XRD, FE-SEM, EDS, TEM, BET, TGA, and ICP. The as-prepared ternary nanocomposite was used as an effective catalyst for the reduction of toxic 4-nitrophenol to useful 4-aminophenol by NaBH4. The rate constant value of reduction reaction reached up to 0.106 s-1 by Au/CeO2@g-C3N4, which was 3.8, and 8.8 times higher than that of Au@CeO2 (0.028 s-1), and Au@g-C3N4 (0.012 s-1) nanocomposites, respectively. The superior catalytic performance of as-prepared catalyst in 4-NP reduction can be attributed to synergistic effect between Au nanoparticles and CeO2@g-C3N4 support, and efficient electron transfer. The reduction reaction was carried out at different temperatures, and the energy of activation ({Ea}), and thermodynamic parameters including, activation of entropy (Δ S^ ≠), enthalpy (Δ H^ ≠), and Gibbs free energy (Δ G^ ≠) were determined. Additionally, the mechanism of reaction was studied in details, and equilibrium constants of 4-NP ( K 4-NP), and {BH}4^{ - } ({K_{{BH}4^{{ - }} }}) were calculated using Langmuir-Hinshelwood model. Furthermore, this nanocomposite exhibited excellent catalytic activity in oxidation of benzyl alcohol by molecular oxygen as a green oxidant. This study revealed that the ternary Au/CeO2@g-C3N4 nanocomposite is an attractive candidate for catalytic applications.

Effect of toll-like receptor 3 agonists on the functionality and metastatic properties of breast cancer cell model.

PubMed

Alizadeh, Nastaran; Amiri, Mohammad Mehdi; Salek Moghadam, Alireza; Zarnani, Amir Hassan; Saadat, Farshid; Safavifar, Farnaz; Berahmeh, Azar; Khorramizadeh, Mohammad Reza

2013-05-15

There exists compelling evidence that Toll-like receptor 3 (TLR3) agonists can directly affect human cancer cells. The aim of this study was to investigate anti-cancer effects of TLR3 agonist in human breast cell line. We assessed potential effects of poly (A:U) on human breast cell line (MDA-MB-231) on a dose-response and time-course basis. Human breast cell line MDA-MB-231 was treated with different concentrations of poly (A:U) and lipopolysaccharide (LPS). Then, the following assays were performed on the treated cells: dose-response and time-course cytotoxicity using colorimetric method; matrix metalloproteinase-2 (MMP-2) activity using gelatin zymography method; apoptosis using annexin-v flowcytometry method; and relative expression of TLR3 and MMP-2 mRNA using reverse transcriptase polymerase chain reaction (RT-PCR) method. Following treatments, dose- response and time-course cytotoxicity using a colorimetric method, (MMP-2) activity (using gelatin zymography), apoptosis (using annexin-v flowcytometry method) assays and expression of TLR3 and MMP-2 genes (using PCR method) were performed. Cytotoxicity and flowcytometry analysis of poly (A:U) showed that poly (A:U) do not have any cytotoxic and apoptotic effects in different concentrations used. MMP-2 activity analysis showed significant decrease in higher concentrations (50 and 100 μg/ ml) between treated and untreated cells. Moreover, poly A:U treated cells demonstrated decreased expression of MMP-2 gene in higher concentrations. Collectively, our data indicated that human breast cancer cell line (MDA-MB-231) was highly responsive to poly (A:U). The antimetastatic effect of direct poly (A:U) and TLR3 interactions in MDA-MB-231 cells could provide new approaches in malignant tumor therapeutic strategy.

Desulfurization of Thiophene on Au/TiC(001): Au−C Interactions and Charge Polarization

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

Rodriguez, J.; Liu, P; Takahashi, Y

2009-01-01

Photoemission and first-principles DF calculations were used to study the interaction of thiophene with TiC(001) and Au/TiC(001) surfaces. The adsorption strength of thiophene on TiC(001) is weak, and the molecule desorbs at temperatures below 200 K. The molecule binds to Ti centers of TiC(001) through its sulfur atom with negligible structural perturbations. In spite of the very poor desulfurization performance of TiC(001) or Au(111), a Au/TiC(001) system displays a hydrodesulfurization activity higher than that of conventional Ni/MoS{sub x} catalysts. The Au?TiC(001) interactions induce a polarization of electron density around Au which substantially increases the chemical reactivity of this metal. Aumore » nanoparticles drastically increase the hydrodesulfurization activity of TiC(001) by enhancing the bonding energy of thiophene and by helping in the dissociation of H{sub 2} to produce the hydrogen necessary for the hydrogenolysis of C-S bonds and the removal of sulfur. H{sub 2} spontaneously dissociates on small two-dimensional clusters of gold in contact with TiC(001). On these systems, the adsorption energy of thiophene is 0.45-0.65 eV larger than that on TiC(001) or Au(111). Thiophene binds in a ?5 configuration with a large elongation ({approx}0.2 {angstrom}) of the C-S bonds.« less

Synergetic enhancement of gold nanoparticles and 2-mercaptobenzothiazole as highly-sensitive sensing strategy for tetrabromobisphenol A

NASA Astrophysics Data System (ADS)

Chen, Xuerong; Ji, Liudi; Zhou, Yikai; Wu, Kangbing

2016-05-01

Various gold nanoparticles (AuNPs) were in-situ prepared on the electrode surface through electrochemical reduction under different potentials such as -0.60, -0.50, -0.40, -0.30 and -0.20 V. The reduction potentials heavily affect the surface morphology and electrochemical activity of AuNPs such as effective area and catalytic ability, as confirmed using atomic force microscopy and electrochemical impedance spectroscopy. The electrochemical behaviors of tetrabromobisphenol A (TBBPA), a widely-existed pollutant with severe adverse health effects, were studied. The oxidation activity of TBBPA enhances obviously on the surface of AuNPs, and the signal improvements of TBBPA show difference on the prepared AuNPs. Interestingly, the existence of 2-mercaptobenzothiazole (MBT) further improves the oxidation signals of TBBPA on AuNPs. The synergetic enhancement effects of AuNPs and MBT were studied using cyclic voltammetry and chronocoulometry. The numerous nano-scaled gold particles together with the strong hydrophobic interaction between TBBPA and the assembled MBT on AuNPs jointly provide highly-effective accumulation for TBBPA. As a result, a sensitive and simple electrochemical method was developed for the direct determination of TBBPA, with detection limit of 0.12 μg L-1 (0.22 nM). The practical applications in water samples manifest that this new sensing system is accurate and feasible.

Comparative catalytic reduction of 4-nitrophenol by polyacrylamide-gold nanocomposite synthesized by hydrothermal autoclaving and conventional heating routes

NASA Astrophysics Data System (ADS)

Salaheldin, Hosam I.

2017-12-01

Gold nanoparticles (AuNPs) in polymeric polyacrylamide (PAAm) matrix were synthesized using conventional heating and autoclaving thermal techniques. The synthesized Au/PAAm nanocomposite was characterized using UV-vis spectroscopy and high-resolution transmission electron microscopy. The size of the synthesized particles was approximately 6.37 nm and 8.19 nm with the conventional heating and autoclaving thermal techniques, respectively. Electron diffraction x-ray spectroscopy and the Fourier transformation infrared spectroscopy were used for the composition and elemental studies, which confirmed that the Au metallic atoms were synthesized and embedded within a PAAm matrix via a coordination bond between the carbonyl (-CONH2) group and the metallic NPs. X-ray diffraction confirmed the crystalline nature of the fabricated AuNPs with face centered cubic of nanocrystals. The catalytic activity of the as-prepared Au/PAAm nanocomposite for the reduction of 4-nitrophenol to 4-aminophenol was studied in the presence of sodium borohydrate. The synthesized AuNPs had an effective catalytic activity; the smaller NPs synthesized NPs with the conventional heating technique had a higher reaction kinetic rate in comparation with those synthesized with the autoclaving technique. Therefore, the Au/PAAm nanocomposite can be widely used as an eco-friendly, non-toxic, a fast and cost-effective product to remove versatile organic pollutants such as aromatic nitro compounds.

Gold nanoparticles synthesized by Brassica oleracea (Broccoli) acting as antimicrobial agents against human pathogenic bacteria and fungi

NASA Astrophysics Data System (ADS)

Piruthiviraj, Prakash; Margret, Anita; Krishnamurthy, Poornima Priyadharsani

2016-04-01

Production of antimicrobial agents through the synthesis of gold nanoparticles using green technology has been extensively made consistent by various researchers; yet, this study uses the flower bud's aqueous extracts of Brassica oleracea (Broccoli) as a reducing agent for chloroauric acid (1 mM). After 30 min of incubation, synthesis of gold nanoparticles (AuNps) was observed by a change in extract color from pale yellow to purple color. Synthesis of AuNps was confirmed in UV-visible spectroscopy at the range of approximately 560 nm. The SEM analysis showed the average nanoparticles size of 12-22 nm. The antimicrobial activity of AuNps was analyzed by subjecting it to human pathogenic bacteria (Gram-positive Staphylococcus aureus and Gram-negative Klebsiella pneumonia) and fungi (Aspergillus flavus, Aspergillus niger and Candida albicans) using disc diffusion method. The broccoli-synthesized AuNps showed the efficient antibacterial and antifungal activity of above-mentioned microbes. It was confirmed that AuNps have the best antimicrobial agent compared to the standard antibiotics (Gentamicin and Fluconazole). When the concentrations of AuNps were increased (10, 25, and 50 µg/ml), the sensitivity zone also increased for all the tested microbes. The synthesized AuNps are capable of rendering high antimicrobial efficacy and, hence, have a great potential in the preparation of drugs used against major bacterial and fungal diseases in humans.

Titanium dioxide-gold nanocomposite materials embedded in silicate sol-gel film catalyst for simultaneous photodegradation of hexavalent chromium and methylene blue.

PubMed

Pandikumar, Alagarsamy; Ramaraj, Ramasamy

2012-02-15

Aminosilicate sol-gel supported titanium dioxide-gold (EDAS/(TiO(2)-Au)(nps)) nanocomposite materials were synthesized by simple deposition-precipitation method and characterized. The photocatalytic oxidation and reduction activity of the EDAS/(TiO(2)-Au)(nps) film was evaluated using hexavalent chromium (Cr(VI)) and methylene blue (MB) dye under irradiation. The photocatalytic reduction of Cr(VI) to Cr(III) was studied in the presence of hole scavengers such as oxalic acid (OA) and methylene blue (MB). The photocatalytic degradation of MB was investigated in the presence and absence of Cr(VI). Presence of Au(nps) on the (TiO(2))(nps) surface and its dispersion in the silicate sol-gel film (EDAS/(TiO(2)-Au)(nps)) improved the photocatalytic reduction of Cr(VI) and oxidation of MB due to the effective interfacial electron transfer from the conduction band of the TiO(2) to Au(nps) by minimizing the charge recombination process when compared to the TiO(2) and (TiO(2)-Au)(nps) in the absence of EDAS. The EDAS/(TiO(2)-Au)(nps) nanocomposite materials provided beneficial role in the environmental remediation and purification process through synergistic photocatalytic activity by an advanced oxidation-reduction processes. Copyright © 2011 Elsevier B.V. All rights reserved.

Artificial neural network and particle swarm optimization for removal of methyl orange by gold nanoparticles loaded on activated carbon and Tamarisk.

PubMed

Ghaedi, M; Ghaedi, A M; Ansari, A; Mohammadi, F; Vafaei, A

2014-11-11

The influence of variables, namely initial dye concentration, adsorbent dosage (g), stirrer speed (rpm) and contact time (min) on the removal of methyl orange (MO) by gold nanoparticles loaded on activated carbon (Au-NP-AC) and Tamarisk were investigated using multiple linear regression (MLR) and artificial neural network (ANN) and the variables were optimized by partial swarm optimization (PSO). Comparison of the results achieved using proposed models, showed the ANN model was better than the MLR model for prediction of methyl orange removal using Au-NP-AC and Tamarisk. Using the optimal ANN model the coefficient of determination (R2) for the test data set were 0.958 and 0.989; mean squared error (MSE) values were 0.00082 and 0.0006 for Au-NP-AC and Tamarisk adsorbent, respectively. In this study a novel and green approach were reported for the synthesis of gold nanoparticle and activated carbon by Tamarisk. This material was characterized using different techniques such as SEM, TEM, XRD and BET. The usability of Au-NP-AC and activated carbon (AC) Tamarisk for the methyl orange from aqueous solutions was investigated. The effect of variables such as pH, initial dye concentration, adsorbent dosage (g) and contact time (min) on methyl orange removal were studied. Fitting the experimental equilibrium data to various isotherm models such as Langmuir, Freundlich, Tempkin and Dubinin-Radushkevich models show the suitability and applicability of the Langmuir model. Kinetic models such as pseudo-first order, pseudo-second order, Elovich and intraparticle diffusion models indicate that the second-order equation and intraparticle diffusion models control the kinetic of the adsorption process. The small amount of proposed Au-NP-AC and activated carbon (0.015 g and 0.75 g) is applicable for successful removal of methyl orange (>98%) in short time (20 min for Au-NP-AC and 45 min for Tamarisk-AC) with high adsorption capacity 161 mg g(-1) for Au-NP-AC and 3.84 mg g(-1) for Tamarisk-AC. Copyright © 2014 Elsevier B.V. All rights reserved.

Artificial neural network and particle swarm optimization for removal of methyl orange by gold nanoparticles loaded on activated carbon and Tamarisk

NASA Astrophysics Data System (ADS)

Ghaedi, M.; Ghaedi, A. M.; Ansari, A.; Mohammadi, F.; Vafaei, A.

2014-11-01

The influence of variables, namely initial dye concentration, adsorbent dosage (g), stirrer speed (rpm) and contact time (min) on the removal of methyl orange (MO) by gold nanoparticles loaded on activated carbon (Au-NP-AC) and Tamarisk were investigated using multiple linear regression (MLR) and artificial neural network (ANN) and the variables were optimized by partial swarm optimization (PSO). Comparison of the results achieved using proposed models, showed the ANN model was better than the MLR model for prediction of methyl orange removal using Au-NP-AC and Tamarisk. Using the optimal ANN model the coefficient of determination (R2) for the test data set were 0.958 and 0.989; mean squared error (MSE) values were 0.00082 and 0.0006 for Au-NP-AC and Tamarisk adsorbent, respectively. In this study a novel and green approach were reported for the synthesis of gold nanoparticle and activated carbon by Tamarisk. This material was characterized using different techniques such as SEM, TEM, XRD and BET. The usability of Au-NP-AC and activated carbon (AC) Tamarisk for the methyl orange from aqueous solutions was investigated. The effect of variables such as pH, initial dye concentration, adsorbent dosage (g) and contact time (min) on methyl orange removal were studied. Fitting the experimental equilibrium data to various isotherm models such as Langmuir, Freundlich, Tempkin and Dubinin-Radushkevich models show the suitability and applicability of the Langmuir model. Kinetic models such as pseudo-first order, pseudo-second order, Elovich and intraparticle diffusion models indicate that the second-order equation and intraparticle diffusion models control the kinetic of the adsorption process. The small amount of proposed Au-NP-AC and activated carbon (0.015 g and 0.75 g) is applicable for successful removal of methyl orange (>98%) in short time (20 min for Au-NP-AC and 45 min for Tamarisk-AC) with high adsorption capacity 161 mg g-1 for Au-NP-AC and 3.84 mg g-1 for Tamarisk-AC.

Photothermal enhancement of chemotherapy mediated by gold-silica nanoshell-loaded macrophages: in vitro squamous cell carcinoma study

NASA Astrophysics Data System (ADS)

Madsen, Steen J.; Shih, En-Chung; Peng, Qian; Christie, Catherine; Krasieva, Tatiana; Hirschberg, Henry

2016-01-01

Moderate hyperthermia (MHT) has been shown to enhance the effects of chemotherapeutic agents in a wide variety of cancers. The purpose of this study was to investigate the combined effects of commonly used chemotherapeutic agents with MHT induced by near-infrared (NIR) activation of gold nanoshell (AuNS)-loaded macrophages (Ma). AuNS-loaded murine Ma combined with human FaDu squamous cells, in hybrid monolayers, were subjected to three cytotoxic drugs (doxorubicin, bleomycin, cisplatin) with or without NIR laser irradiation. For all three drugs, efficacy was increased by NIR activation of AuNS-loaded Ma. The results of this in vitro study provide proof-of-concept for the use of AuNS-loaded Ma for photothermal enhancement of the effects of chemotherapy on squamous cell carcinoma.

A label-free fluorescent biosensor for the detection of protein kinase activity based on gold nanoclusters/graphene oxide hybrid materials.

PubMed

Liu, Qing; Li, Ning; Wang, Mengke; Wang, Lei; Su, Xingguang

2018-07-12

Protein kinase (PKA) can regulate many cellular biological processes by phosphorylation substrate peptide or protein. A new fluorescent biosensing method for the detection of PKA activity was developed by using 11-mercaptoundecanoic acid-capped gold nanoclusters (MUA-Au NCs) and graphene oxide (GO) with low background noise. In this strategy, the special designed peptide could be anchored on the surface of MUA-Au NCs by the Au-S bond and also adsorbed on the surface of GO owing to the electrostatic interaction. As a result, the fluorescence of MUA-Au NCs was quenched leading to low background fluorescence due to the forster resonance energy transfer (FRET) between MUA-Au NCs and GO via peptide as a bridge. However, when the substrate peptide was phosphorylated by PKA, the FRET between GO and MUA-Au NCs was disrupted because of the weakened interaction between the phosphorylated peptide and the GO, resulting in recovery of the fluorescence intensity. The developed label-free fluorescence "turn-off-on" method can detect protein kinase activity in the range of 0.6-2.0 U mL -1 with a detection limit of 0.17 U mL -1 (3σ). The feasibility of this present method for kinase inhibitor screening was also studied by assessment of H-89 kinase inhibition with an IC 50 value of 0.049 μmol L -1 . Copyright © 2018. Published by Elsevier B.V.

Biosynthesized gold and silver nanoparticles by aqueous fruit extract of Chaenomeles sinensis and screening of their biomedical activities.

PubMed

Oh, Keun Hyun; Soshnikova, Veronika; Markus, Josua; Kim, Yeon Ju; Lee, Sang Chul; Singh, Priyanka; Castro-Aceituno, Verónica; Ahn, Sungeun; Kim, Dong Hyun; Shim, Yeon Jae; Kim, Yu Jin; Yang, Deok Chun

2018-05-01

The design of mild and non-toxic synthesis of metallic nanoparticles is a topical subject in the nanotechnology field. The objective of this present study is to screen the bioactivity of biosynthesized nanoparticles by aqueous fruit extract of Chaenomeles sinensis. The reducing and stabilizing ability of C. sinensis to fabricate gold (Cs-AuNps) and silver (Cs-AgNps) nanoparticles was confirmed by UV-visible (UV-Vis) spectroscopy at 562 nm and 477 nm, respectively. The field-emission transmission electron microscopy (FE-TEM) and X-ray diffraction analysis (XRD) verify the nano-scale morphology and crystallinity of Cs-AuNps (20-40 nm) and Cs-AgNps (5-20 nm). Furthermore, we evaluated the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical-scavenging capacity, antimicrobial activity against Staphylococcus aureus and Escherichia coli and cytotoxicity against breast cancer cells. The results showed that Cs-AuNps (IC 50 : 725.93 μg/mL) displayed superior inhibitory activities on DPPH than Cs-AuNps. The biosynthesized Cs-AuNps successfully inhibited the growth of pathogenic bacteria S. aureus (ATCC 6538) and E. coli (BL21). The cytotoxic effect of Cs-AuNps and Cs-AgNps was evaluated in murine macrophage (RAW264.7) and human breast cancer cell lines (MCF7) by MTT assay. Thus, the present study explores the biomedical applications of gold and silver nanoparticles synthesized by C. sinensis.

Hyaluronic acid-fabricated nanogold delivery of the inhibitor of apoptosis protein-2 siRNAs inhibits benzo[a]pyrene-induced oncogenic properties of lung cancer A549 cells

NASA Astrophysics Data System (ADS)

Lin, Chung-Ming; Kao, Wei-Chien; Yeh, Chun-An; Chen, Hui-Jye; Lin, Shinn-Zong; Hsieh, Hsien-Hsu; Sun, Wei-Shen; Chang, Chih-Hsuan; Hung, Huey-Shan

2015-03-01

Benzo[a]pyrene (BaP), a component of cooking oil fumes (COF), promotes lung cancer cell proliferation and survival via the induction of inhibitor of apoptosis protein-2 (IAP-2) proteins. Thus knockdown of IAP-2 would be a promising way to battle against lung cancer caused by COF. Functionalized gold nanoparticle (AuNP) is an effective delivery system for bio-active materials. Here, biocompatible hyaluronic acid (HA) was fabricated into nanoparticles to increase the target specificity by binding to CD44-over-expressed cancer cells. IAP-2-specific small-interfering RNA (siRNAs) or fluorescein isothiocyanate (FITC) were then incorporated into AuNP-HA. Conjugation of IAP-2 siRNA into AuNPs-HA was verified by the UV-vis spectrometer and Fourier transform infrared spectrometer. Further studies showed that AuNP-HA/FITC were effectively taken up by A549 cells through CD44-mediated endocytosis. Incubation of BaP-challenged cells with AuNP-HA-IAP-2 siRNAs silenced the expression of IAP-2, decreased cell proliferation and triggered pronounced cell apoptosis by the decrease in Bcl-2 protein and the increase in Bax protein as well as the active form of caspases-3. The BaP-elicited cell migration and enzymatic activity of the secreted matrix metalloproteinase-2 were also substantially suppressed by treatment with AuNP-HA-IAP-2 siRNAs. These results indicated that IAP-2 siRNAs can be efficiently delivered into A549 cells by functionalized AuNP-HA to repress the IAP-2 expression and BaP-induced oncogenic events, suggesting the potential therapeutic application of IAP-2 siRNA or other siRNA-conjugated AuNP-HA composites to COF-induced lung cancer and other gene-caused diseases in the future.

A new bimetallic plasmonic photocatalyst consisting of gold(core)-copper(shell) nanoparticle and titanium(IV) oxide support

NASA Astrophysics Data System (ADS)

Sato, Yuichi; Naya, Shin-ichi; Tada, Hiroaki

2015-10-01

Ultrathin Cu layers (˜2 atomic layers) have been selectively formed on the Au surfaces of Au nanoparticle-loaded rutile TiO2 (Au@Cu/TiO2) by a deposition precipitation-photodeposition technique. Cyclic voltammetry and photochronopotentiometry measurements indicate that the reaction proceeds via the underpotential deposition. The ultrathin Cu shell drastically increases the activity of Au/TiO2 for the selective oxidation of amines to the corresponding aldehydes under visible-light irradiation (λ > 430 nm). Photochronoamperometry measurements strongly suggest that the striking Cu shell effect stems from the enhancement of the charge separation in the localized surface plasmon resonance-excited Au/TiO2.

A rapid green strategy for the synthesis of Au "meatball"-like nanoparticles using green tea for SERS applications

NASA Astrophysics Data System (ADS)

Wu, Shichao; Zhou, Xi; Yang, Xiangrui; Hou, Zhenqing; Shi, Yanfeng; Zhong, Lubin; Jiang, Qian; Zhang, Qiqing

2014-09-01

We report a simple and rapid biological approach to synthesize water-soluble and highly roughened "meatball"-like Au nanoparticles using green tea extract under microwave irradiation. The synthesized Au meatball-like nanoparticles possess excellent monodispersity and uniform size (250 nm in diameter). Raman measurements show that these tea-generated meatball-like gold nanostructures with high active surface areas exhibit a high enhancement of surface-enhanced Raman scattering. In addition, the Au meatball-like nanoparticles demonstrate good biocompatibility and remarkable in vitro stability at the biological temperature. Meanwhile, the factors that influence the Au meatball-like nanoparticles morphology are investigated, and the mechanisms behind the nonspherical shape evolution are discussed.

Primary auditory cortex regulates threat memory specificity.

PubMed

Wigestrand, Mattis B; Schiff, Hillary C; Fyhn, Marianne; LeDoux, Joseph E; Sears, Robert M

2017-01-01

Distinguishing threatening from nonthreatening stimuli is essential for survival and stimulus generalization is a hallmark of anxiety disorders. While auditory threat learning produces long-lasting plasticity in primary auditory cortex (Au1), it is not clear whether such Au1 plasticity regulates memory specificity or generalization. We used muscimol infusions in rats to show that discriminatory threat learning requires Au1 activity specifically during memory acquisition and retrieval, but not during consolidation. Memory specificity was similarly disrupted by infusion of PKMζ inhibitor peptide (ZIP) during memory storage. Our findings show that Au1 is required at critical memory phases and suggest that Au1 plasticity enables stimulus discrimination. © 2016 Wigestrand et al.; Published by Cold Spring Harbor Laboratory Press.

Solid-state dewetting of magnetic binary multilayer thin films

NASA Astrophysics Data System (ADS)

Esterina, Ria; Liu, X. M.; Adeyeye, A. O.; Ross, C. A.; Choi, W. K.

2015-10-01

We examined solid-state dewetting behavior of magnetic multilayer thin film in both miscible (CoPd) and immiscible (CoAu) systems and found that CoPd and CoAu dewetting stages follow that of elemental materials. We established that CoPd alloy morphology and dewetting rate lie in between that of the elemental materials. Johnson-Mehl-Avrami analysis was utilized to extract the dewetting activation energy of CoPd. For CoAu, Au-rich particles and Co-rich particles are distinguishable and we are able to predict the interparticle spacings and particle densities for the particles that agree well with the experimental results. We also characterized the magnetic properties of CoPd and CoAu nanoparticles.

Synthesis and comparative photocatalytic activity of Pt/WO 3 and Au/WO 3 nanocomposites under sunlight-type excitation

NASA Astrophysics Data System (ADS)

Qamar, M.; Yamani, Z. H.; Gondal, M. A.; Alhooshani, K.

2011-09-01

The article deals with the synthesis of highly active visible-light-driven nanocomposite for the decontamination of water hazards under sunlight-type excitation. The surface of visible-light-active nanostructured photocatalyst tungsten oxide (WO 3) was modified with noble metals, such as platinum (Pt) and gold (Au) nanoparticles, and the resulting photocatalytic activity of the nanocomposites was investigated by studying the removal of Methyl Orange and 2,4-Dichlorophenoxyacetic acid (2,4-D) under sunlight-type excitation. The study revealed that the deposited noble metals are not always favorable for the enhancement of photocatalytic response of catalysts; the activity of WO 3 was enhanced manyfold (˜8 times) by depositing an optimum amount of Pt nanoparticles after certain photodeposition time whereas the presence of Au nanoparticles onto the WO 3 surface, under identical experimental conditions, affected the removal process negatively. The variation in the photocatalytic activity of nanocomposites was attributed to the size of the deposited metals; Pt nanoparticles were uniformly dispersed with narrow size distribution (2-4 nm) while the size distribution of Au nanoparticles was found to be 10-15 nm for similar preparation conditions. The effects of critical parameters, such as metal deposition time and metal contents, on the photocatalytic activity of WO 3 were investigated. Furthermore, Pt/WO 3 nanocomposites showed good stability and recyclability under the conditions studied.

Assay of enterocin AS-48 for inhibition of foodborne pathogens in desserts.

PubMed

Martinez Viedma, Pilar; Abriouel, Hikmate; Ben Omar, Nabil; Lucas López, Rosario; Valdivia, Eva; Gálvez, Antonio

2009-08-01

Enterocin AS-48 was tested against Staphylococcus aureus, Bacillus cereus, and Listeria monocytogenes in different kinds of desserts. The highest activity against S. aureus was detected in baker cream. However, in yogurt-type soy-based desserts and in gelatin pudding, AS-48 (175 arbitrary units [AU]/g) reduced viable cell counts of S. aureus by only 1.5 to 1.8 log units at most. The efficacy of AS-48 in puddings greatly depended on inoculum size, and viable S. aureus counts decreased below detection levels within 24 h for inocula lower than 4 to 5.5 log CFU/g. For L. monocytogenes, bacteriocin concentrations of 52.5 to 87.5 AU/g reduced viable counts below detection levels and avoided regrowth of survivors. The lowest activity was detected in yogurt-type desserts. For B. cereus, viable cell counts were reduced below detection levels for bacteriocin concentrations of 52.5 AU/g in instant pudding without soy or by 175 AU/g in the soy pudding. In gelatin pudding, AS-48 (175 AU/g) reduced viable cell counts of B. cereus below detection levels after 8 h at 10 degrees C or after 48 h at 22 degrees C. Bacteriocin addition also inhibited gelatin liquefaction caused by the proteolytic activity of B. cereus.

Immunomodulatory activity of polysaccharides isolated from Clerodendrum splendens: Beneficial effects in experimental autoimmune encephalomyelitis

PubMed Central

2013-01-01

Background Extracts of leaves from Clerodendrum have been used for centuries to treat a variety of medicinal problems in tropical Africa. However, little is known about the high-molecular weight active components conferring therapeutic properties to these extracts. Methods Polysaccharides from the leaves of Clerodendrum splendens were extracted and fractionated by ion exchange and size-exclusion chromatography. Molecular weight determination, sugar analysis, degree of methyl esterification, and other chemical characterization of the fractions were performed. Immunomodulatory activity of the fractions was evaluated by determining their ability to induce monocyte/macrophage nitric oxide (NO), cytokine production, and mitogen-activated protein kinase (MAPK) phosphorylation. Experimental autoimmune encephalomyelitis (EAE) was induced in C57BL/6 mice, and severity of EAE was monitored in mice treated with intraperitoneal (i.p.) injections of the most active polysaccharide fraction. Lymph nodes (LN) and spleen were harvested, and levels of cytokines in supernatants from LN cells and splenocytes challenged with myelin oligodendrocyte glycoprotein peptide were determined. Results Fractions containing type II arabinogalactan had potent immunomodulatory activity. Specifically, the high-molecular weight sub-fraction CSP-AU1 (average of 38.5 kDa) induced NO and cytokine [interleukin (IL)-1α, -1β, -6, -10, tumor necrosis factor (TNF; designated previously as TNF-α), and granulocyte macrophage-colony stimulating factor (GM-CSF)] production by human peripheral blood mononuclear cells (PBMCs) and monocyte/macrophages. CSP-AU1-induced secretion of TNF was prevented by Toll-like receptor 4 (TLR4) antagonist LPS-RS, indicating a role for TLR4 signaling. Treatment with CSP-AU1 also induced phosphorylation of a number of MAPKs in human PBMC and activated AP-1/NF-κB. In vivo treatment of mice with CSP-AU1 and CSP-NU1 resulted in increased serum IL-6, IL-10, TNF, monocyte chemoattractant protein-1 (MCP-1), macrophage inflammatory protein (MIP)-1α/CCL3, and MIP-1β/CCL4. CSP-AU1 treatment of mice with EAE (50 mg/kg, i.p., daily, 13 days) resulted in significantly reduced disease severity in this experimental model of multiple sclerosis. Levels of IL-13, TNF, interferon (IFN)-γ, IL-17, and GM-CSF were also significantly decreased, whereas transforming growth factor (TGF)-β was increased in LN cells from CSP-AU1-treated EAE mice. Conclusions Polysaccharide CSP-AU1 is a potent natural innate immunomodulator with a broad spectrum of agonist activity in vitro and immunosupressive properties after chronic administration in vivo. PMID:23806004

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

Li, Gao; Jiang, Deen; Kumar, Santosh

We here investigate the catalytic properties of water-soluble Aun(SG)m nanocluster catalysts (H-SG = glutathione) of different sizes, including Au15(SG)13, Au18(SG)14, Au25(SG)18, Au38(SG)24, and captopril-capped Au25(Capt)18 nanoclusters. These Aun(SR)m nanoclusters (-SR represents thiolate generally) are used as homogeneous catalysts (i.e., without supports) in the chemoselective hydrogenation of 4-nitrobenzaldehyde (4-NO2PhCHO) to 4-nitrobenzyl alcohol (4-NO2PhCH2OH) in water with H2 gas (20 bar) as the hydrogen source. These nanocluster catalysts, except Au18(SG)14, remain intact after the catalytic reaction, evidenced by UV-vis spectra which are characteristic of each sized nanoclusters and thus serve as spectroscopic fingerprints . We observe a drastic size-dependence and steric effectmore » of protecting ligands on the gold nanocluster catalysts in the hydrogenation reaction. Density functional theory (DFT) modeling of the 4-nitrobenzaldehyde adsorption shows that both the CHO and NO2 groups are in close interact with the S-Au-S staples on the gold nanocluster surface; the adsorption of the 4-nitrobenzaldehyde molecule on the four different sized Aun(SR)m nanoclusters are moderately strong and similar in strength. The DFT results suggest that the catalytic activity of the Aun(SR)m nanoclusters is primarily determined by the surface area of the Au nanocluster, consistent with the observed trend of the conversion of 4-nitrobenzaldehyde versus the cluster size. Overall, this work offers the molecular insight into the hydrogenation of 4-nitrobenzaldehyde and the catalytically active site structure on gold nanocluster catalysts.« less

Electron transfer catalysis with monolayer protected Au25 clusters

NASA Astrophysics Data System (ADS)

Antonello, Sabrina; Hesari, Mahdi; Polo, Federico; Maran, Flavio

2012-08-01

Au25L18 (L = S(CH2)2Ph) clusters were prepared and characterized. The resulting monodisperse clusters were reacted with bis(pentafluorobenzoyl) peroxide in dichloromethane to form Au25L18+ quantitatively. The kinetics and thermodynamics of the corresponding electron transfer (ET) reactions were characterized via electrochemistry and thermochemical calculations. Au25L18+ was used in homogeneous redox catalysis experiments with a series of sym-substituted benzoyl peroxides, including the above peroxide, bis(para-cyanobenzoyl) peroxide, dibenzoyl peroxide, and bis(para-methoxybenzoyl) peroxide. Peroxide dissociative ET was catalyzed using both the Au25L18/Au25L18- and the Au25L18+/Au25L18 redox couples as redox mediators. Simulation of the CV curves led to determination of the ET rate constant (kET) values for concerted dissociative ET to the peroxides. The ET free energy ΔG° could be estimated for all donor-acceptor combinations, leading to observation of a nice activation-driving force (log kETvs. ΔG°) relationship. Comparison with the kET obtained using a ferrocene-type donor with a formal potential similar to that of Au25L18/Au25L18- showed that the presence of the capping monolayer affects the ET rate rather significantly, which is attributed to the intrinsic nonadiabaticity of peroxide acceptors.Au25L18 (L = S(CH2)2Ph) clusters were prepared and characterized. The resulting monodisperse clusters were reacted with bis(pentafluorobenzoyl) peroxide in dichloromethane to form Au25L18+ quantitatively. The kinetics and thermodynamics of the corresponding electron transfer (ET) reactions were characterized via electrochemistry and thermochemical calculations. Au25L18+ was used in homogeneous redox catalysis experiments with a series of sym-substituted benzoyl peroxides, including the above peroxide, bis(para-cyanobenzoyl) peroxide, dibenzoyl peroxide, and bis(para-methoxybenzoyl) peroxide. Peroxide dissociative ET was catalyzed using both the Au25L18/Au25L18- and the Au25L18+/Au25L18 redox couples as redox mediators. Simulation of the CV curves led to determination of the ET rate constant (kET) values for concerted dissociative ET to the peroxides. The ET free energy ΔG° could be estimated for all donor-acceptor combinations, leading to observation of a nice activation-driving force (log kETvs. ΔG°) relationship. Comparison with the kET obtained using a ferrocene-type donor with a formal potential similar to that of Au25L18/Au25L18- showed that the presence of the capping monolayer affects the ET rate rather significantly, which is attributed to the intrinsic nonadiabaticity of peroxide acceptors. This article was submitted as part of a Themed Issue on metallic clusters. Other papers on this topic can be found in issue 14 of vol. 4 (2012). This issue can be found from the Nanoscale homepage [http://www.rsc.org/nanoscale].

Non-centrosymmetric Au-SnO2 hybrid nanostructures with strong localization of plasmonic for enhanced photocatalysis application

NASA Astrophysics Data System (ADS)

Wu, Wei; Liao, Lei; Zhang, Shaofeng; Zhou, Juan; Xiao, Xiangheng; Ren, Feng; Sun, Lingling; Dai, Zhigao; Jiang, Changzhong

2013-05-01

We present an innovative approach to the production of sub-100 nm hollow Au-SnO2 hybrid nanospheres, employing a low-cost, surfactant-free and environmentally friendly solution-based route. The hollow hybrid nanostructures were synthesized using a seed-mediated hydrothermal method, which can be divided into two stages: (1) formation of multicore-shell Au@SnO2 nanoparticles (NPs) and (2) thermal diffusion and ripening to form hollow Au-SnO2 hybrid NPs. The morphology, optical properties and formation mechanism were determined by a collection of joint techniques. Photocatalytic degradation of Rhodamine B (RhB) in the liquid phase served as a probe reaction to evaluate the activity of the as-prepared hollow hybrid Au-SnO2 NPs under the irradiation of both visible light and ultraviolet light. Significantly, the as-obtained Au-SnO2 hybrid nanostructures exhibited enhanced visible light or UV photocatalytic abilities, remarkably superior to commercial pure SnO2 products and P25 TiO2, mainly owing to the effective electron hole separation at the SnO2-Au interfaces and strong localization of plasmonic near-fields effects.We present an innovative approach to the production of sub-100 nm hollow Au-SnO2 hybrid nanospheres, employing a low-cost, surfactant-free and environmentally friendly solution-based route. The hollow hybrid nanostructures were synthesized using a seed-mediated hydrothermal method, which can be divided into two stages: (1) formation of multicore-shell Au@SnO2 nanoparticles (NPs) and (2) thermal diffusion and ripening to form hollow Au-SnO2 hybrid NPs. The morphology, optical properties and formation mechanism were determined by a collection of joint techniques. Photocatalytic degradation of Rhodamine B (RhB) in the liquid phase served as a probe reaction to evaluate the activity of the as-prepared hollow hybrid Au-SnO2 NPs under the irradiation of both visible light and ultraviolet light. Significantly, the as-obtained Au-SnO2 hybrid nanostructures exhibited enhanced visible light or UV photocatalytic abilities, remarkably superior to commercial pure SnO2 products and P25 TiO2, mainly owing to the effective electron hole separation at the SnO2-Au interfaces and strong localization of plasmonic near-fields effects. Electronic supplementary information (ESI) available: The EDX of Au-SnO2 samples (reaction time = 12 h) and plasmonic near-field maps simulated using 3D-FDTD for Au seeds. See DOI: 10.1039/c3nr00985h

Gold nanoclusters-Cu(2+) ensemble-based fluorescence turn-on and real-time assay for acetylcholinesterase activity and inhibitor screening.

PubMed

Sun, Jian; Yang, Xiurong

2015-12-15

Based on the specific binding of Cu(2+) ions to the 11-mercaptoundecanoic acid (11-MUA)-protected AuNCs with intense orange-red emission, we have proposed and constructed a novel fluorescent nanomaterials-metal ions ensemble at a nonfluorescence off-state. Subsequently, an AuNCs@11-MUA-Cu(2+) ensemble-based fluorescent chemosensor, which is amenable to convenient, sensitive, selective, turn-on and real-time assay of acetylcholinesterase (AChE), could be developed by using acetylthiocholine (ATCh) as the substrate. Herein, the sensing ensemble solution exhibits a marvelous fluorescent enhancement in the presence of AChE and ATCh, where AChE hydrolyzes its active substrate ATCh into thiocholine (TCh), and then TCh captures Cu(2+) from the ensemble, accompanied by the conversion from fluorescence off-state to on-state of the AuNCs. The AChE activity could be detected less than 0.05 mU/mL within a good linear range from 0.05 to 2.5 mU/mL. Our proposed fluorescence assay can be utilized to evaluate the AChE activity quantitatively in real biological sample, and furthermore to screen the inhibitor of AChE. As far as we know, the present study has reported the first analytical proposal for sensing AChE activity in real time by using a fluorescent nanomaterials-Cu(2+) ensemble or focusing on the Cu(2+)-triggered fluorescence quenching/recovery. This strategy paves a new avenue for exploring the biosensing applications of fluorescent AuNCs, and presents the prospect of AuNCs@11-MUA-Cu(2+) ensemble as versatile enzyme activity assay platforms by means of other appropriate substrates/analytes. Copyright © 2015 Elsevier B.V. All rights reserved.

Photothermal effects of laser-activated surface plasmonic gold nanoparticles on the apoptosis and osteogenesis of osteoblast-like cells

PubMed Central

Rau, Lih-Rou; Huang, Wan-Yu; Liaw, Jiunn-Woei; Tsai, Shiao-Wen

2016-01-01

The specific properties of gold nanoparticles (AuNPs) make them a novel class of photothermal agents that can induce cancer cell damage and even death through the conversion of optical energy to thermal energy. Most relevant studies have focused on increasing the precision of cell targeting, improving the efficacy of energy transfer, and exploring additional functions. Nevertheless, most cells can uptake nanosized particles through nonspecific endocytosis; therefore, before hyperthermia via AuNPs can be applied for clinical use, it is important to understand the adverse optical–thermal effects of AuNPs on nontargeted cells. However, few studies have investigated the thermal effects induced by pulsed laser-activated AuNPs on nearby healthy cells due to nonspecific treatment. The aim of this study is to evaluate the photothermal effects induced by AuNPs plus a pulsed laser on MG63, an osteoblast-like cell line, specifically examining the effects on cell morphology, viability, death program, and differentiation. The cells were treated with media containing 50 nm AuNPs at a concentration of 5 ppm for 1 hour. Cultured cells were then exposed to irradiation at 60 mW/cm2 and 80 mW/cm2 by a Nd:YAG laser (532 nm wavelength). We observed that the cytoskeletons of MG63 cells treated with bare AuNPs followed by pulsed laser irradiation were damaged, and these cells had few bubbles on the cell membrane compared with those that were not treated (control) or were treated with AuNPs or the laser alone. There were no significant differences between the AuNPs plus laser treatment group and the other groups in terms of cell viability, death program analysis results, or alkaline phosphatase and calcium accumulation during culture for up to 21 days. However, the calcium deposit areas in the cells treated with AuNPs plus laser were larger than those in other groups during the early culture period. PMID:27555768

Photothermal effects of laser-activated surface plasmonic gold nanoparticles on the apoptosis and osteogenesis of osteoblast-like cells.

PubMed

Rau, Lih-Rou; Huang, Wan-Yu; Liaw, Jiunn-Woei; Tsai, Shiao-Wen

2016-01-01

The specific properties of gold nanoparticles (AuNPs) make them a novel class of photothermal agents that can induce cancer cell damage and even death through the conversion of optical energy to thermal energy. Most relevant studies have focused on increasing the precision of cell targeting, improving the efficacy of energy transfer, and exploring additional functions. Nevertheless, most cells can uptake nanosized particles through nonspecific endocytosis; therefore, before hyperthermia via AuNPs can be applied for clinical use, it is important to understand the adverse optical-thermal effects of AuNPs on nontargeted cells. However, few studies have investigated the thermal effects induced by pulsed laser-activated AuNPs on nearby healthy cells due to nonspecific treatment. The aim of this study is to evaluate the photothermal effects induced by AuNPs plus a pulsed laser on MG63, an osteoblast-like cell line, specifically examining the effects on cell morphology, viability, death program, and differentiation. The cells were treated with media containing 50 nm AuNPs at a concentration of 5 ppm for 1 hour. Cultured cells were then exposed to irradiation at 60 mW/cm(2) and 80 mW/cm(2) by a Nd:YAG laser (532 nm wavelength). We observed that the cytoskeletons of MG63 cells treated with bare AuNPs followed by pulsed laser irradiation were damaged, and these cells had few bubbles on the cell membrane compared with those that were not treated (control) or were treated with AuNPs or the laser alone. There were no significant differences between the AuNPs plus laser treatment group and the other groups in terms of cell viability, death program analysis results, or alkaline phosphatase and calcium accumulation during culture for up to 21 days. However, the calcium deposit areas in the cells treated with AuNPs plus laser were larger than those in other groups during the early culture period.

Immunomodulatory and Hemagglutinating Activities of Acidic Polysaccharides Isolated from Combretum racemosum

PubMed Central

Schepetkin, Igor A.; Kouakou, Koffi; Yapi, Ahoua; Kirpotina, Liliya N.; Jutila, Mark A.; Quinn, Mark T.

2013-01-01

Extracts of leaves of different species of the genus Combretum have been used historically to treat a variety of medicinal problems. However, little is known about the active components conferring therapeutic properties to these extracts. In the present studies, we evaluated biochemical properties and immunomodulatory activity of polysaccharides isolated from the leaves of Combretum racemosum. Water-soluble polysaccharides from leaves of C. racemosum were extracted and fractionated by DEAE-cellulose and Diaion HP-20 to obtain a Diaion-bound fraction, designated Combretum polysaccharide-acidic bound or CP-AB, which was eluted with methanol, and an unbound fraction, designated as CP-AU. Molecular weight determination, sugar analysis, and other physical and chemical characterization of the fractions were performed. Fraction CP-AU (mol. weight 5.0 kDa) contained type II arabinogalactan and had potent immunomodulatory activity, inducing the production of interleukin (IL)-1β, -6, -10, and tumor necrosis factor-α (TNF-α) by human peripheral blood mononuclear cells (PBMC) and MonoMac-6 monocytic cells. Likewise, intraperitoneal administration of CP-AU increased in vivo serum levels of IL-6 and monocyte chemoattractant protein-1 (MCP-1) in mice. CP-AU-induced secretion of TNF-α in PBMC was prevented by Toll-like receptor 4 (TLR4) antagonist LPS-RS. Treatment with CP-AU induced phosphorylation of Akt2, Akt3, GSK-3β, HSP27, mTOR, and all p38 MAPK isoforms (α, β, δ, and γ), as well as stimulation of AP-1/NF-κB transcriptional activity. In addition, CP-AU effectively agglutinated erythrocytes from several species, including human, mouse, and rabbit. In contrast, fraction CP-AB was inactive in all biological tests, including cytokine production and hemagglutination. These data suggest that at least part of the beneficial therapeutic effects reported for the water extracts of leaves from C. racemosum are due to modulation of leukocyte functions. PMID:23380150

Protein Viability on Au Nanoparticles during an Electrospray and Electrostatic-Force-Directed Assembly Process

DOE PAGES

Mao, Shun; Lu, Ganhua; Yu, Kehan; ...

2010-01-01

We study the protein viability on Au nanoparticles during an electrospray and electrostatic-force-directed assembly process, through which Au nanoparticle-antibody conjugates are assembled onto the surface of carbon nanotubes (CNTs) to fabricate carbon nanotube field-effect transistor (CNTFET) biosensors. Enzyme-linked immunosorbent assay (ELISA) and field-effect transistor (FET) measurements have been used to investigate the antibody activity after the nanoparticle assembly. Upon the introduction of matching antigens, the colored reaction from the ELISA and the change in the electrical characteristic of the CNTFET device confirm that the antibody activity is preserved during the assembly process.

Radio frequency-mediated local thermotherapy for destruction of pancreatic tumors using Ni-Au core-shell nanowires

NASA Astrophysics Data System (ADS)

Hopkins, Xiaoping; Gill, Waqas Amin; Kringel, Rosemarie; Wang, Guankui; Hass, Jamie; Acharya, Suresh; Park, Jungrae; Tak Jeon, In; An, Boo Hyun; Lee, Ji Sung; Ryu, Jong Eun; Hill, Rod; McIlroy, David; Kim, Young Keun; Choi, Daniel S.

2017-01-01

We present a novel method of radio frequency (RF)-mediated thermotherapy in tumors by remotely heating nickel (Ni)-gold (Au) core-shell nanowires (CSNWs). Ectopic pancreatic tumors were developed in nude mice to evaluate the thermotherapeutic effects on tumor progression. Tumor ablation was produced by RF-mediated thermotherapy via activation of the paramagnetic properties of the Ni-Au CSNWs. Histopathology demonstrated that heat generated by RF irradiation caused significant cellular death with pyknotic nuclei and nuclear fragmentation dispersed throughout the tumors. These preliminary results suggest that thermotherapy ablation induced via RF activation of nanowires provides a potential alternative therapy for cancer treatment.

Determination of the activity of telomerase in cancer cells by using BSA-protected gold nanoclusters as a fluorescent probe.

PubMed

Xu, Yujuan; Zhang, Peng; Wang, Zhen; Lv, Shaoping; Ding, Caifeng

2018-02-27

Gold nanoclusters (AuNCs) protected with a bovine serum albumin (BSA) coating are known to emit red fluorescence (peaking at 650 nm) on photoexcitation with ultraviolet light (365 nm). On addition of Cu(II) ions, fluorescence is quenched because Cu(II) complexes certain amino acid units in the BSA chain. Fluorescence is, however, restored if pyrophosphate (PPi) is added because it will chelate Cu(II) and remove it from the BSA coating on the AuNCs. Because PPi is involved in the function of telomerase, the BSA@AuNCs loaded with Cu(II) can act as a fluorescent probe for determination of the activity of telomerase. A fluorescent assay was worked out for telomerase that is highly sensitive and has a wide linear range (10 nU to 10 fM per mL). The fluorescent probe was applied to the determination of telomerase activity in cervix carcinoma cells via imaging. It is shown that tumor cells can be well distinguished from normal cells by monitoring the differences in intracellular telomerase activity. Graphical abstract Gold nanoclusters (AuNCs) protected by bovine serum albumin (BSA) and displaying red photoluminescence were prepared as fluorescent probe for the determination of telomerase activity and used for imaging of cervix carcinoma (HeLa) cells.

Sodium citrate assisted facile synthesis of AuPd alloy networks for ethanol electrooxidation with high activity and durability

NASA Astrophysics Data System (ADS)

Zhai, Yanling; Zhu, Zhijun; Lu, Xiaolin; Zhou, H. Susan

2016-10-01

The direct ethanol fuel cell is an emerging energy conversion device for which palladium is considered as the one of the most effective components for anode catalyst, however, its widespread application has been still limited by the activity and durability of the anode catalyst. In this work, AuPd alloy networks (NWs) are synthesized using H2PdCl4 and HAuCl4 as precursors reduced by NaBH4 in the presence of sodium citrate (SC). The results reveal that SC plays significant role in network structure, resulting in the enhanced electrocatalytic activity of the catalyst. This self-supported AuPd NWs catalyst exhibits much higher electrochemical catalytic activity than commercial Pd/C catalyst toward ethanol electrooxidation in alkaline solution. Significantly, AuPd NWs catalyst shows extremely high durability at the beginning of the chronoamperometry test, and as high as 49% of the mass current density (1.41 A/mgPd) remains after 4000 s current-time test at -0.3 V (vs. Ag/AgCl) in N2-saturated KOH-ethanol solution. This strategy provides a facile method for the preparation of alloy networks with high electrochemical activity, and can be potentially expanded to a variety of electrochemical applications.

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

NASA Astrophysics Data System (ADS)

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

2013-02-01

Curcumin ((1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione) is an active component of turmeric; it is responsible for its characteristic yellow color and therapeutic potential, but its poor bioavailability remains a major challenge. In order to improve the bioavailability of curcumin, various approaches have been used. One of the possible approaches to increase the bioavailability of curcumin is its conjugation on the surface of metal nanoparticles. Therefore, in the present study, we report the binding of curcumin on the surface of gold nanoparticles (AuNPs). The AuNPs were synthesized by the direct reduction of HAuCl4 using curcumin in the aqueous phase, without the use of any other reducing agents. We found that curcumin acts both as a reducing and capping agent, stabilizing the gold sol for many months. Moreover, these curcumin-capped AuNPs also show good antioxidant activity which was confirmed by the DPPH (2,2-diphenyl-l-picrylhydrazyl) radical test. Thus, the surface functionalization of AuNPs with curcumin may pave a new way of using the curcuminoids towards possible drug delivery and therapeutics. Apart from the experimental study, a detailed quantum chemical calculation using density functional theory (DFT) has been performed, in order to investigate the formation of a complex of curcumin with Au3+ ions in different possible conformational isomeric forms. Our theoretical calculations indicate the evidence of electron transfer from curcumin into the Au center and essentially indicate that as a consequence of complexation, Au3+ ions are reduced to Au0. Our theoretical results also propose that it is the breakage of intramolecular H-bonding that probably leads to the increased availability of curcumin in the presence of gold ions and water molecules.Curcumin ((1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione) is an active component of turmeric; it is responsible for its characteristic yellow color and therapeutic potential, but its poor bioavailability remains a major challenge. In order to improve the bioavailability of curcumin, various approaches have been used. One of the possible approaches to increase the bioavailability of curcumin is its conjugation on the surface of metal nanoparticles. Therefore, in the present study, we report the binding of curcumin on the surface of gold nanoparticles (AuNPs). The AuNPs were synthesized by the direct reduction of HAuCl4 using curcumin in the aqueous phase, without the use of any other reducing agents. We found that curcumin acts both as a reducing and capping agent, stabilizing the gold sol for many months. Moreover, these curcumin-capped AuNPs also show good antioxidant activity which was confirmed by the DPPH (2,2-diphenyl-l-picrylhydrazyl) radical test. Thus, the surface functionalization of AuNPs with curcumin may pave a new way of using the curcuminoids towards possible drug delivery and therapeutics. Apart from the experimental study, a detailed quantum chemical calculation using density functional theory (DFT) has been performed, in order to investigate the formation of a complex of curcumin with Au3+ ions in different possible conformational isomeric forms. Our theoretical calculations indicate the evidence of electron transfer from curcumin into the Au center and essentially indicate that as a consequence of complexation, Au3+ ions are reduced to Au0. Our theoretical results also propose that it is the breakage of intramolecular H-bonding that probably leads to the increased availability of curcumin in the presence of gold ions and water molecules. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr33776b

Synthesis of Gold Nanoparticles Using Garcinia Indica Fruit Rind Extract

NASA Astrophysics Data System (ADS)

Krishnaprabha, M.; Pattabi, Manjunatha

2016-10-01

This report presents the easily reproducible biosynthesis of gold nanoparticles (AuNPs) at room temperature with extract prepared using three year old dried Garcinia Indica (GI) fruit rind. Due to the presence of two major bioactive compounds garcinol and hydroxy citric acid, rinds of GI fruit exhibit anti-cancer and anti-obesity properties. The quantity of fruit rind extract directed the morphology of the as synthesized particles. The nucleation and growth of AuNPs and catalytic activity are studied using UV-Vis spectroscopy. The crystalline nature of biosynthesized AuNPs is corroborated by X-ray Diffraction techniques. The morphology is studied using field emission scanning electron microscopy (FESEM). Fourier transform infra-red (FTIR) spectroscopy analysis revealed that biomolecules were involved in the synthesis and capping of AuNPs. As the Fermi potential of noble metal NPs becomes more negative, they are used in various electron transfer processes. The AuNPs produced using GI extract showed excellent catalytic activity when used as a catalyst in the reduction of well-known toxic pollutant 4-Nitrophenol (4-NP) to 4-Aminophenol (4-AP) in the presence of excess sodium borohydride.

Two-dimensional ZnO ultrathin nanosheets decorated with Au nanoparticles for effective photocatalysis

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

Hu, Jin; You, Ning; Yu, Zhe

Two-dimensional (2D) materials, especially the inorganic 2D nanosheets (NSs), are of particular interest due to their unique structural and electronic properties, which are favorable for photoelectronic applications such as photocatalysis. Here, we design and fabricate the ultrathin 2D ZnO NSs decorated with Au nanoparticles (AuNPs), though molecular modelling 2D hydrothermal growth and followed by surface modification are used as an effective photocatalyst for photocatalytic organic dye degradation and hydrogen production. The ultrathin 2D nature enables ultrahigh atom ratio near surface to proliferate the active sites, and the Au plasmon plays a promoting role in the visible-light absorption and photogenerated chargemore » separation, thus integrating the synergistic benefits to boost the redox reactions at catalyst/electrolyte interface. The AuNPs-decorated ZnO NSs yield the impressive photocatalytic activities such as the dye degradation rate constant of 7.69 × 10{sup −2} min{sup −1} and the hydrogen production rate of 350 μmol h{sup −1} g{sup −1}.« less

Fast and simple microwave synthesis of TiO2/Au nanoparticles for gas-phase photocatalytic hydrogen generation

NASA Astrophysics Data System (ADS)

May-Masnou, Anna; Soler, Lluís; Torras, Miquel; Salles, Pol; Llorca, Jordi; Roig, Anna

2018-04-01

The fabrication of small anatase titanium dioxide (TiO2) nanoparticles (NPs) attached to larger anisotropic gold (Au) morphologies by a very fast and simple two-step microwave-assisted synthesis is presented. The TiO2/Au NPs are synthesized using polyvinylpyrrolidone (PVP) as reducing, capping and stabilizing agent through a polyol approach. To optimize the contact between the titania and the gold and facilitate electron transfer, the PVP is removed by calcination at mild temperatures. The nanocatalysts activity is then evaluated in the photocatalytic production of hydrogen from water/ethanol mixtures in gas-phase at ambient temperature. A maximum value of 5.3 mmol·gcat-1·h-1 (7.4 mmol·gTiO2-1·h-1) of hydrogen is recorded for the system with larger gold particles at an optimum calcination temperature of 450 °C. Herein we demonstrate that TiO2-based photocatalysts with high Au loading and large Au particle size (≈ 50 nm) NPs have photocatalytic activity.

Effect of Phenolic Compounds on the Synthesis of Gold Nanoparticles and Its Catalytic Activity in the Reduction of Nitro Compounds

PubMed Central

Mendes, Marta; Pombeiro, Armando J. L.

2018-01-01

Gold nanoparticles (AuNPs) were prepared using an eco-friendly approach in a single step by reduction of HAuCl4 with polyphenols from tea extracts, which act as both reducing and capping agents. The obtained AuNPs were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet–visible spectroscopy (UV–vis), and X-ray photoelectron spectroscopy (XPS). They act as highly efficient catalysts in the reduction of various aromatic nitro compounds in aqueous solution. The effects of a variety of factors (e.g., reaction time, type and amount of reducing agent, shape, size, or amount of AuNPs) were studied towards the optimization of the processes. The total polyphenol content (TPC) was determined before and after the catalytic reaction and the results are discussed in terms of the tea extract percentage, the size of the AuNPs, and their catalytic activity. The reusability of the AuNP catalyst in the reduction of 4-nitrophenol was also tested. The reactions follow pseudo first-order kinetics. PMID:29748502

Effect of Phenolic Compounds on the Synthesis of Gold Nanoparticles and its Catalytic Activity in the Reduction of Nitro Compounds.

PubMed

Alegria, Elisabete C B A; Ribeiro, Ana P C; Mendes, Marta; Ferraria, Ana M; do Rego, Ana M Botelho; Pombeiro, Armando J L

2018-05-10

Gold nanoparticles (AuNPs) were prepared using an eco-friendly approach in a single step by reduction of HAuCl₄ with polyphenols from tea extracts, which act as both reducing and capping agents. The obtained AuNPs were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet⁻visible spectroscopy (UV⁻vis), and X-ray photoelectron spectroscopy (XPS). They act as highly efficient catalysts in the reduction of various aromatic nitro compounds in aqueous solution. The effects of a variety of factors (e.g., reaction time, type and amount of reducing agent, shape, size, or amount of AuNPs) were studied towards the optimization of the processes. The total polyphenol content (TPC) was determined before and after the catalytic reaction and the results are discussed in terms of the tea extract percentage, the size of the AuNPs, and their catalytic activity. The reusability of the AuNP catalyst in the reduction of 4-nitrophenol was also tested. The reactions follow pseudo first-order kinetics.

Comparative cytotoxicity of gold-doxorubicin and InP-doxorubicin conjugates.

PubMed

Zhang, Xuan; Chibli, Hicham; Kong, Dekun; Nadeau, Jay

2012-07-11

Direct comparisons of different types of nanoparticles for drug delivery have seldom been performed. In this study we compare the physical properties and cellular activity of doxorubicin (Dox) conjugates to gold nanoparticles (Au) and InP quantum dots of comparable diameter. Although the Au particles alone are non-toxic and InP is moderately toxic, Au-Dox is more effective than InP-Dox against the Dox-resistant B16 melanoma cell line. Light exposure does not augment the efficacy of InP-Dox, suggesting that conjugates are breaking down. Electron and confocal microscopy and atomic absorption spectroscopy reveal that over 60% of the Au-Dox conjugates reach the cell nucleus. In contrast, InP-Dox enters cell nuclei to a very limited extent, although liberated Dox from the conjugates does eventually reach the nucleus. These observations are attributed to faster Dox release from Au conjugates under endosomal conditions, greater aggregation of InP-Dox with cytoplasmic proteins, and adherence of InP to membranes. These findings have important implications for design of active drug-nanoparticle conjugates.

Depth profile of production yields of natPb(p, xn) 206,205,204,203,202,201Bi nuclear reactions

NASA Astrophysics Data System (ADS)

Mokhtari Oranj, Leila; Jung, Nam-Suk; Kim, Dong-Hyun; Lee, Arim; Bae, Oryun; Lee, Hee-Seock

2016-11-01

Experimental and simulation studies on the depth profiles of production yields of natPb(p, xn) 206,205,204,203,202,201Bi nuclear reactions were carried out. Irradiation experiments were performed at the high-intensity proton linac facility (KOMAC) in Korea. The targets, irradiated by 100-MeV protons, were arranged in a stack consisting of natural Pb, Al, Au foils and Pb plates. The proton beam intensity was determined by activation analysis method using 27Al(p, 3p1n)24Na, 197Au(p, p1n)196Au, and 197Au(p, p3n)194Au monitor reactions and also by Gafchromic film dosimetry method. The yields of produced radio-nuclei in the natPb activation foils and monitor foils were measured by HPGe spectroscopy system. Monte Carlo simulations were performed by FLUKA, PHITS/DCHAIN-SP, and MCNPX/FISPACT codes and the calculated data were compared with the experimental results. A satisfactory agreement was observed between the present experimental data and the simulations.

A rational design approach to nanostructured catalysts for the oxidation of carbon monoxide

NASA Astrophysics Data System (ADS)

Karwacki, Christopher

The extraordinary energetic properties of subnanometer (<10 nm) structures consisting of reduced metals, metal oxides, and graphitic carbons are emerging as the principal technologies involving catalytic reactions at ambient temperatures, for such applications as respiratory protection, pollution abatement, chemical synthesis, sensors, and energy conversion. Gold nanoparticles (Au NP) possess unique reactive properties not present in the bulk state and have served in the past decade as a model for the nanosciences, where molecular species are synthesized, scaled, and engineered into functional materials. Gold nanoparticles as isolated structures are not useful as real catalysts and must co-exist with supports that provide enhanced stability and activity. Support oxides such as TiO2, Fe2O 3, CeO2, SiO2, Al2O3, ZrO 2, and graphitic (active) carbons have been shown to increase the active nature of AuNP and have been the subject of several thousand publications in the past decade. Zirconia compared to titania as a support for Au NP catalysis has been studied with limited success. In fact, the majority of observations show that zirconia is one of the lowest performing metal oxide supports involving Au NP oxidation catalysis. The likely reason for these observations is a lack of understanding of the relationship between structure and surface functionality as it pertains to ambient temperature oxidation catalysis (ATOC). Furthermore, virtually all substrate and catalyst preparations in earlier work were performed at high temperatures, typically 400--900°C, thus forming progressively monomorphic structures containing larger crystals with reduced surface functionality and porosity. In this research, I established the hypothesis based on a structural model that surface functional hydroxides are important to sustained hydrolytic reactions, such as those involving Au NP for the oxidation of CO to CO 2. Theoretical calculations by Ignatchenko, Vittadini, et al. show that zirconia readily dissociates adsorbed water on the most active and stable crystal structures (111) compared to other metal oxides, such as the common anatase (101) form of titania. Also, the support must provide a source of activated oxygen as a means to oxidize intermediate carbonates with CO 2 formation. The role of the support is to provide lattice oxygen in an activated state (O2-) for oxidation of adsorbed CO the Au NP:support interface. Furthermore, the primary interest is the energy associated Au NP in proximity to the support surface. Advancing the understanding of this region is believed to be crucial to the future design of active nanostructured materials that function under ambient conditions. The proposed model involves a structure consisting of properly sized and highly dispersed Au NP supported on a hydroxylated form of nanocrystalline zirconia. This type of zirconia is in a highly polymorphic form consisting of aggregates of small crystals less than 10 nm. The structure is highly porous, containing undercoordinated zirconium atoms, and provides an environment for rapid dissociation of molecular water. In this research and in collaboration with Mogilevsky et al., 37 I introduce a novel method for quantifying the surface concentration of two major forms of hydroxide that form on zirconia. Furthermore, in this research I show how both the porosity of the zirconia support and the size of the crystalline aggregates affect the type and surface concentration of hydroxyl groups. This relationship is thus directly related to the oxidation activity of the catalyst consisting of Au NP supported on hydroxylated ZrO 2. These phenomena are exemplified by a reduction in structural porosity and surface hydroxyl groups with increasing temperature treatments of the zirconia support. Gold NP and ZrO2 supports were extended to studies that included interactions with activated carbons. This work was done on the premise that graphitic carbons, based on their tunable porosities and surface chemistries, can enhance or stabilize the catalytic activity of neighboring Au NP. Gold dispersed on active carbon and hybrid structures consisting of Au/ZrO 2/C shows interesting properties, which lend themselves to catalytic particle stabilization and to the advancement of multifunctional material design.

Formation of Au nano-patterns on various substrates using simplified nano-transfer printing method

NASA Astrophysics Data System (ADS)

Kim, Jong-Woo; Yang, Ki-Yeon; Hong, Sung-Hoon; Lee, Heon

2008-06-01

For future device applications, fabrication of the metal nano-patterns on various substrates, such as Si wafer, non-planar glass lens and flexible plastic films become important. Among various nano-patterning technologies, nano-transfer print method is one of the simplest techniques to fabricate metal nano-patterns. In nano-transfer printing process, thin Au layer is deposited on flexible PDMS mold, containing surface protrusion patterns, and the Au layer is transferred from PDMS mold to various substrates due to the difference of bonding strength of Au layer to PDMS mold and to the substrate. For effective transfer of Au layer, self-assembled monolayer, which has strong bonding to Au, is deposited on the substrate as a glue layer. In this study, complicated SAM layer coating process was replaced to simple UV/ozone treatment, which can activates the surface and form the -OH radicals. Using simple UV/ozone treatments on both Au and substrate, Au nano-pattern can be successfully transferred to as large as 6 in. diameter Si wafer, without SAM coating process. High fidelity transfer of Au nano-patterns to non-planar glass lens and flexible PET film was also demonstrated.

Gold nanoparticle should understand protein corona for being a clinical nanomaterial.

PubMed

Charbgoo, Fahimeh; Nejabat, Mojgan; Abnous, Khalil; Soltani, Fatemeh; Taghdisi, Seyed Mohammad; Alibolandi, Mona; Thomas Shier, W; Steele, Terry W J; Ramezani, Mohammad

2018-02-28

Gold nanoparticles (AuNPs) have attracted great attention in biomedical fields due to their unique properties. However, there are few reports on clinical trial of these nanoparticles. In vivo, AuNPs face complex biological fluids containing abundant proteins, which challenge the prediction of their fate that is known as "bio-identity". These proteins attach onto the AuNPs surface forming protein corona that makes the first step of nano-bio interface and dictates the subsequent AuNPs fate. Protein corona formation even stealth active targeting effect of AuNPs. Manipulating the protein corona identity based on the researcher goal is the way to employ corona to achieve maximum effect in therapy or other applications. In this review, we provide details on the biological identity of AuNPs under various environmental- and/or physiological conditions. We also highlight how the particular corona can direct the biodistribution of AuNPs. We further discuss the strategies available for controlling or reducing corona formation on AuNPs surface and achieving desired effects using AuNPs in vivo by engineering protein corona on their surface. Copyright © 2018 Elsevier B.V. All rights reserved.

Electrochemical DNA sensor for Neisseria meningitidis detection.

PubMed

Patel, Manoj K; Solanki, Pratima R; Kumar, Ashok; Khare, Shashi; Gupta, Sunil; Malhotra, Bansi D

2010-08-15

Meningitis sensor based on nucleic acid probe of Neisseria meningitidis has been fabricated by immobilization of 5'-thiol end labeled single stranded deoxyribonucleic acid probe (ssDNA-SH) onto gold (Au) coated glass electrode. This ssDNA-SH/Au electrode hybridized with the genomic DNA (G-dsDNA/Au) and amplified DNA (PCR-dsDNA/Au) has been characterized using atomic force microscopy (AFM), Fourier transforms infrared spectroscopy (FT-IR) and electrochemical techniques. The ssDNA-SH/Au electrode can specifically detect upto 10-60 ng/microl of G-dsDNA-SH/Au and PCR-dsDNA-SH/Au of meningitis within 60s of hybridization time at 25 degrees C by cyclic voltammetry (CV) using methylene blue (MB) as electro-active DNA hybridization indicator. The values of sensitivities of the G-dsDNA-SH/Au and PCR-dsDNA-SH/Au electrodes have been determined as 0.0115 microA/ng cm(-2) and 0.0056 microA/ng cm(-2), respectively with regression coefficient (R) as 0.999. This DNA bioelectrode is stable for about 4 months when stored at 4 degrees C. Copyright 2010 Elsevier B.V. All rights reserved.

Ultra-fast catalytic reduction of dyes by ionic liquid recoverable and reusable mefenamic acid derived gold nanoparticles.

PubMed

Hassan, Syeda Sara; Sirajuddin; Solangi, Amber Rehana; Agheem, Mohammad Hassan; Junejo, Yasmeen; Kalwar, Nazar Hussain; Tagar, Zulfiqar Ali

2011-06-15

We synthesized mefenamic acid (MA) derived gold nanoparticles (MA-AuNps) in aqueous solution (MA-Au sol). Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) of the sol at 1, 5, 15 and 60 min showed changes in size and shape of formed AuNps. Fourier Transform Infrared (FTIR) Spectroscopy revealed the interaction between AuNps and MA. Each Au sol exhibited exceptional catalytic activity for the reduction of Methylene Blue (MB), Rose Bengal (RB) and Eosin B (EB) dye individually as well as collectively. However, complete reduction of dye(s) was accomplished by Au sol of 5 min in just 15s. The catalytic performance of Ma-Au sol was far superior to that adsorbed on glass. AuNps were recovered with the help of water insoluble room temperature ionic liquid and reused with enhanced catalytic potential. This finding is a novel, rapid and highly economical alternative for environmental safety against pollution by dyes and extendable for control of other reducible contaminants as well. Copyright © 2011 Elsevier B.V. All rights reserved.

Highly selective and sensitive method for Cu2+ detection based on chiroptical activity of L-Cysteine mediated Au nanorod assemblies.

PubMed

Abbasi, Shahryar; Khani, Hamzeh

2017-11-05

Herein, we demonstrated a simple and efficient method to detect Cu 2+ based on amplified optical activity in the chiral nanoassemblies of gold nanorods (Au NRs). L-Cysteine can induce side-by-side or end-to-end assembly of Au NRs with an evident plasmonic circular dichroism (PCD) response due to coupling between surface plasmon resonances (SPR) of Au NRs and the chiral signal of L-Cys. Because of the obvious stronger plasmonic circular dichrosim (CD) response of the side-by-side assembly compared with the end-to-end assemblies, SS assembled Au NRs was selected as a sensitive platform and used for Cu 2+ detection. In the presence of Cu 2+ , Cu 2+ can catalyze O 2 oxidation of cysteine to cystine. With an increase in Cu 2+ concentration, the L-Cysteine-mediated assembly of Au NRs decreased because of decrease in the free cysteine thiol groups, and the PCD signal decreased. Taking advantage of this method, Cu 2+ could be detected in the concentration range of 20pM-5nM. Under optimal conditions, the calculated detection limit was found to be 7pM. Copyright © 2017 Elsevier B.V. All rights reserved.

Study on surface-enhanced Raman scattering efficiency of Ag core-Au shell bimetallic nanoparticles

NASA Astrophysics Data System (ADS)

Dong, Xiao; Gu, Huaimin; Kang, Jian; Yuan, Xiaojuan

2009-08-01

In this article, the relationship between the states of Ag core-Au shell (core-shell) nanoparticles (NP) and the intensity of Raman scattering of analytes dissolved in the water and adsorbed on the NP was studied. The core-shell NP were synthesised by coating Au layers over Ag seeds by the method of "seed-growth". To highlight the advantage of the core-shell NP, Ag colloid and Au colloid were chosen for contrasting. The analyte that were chosen for this testing were methylene blue (MB) for the reason that MB has very strong signal in surface-enhanced Raman scattering (SERS). The SERS activity of optimalizing states of Ag and Au colloids were compared with that of core-shell NP when MB was used as analyte. In this study, sodium chloride, sodium sulfate and sodium nitrate were used as aggregating agents for Ag, Au colloids and core-shell NP, because anions have a strong influence on the SERS efficiency and the stability of colloids. The results indicate that core-shell NP can obviously enhance the SERS of MB. The aim of this study is to prove that compared with the metal colloid, the core-shell NP is a high efficiency SERS active substrate.

A novel colorimetric aptasensor for ultrasensitive detection of cocaine based on the formation of three-way junction pockets on the surfaces of gold nanoparticles.

PubMed

Abnous, Khalil; Danesh, Noor Mohammad; Ramezani, Mohammad; Taghdisi, Seyed Mohammad; Emrani, Ahmad Sarreshtehdar

2018-08-22

Herein, a novel colorimetric aptasensor was introduced for detection of cocaine based on the formation of three-way junction pockets on the surfaces of gold nanoparticles (AuNPs) and the catalytic activity of the surfaces of AuNPs. Simplicity and detection of cocaine in a short time (only 35 min) are some of the unique features of the proposed sensing strategy. In the presence of cocaine, triple-fragment aptamer (TFA) forms on the surfaces of AuNPs, leading to a significant decrease of the catalytic activity of AuNPs and the color of samples remains yellow. In the absence of target, TFA does not form on the surfaces of AuNPs and 4-Nitrophenol, as a colorimetric agent, has more access to the surfaces of AuNPs, resulting in the reduction of 4-Nitrophenol and the color of sample changes from yellow to colorless. The sensing strategy showed good specificity, a limit of detection (LOD) of 440 pM and a dynamic range over 2-100 nM. The sensing method was also successfully applied to detect cocaine in spiked human serum samples with recovery of 94.71-98.63%. Copyright © 2018 Elsevier B.V. All rights reserved.

A simple process based on NH2- and CH3-terminated monolayers for low contact resistance and adherent Au electrode in bottom-contact OTFTs

NASA Astrophysics Data System (ADS)

Abdur, Rahim; Lim, Jeongeun; Jeong, Kyunghoon; Rahman, Mohammad Arifur; Kim, Jiyoung; Lee, Jaegab

2016-03-01

An efficient process for the low contact resistance and adherent source/drain Au electrode in bottom-contact organic thin film transistors (OTFTs) was developed. This was achieved by using two different surface-functional groups of self-assembled monolayers, 3-aminopropyltriethoxysilane (APS), and octadecyltrichlorosilane (OTS), combined with atmospheric-pressure (AP) plasma treatment. Prior to the deposition of Au electrode, the aminoterminated monolayer self-assembles on SiO2 dielectrics, enhancing the adhesion of Au electrode as a result of the acid-base interaction of Au with the amino-terminal groups. AP plasma treatment of the patterned Au electrode on the APS-coated surface activates the entire surface to form an OTS monolayer, allowing the formation of a high quality pentacene layer on both the electrode and active region by evaporation. In addition, negligible damage by AP plasma was observed for the device performance. The fabricated OTFTs based on the two monolayers by AP plasma treatment showed the mobility of 0.23 cm2/Vs, contact resistance of 29 kΩ-cm, threshold voltage of -1.63 V, and on/off ratio of 9.8 × 105, demonstrating the application of the simple process for robust and high-performance OTFTs. [Figure not available: see fulltext.

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

Kim H. Y.; Henkelman, G.

To reveal the richer chemistry of CO oxidation by CeO2 supported Au Nanoclusters NCs)/Nanoparticles, we design a Au12 supported on a stepped-CeO2 model (Au/CeO2-step) and study various kinds of CO oxidation mechanisms at the interface of the Au/CeO2-step: oxygen spillover from the CeO2 to the Au NCs;2 CO oxidation by the O2 bound to the Au-Ce3+ interface;3 and CO oxidation by the Mars-van Krevelen (M-vK) mechanism.4 DFT+U calculations show that lattice oxygen at the CeO2 step edge oxidizes CO bound to Au NCs by the M-vK mechanism. CO2 desorption determines the rate of CO oxidation and the vacancy formation energymore » (Evac) is a reactivity descriptor for CO oxidation. The maximum Evac that insures spontaneous CO2 production is higher for the Au/CeO2-step than the Au/CeO2-surface suggesting that the CeO2-step is a better supporting material than the CeO2-surface for CO oxidation by the Au/CeO2. Our results also suggest that for CO oxidation by Au NCs supported on nano- or meso-structured CeO2, which is the case of industrial catalysts, the M-vK mechanism accounts for a large portion of the total activity.« less

On-Chip Supercapacitor Electrode Based On Polypyrrole Deposited Into Nanoporous Au Scaffold

NASA Astrophysics Data System (ADS)

Lu, P.; Ohlckers, P.; Chen, X. Y.

2016-11-01

On-chip supercapacitors hold the potential promise for serving as the energy storage units in integrated circuit system, due to their much higher energy density in comparison with conventional dielectric capacitors, high power density and long-term cycling stability. In this study, nanoporous Au (NP-Au) film on-chip was employed as the electrode scaffold to help increase the electrolyte-accessible area for active material. Pseudo-capacitive polypyrrole (PPY) with high theoretical capacitance was deposited into the NP-Au scaffold, to construct the tailored NP-Au/PPY hybrid on-chip electrode with improved areal capacitance. Half cell test in three- electrode system revealed the improved capacitor performance of nanoporous Au supported PPY electrode, compared to the densely packed PPY nanowire film electrode on planer Au substrate (Au/PPY). The areal capacitance of 37 mF/cm2∼10 mV/s, 32 mF/cm2∼50 mV/s, 28 mF/cm2∼100 mV/s, 16 mF/cm2∼500 mV/s, were offered by NP-Au/PPY. Also, the cycling performance was enhanced via using NP-Au scaffold. The developed NP-Au/PPY on-chip electrode demonstrated herein paves a feasible pathway to employ dealloying derived porous metal as the scaffold for improving both the energy density and cycling performance for supercapacitor electrodes.

Influence of graphene coating on the adsorption and tribology of Xe on Au(1 1 1) substrate.

PubMed

Zhang, Y N; Bortolani, V; Mistura, G

2014-11-05

The adsorption and tribological properties of graphene have received increasing attention for the further development of graphene-based coatings in applications. In this work, we performed first principles calculations with the inclusion of the nonlocal van der Waals correction to study the effect of graphene coating on the adsorption geometries, sliding frictions and electronic properties of Xe monolayer on the Au(1 1 1) substrate. The calculated activation energies indicate that Xe becomes movable on pure Au(1 1 1) surface at a temperature of around 30 K, whereas its motion can be activated only at a high temperature of ~50 K on graphene and on graphene-coated Au(1 1 1) substrates, in good agreement with recent experimental measurements by quartz crystal microbalance technique.

Fabrication of Te@Au core-shell hybrids for efficient ethanol oxidation

NASA Astrophysics Data System (ADS)

Jin, Huile; Wang, Demeng; Zhao, Yuewu; Zhou, Huan; Wang, Shun; Wang, Jichang

2012-10-01

Using Au nanoparticles to catalyze the oxidation of alcohols has garnered increasing attention due to its potential application in direct alcohol fuel cells. In this research Te@Au core-shell hybrids were fabricated for the catalytic oxidation of ethanol, where the preparation procedure involved the initial production of Te crystals with different microstructures and the subsequent utilization of the Te crystal as a template and reducing agent for the production of Te@Au hybrids. The as-prepared core-shell hybrids were characterized by scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction techniques. Electrochemical measurements illustrate that the hybrids have great electrocatalytic activity and stability toward ethanol oxidation in alkaline media. The enhanced electrocatalytic property may be attributed to the cooperative effects between the metal and semiconductor and the presence of a large number of active sites on the hybrids surface.

Electrochemical sensor for rutin detection based on Au nanoparticle-loaded helical carbon nanotubes

NASA Astrophysics Data System (ADS)

Yang, Haitang; Li, Bingyue; Cui, Rongjing; Xing, Ruimin; Liu, Shanhu

2017-10-01

The key step in the fabrication of highly active electrochemical sensors is seeking multifunctional nanocomposites as electrode modified materials. In this study, the gold nanoparticle-decorated helical carbon nanotube nanocomposites (AuNPs-HCNTs) were fabricated for rutin detection because of its superior sensitivity, the chemical stability of AuNPs, and the superior conductivity and unique 3D-helical structure of helical carbon nanotubes. Results showed the prepared nanocomposites exhibited superior electrocatalytic activity towards rutin due to the synergetic effects of AuNPs and HCNTs. Under the optimized conditions, the developed sensor exhibited a linear response range from 0.1 to 31 μmol/L for rutin with a low detectable limit of 81 nmol/L. The proposed method might offer a possibility for electrochemical analysis of rutin in Chinese medical analysis or serum monitoring owing to its low cost, simplicity, high sensitivity, good stability, and few interferences against common coexisting ions in real samples.

Fabrication of biomolecules self-assembled on Au nanodot array for bioelectronic device.

PubMed

Lee, Taek; Kumar, Ajay Yagati; Yoo, Si-Youl; Jung, Mi; Min, Junhong; Choi, Jeong-Woo

2013-09-01

In the present study, an nano-platform composed of Au nanodot arrays on which biomolecules could be self-assembled was developed and investigated for a stable bioelectronic device platform. Au nanodot pattern was fabricated using a nanoporous alumina template. Two different biomolecules, a cytochrome c and a single strand DNA (ssDNA), were immobilized on the Au nanodot arrays. Cytochorme c and single stranded DNA could be immobilized on the Au nanodot using the chemical linker 11-MUA and thiol-modification by covalent bonding, respectively. The atomic structure of the fabricated nano-platform device was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The electrical conductivity of biomolecules immobilized on the Au nanodot arrays was confirmed by scanning tunneling spectroscopy (STS). To investigate the activity of biomolecule-immobilized Au-nano dot array, the cyclic voltammetry was carried out. This proposed nano-platform device, which is composed of biomolecules, can be used for the construction of a novel bioelectronic device.

Surface plasmon aided high sensitive non-enzymatic glucose sensor using Au/NiAu multilayered nanowire arrays.

PubMed

Wang, Lanfang; Zhu, Weiqi; Lu, Wenbo; Qin, Xiufang; Xu, Xiaohong

2018-07-15

A novel plasmon aided non-enzymatic glucose sensor was first constructed based on the unique half-rough Au/NiAu multilayered nanowire arrays. These multilayered and half-rough nanowires provide high chemical activity and large surface area for glucose oxidation in an alkaline solution. Under visible light irradiation, the surface plasmons originated from Au part enhance the electron transfer in the vertically aligned nanowires, leading to high sensitivity and wide detection range. The resulting sensor exhibits a wide glucose detection concentration range, low detection limit, and high sensitivity for plasmon aided non-enzymatic glucose sensor. Moreover, the detection sensitivity is enhanced by almost 2 folds compared to that in the dark, which significantly enhanced the performance of Au/NiAu multilayered nanowire arrays sensor. An excellent selectivity and acceptable stability were also achieved. These results indicate that surface plasmon aided nanostructures are promising new platforms for the construction of non-enzymatic glucose sensors. Copyright © 2018 Elsevier B.V. All rights reserved.

Easy on-demand single-pass self-assembly and modification to fabricate gold@graphene-based anti-inflammatory nanoplatforms

NASA Astrophysics Data System (ADS)

Byeon, Jeong Hoon; Park, Jae Hong

2016-10-01

Zwitterionic chitosan (ZC) was modified by fully (both for lateral dimension and thickness) nanodimensional gold-graphene oxide (Au@GO) flakes under visible light and the potential of the resulting materials as biomedical nanoplatforms was investigated. Fully nanodimensional GO flakes floating in nitrogen gas were incorporated with Au nanoparticles to form Au@GO nanoflakes, and the Au@GO was then incorporated with ZC droplets to form the Au@GO-ZC hybrid nanoparticles. The collected particles were exposed to visible light to induce the photocatalytic activity of the Au@GO nanoflakes towards the ZC derivatives. The visible-light-exposed particles show different chemical and surface properties from the unexposed particles, while there were no significant differences in cytotoxicity and macrophage inflammatory protein production. This work suggests that incorporating fully nanodimensional Au@GO flakes with ZC is a suitable technique for ambient photo-modification of the chitosans’ surface property without significant changes in size and shape and increases in cytotoxicity and inflammatory response.

Tri-metallic PtPdAu mesoporous nanoelectrocatalysts.

PubMed

Li, Chunjie; Wang, Hongjing; Li, Yinghao; Yu, Hongjie; Yin, Shuli; Xue, Hairong; Li, Xiaonian; Xu, You; Wang, Liang

2018-06-22

The design of mesoporous materials with multi-metallic compositions is highly important for various electrocatalytic applications. In this paper, we demonstrate an efficient method to directly fabricate tri-metallic PtPdAu mesoporous nanoparticles (PtPdAu MNs) in a high yield, which is simply performed by heating treatment of the reaction mixture aqueous solution at 40 °C for 4 h. Profiting from its mesoporous structure and multi-metallic components, the as-prepared PtPdAu MNs exhibit enhanced electrocatalytic activities toward both methanol oxidation reaction and oxygen reduction reaction in comparison with bi-metallic PtPd MNs and commercial Pt/C catalyst.

Tri-metallic PtPdAu mesoporous nanoelectrocatalysts

NASA Astrophysics Data System (ADS)

Li, Chunjie; Wang, Hongjing; Li, Yinghao; Yu, Hongjie; Yin, Shuli; Xue, Hairong; Li, Xiaonian; Xu, You; Wang, Liang

2018-06-01

The design of mesoporous materials with multi-metallic compositions is highly important for various electrocatalytic applications. In this paper, we demonstrate an efficient method to directly fabricate tri-metallic PtPdAu mesoporous nanoparticles (PtPdAu MNs) in a high yield, which is simply performed by heating treatment of the reaction mixture aqueous solution at 40 °C for 4 h. Profiting from its mesoporous structure and multi-metallic components, the as-prepared PtPdAu MNs exhibit enhanced electrocatalytic activities toward both methanol oxidation reaction and oxygen reduction reaction in comparison with bi-metallic PtPd MNs and commercial Pt/C catalyst.

Evaluating differences in the active-site electronics of supported Au nanoparticle catalysts using Hammett and DFT studies

NASA Astrophysics Data System (ADS)

Kumar, Gaurav; Tibbitts, Luke; Newell, Jaclyn; Panthi, Basu; Mukhopadhyay, Ahana; Rioux, Robert M.; Pursell, Christopher J.; Janik, Michael; Chandler, Bert D.

2018-03-01

Supported metal catalysts, which are composed of metal nanoparticles dispersed on metal oxides or other high-surface-area materials, are ubiquitous in industrially catalysed reactions. Identifying and characterizing the catalytic active sites on these materials still remains a substantial challenge, even though it is required to guide rational design of practical heterogeneous catalysts. Metal-support interactions have an enormous impact on the chemistry of the catalytic active site and can determine the optimum support for a reaction; however, few direct probes of these interactions are available. Here we show how benzyl alcohol oxidation Hammett studies can be used to characterize differences in the catalytic activity of Au nanoparticles hosted on various metal-oxide supports. We combine reactivity analysis with density functional theory calculations to demonstrate that the slope of experimental Hammett plots is affected by electron donation from the underlying oxide support to the Au particles.

Peroxidase-like activity of apoferritin paired gold clusters for glucose detection.

PubMed

Jiang, Xin; Sun, Cuiji; Guo, Yi; Nie, Guangjun; Xu, Li

2015-02-15

The discovery and application of noble metal nanoclusters have received considerable attention. In this paper, we reported that apoferritin paired gold clusters (Au-Ft) could efficiently catalyze oxidation of 3.3',5.5'-tetramethylbenzidine (TMB) by H2O2 to produce a blue color reaction. Compared with natural enzyme, Au-Ft exhibited higher activity near acidic pH and could be used over a wide range of temperatures. Apoferritin nanocage enhanced the reaction activity of substrate TMB by H2O2. The reaction catalyzed by Au-Ft was found to follow a typical Michaelis-Menten kinetics. The kinetic parameters exhibited a lower K(m) value (0.097 mM) and a higher K(cat) value (5.8 × 10(4) s(-1)) for TMB than that of horse radish peroxidase (HRP). Base on these findings, Au-Ft, acting as a peroxidase mimetic, performed enzymatic spectrophotometric analysis of glucose. This system exhibited acceptable reproducibility and high selectivity in biosening, suggesting that it could have promising applications in the future. Copyright © 2014 Elsevier B.V. All rights reserved.

Comparative serum albumin interactions and antitumor effects of Au(III) and Ga(III) ions.

PubMed

Sarioglu, Omer Faruk; Ozdemir, Ayse; Karaboduk, Kuddusi; Tekinay, Turgay

2015-01-01

In the present study, interactions of Au(III) and Ga(III) ions on human serum albumin (HSA) were studied comparatively via spectroscopic and thermal analysis methods: UV-vis absorbance spectroscopy, fluorescence spectroscopy, Fourier transform infrared (FT-IR) spectroscopy and isothermal titration calorimetry (ITC). The potential antitumor effects of these ions were studied on MCF-7 cells via Alamar blue assay. It was found that both Au(III) and Ga(III) ions can interact with HSA, however; Au(III) ions interact with HSA more favorably and with a higher affinity. FT-IR second derivative analysis results demonstrated that, high concentrations of both metal ions led to a considerable decrease in the α-helix content of HSA; while Au(III) led to around 5% of decrease in the α-helix content at 200μM, it was around 1% for Ga(III) at the same concentration. Calorimetric analysis gave the binding kinetics of metal-HSA interactions; while the binding affinity (Ka) of Au(III)-HSA binding was around 3.87×10(5)M(-1), it was around 9.68×10(3)M(-1) for Ga(III)-HSA binding. Spectroscopy studies overall suggest that both metal ions have significant effects on the chemical structure of HSA, including the secondary structure alterations. Antitumor activity studies on MCF7 tumor cell line with both metal ions revealed that, Au(III) ions have a higher antiproliferative activity compared to Ga(III) ions. Copyright © 2014 Elsevier GmbH. All rights reserved.

One-Step Electrochemical Fabrication of Reduced Graphene Oxide/Gold Nanoparticles Nanocomposite-Modified Electrode for Simultaneous Detection of Dopamine, Ascorbic Acid, and Uric Acid

PubMed Central

Lee, Chang-Seuk; Yu, Su Hwan; Kim, Tae Hyun

2017-01-01

Here, we introduce the preparation of the hybrid nanocomposite-modified electrode consisting of reduced graphene oxide (RGO) and gold nanoparticles (AuNPs) using the one-step electrochemical method, allowing for the simultaneous and individual detection of dopamine (DA), ascorbic acid (AA), and uric acid (UA). RGO/AuNPs nanocomposite was formed on a glassy carbon electrode by the co-reduction of GO and Au3+ using the potentiodynamic method. The RGO/AuNPs nanocomposite-modified electrode was produced by subjecting a mixed solution of GO and Au3+ to cyclic sweeping from −1.5 V to 0.8 V (vs. Ag/AgCl) at a scan rate 10 mV/s for 3 cycles. The modified electrode was characterized by scanning electron microscopy, Raman spectroscopy, contact angle measurement, electrochemical impedance spectroscopy, and cyclic voltammetry. Voltammetry results confirm that the RGO/AuNPs nanocomposite-modified electrode has high catalytic activity and good resolution for the detection of DA, AA, and UA. The RGO/AuNPs nanocomposite-modified electrode exhibits stable amperometric responses for DA, AA, and UA, respectively, and its detection limits were estimated to be 0.14, 9.5, and 25 μM. The modified electrode shows high selectivity towards the determination of DA, AA, or UA in the presence of potentially active bioelements. In addition, the resulting sensor exhibits many advantages such as fast amperometric response, excellent operational stability, and appropriate practicality. PMID:29301209

Preparation, Spectroscopic Characterization, and Frontier MO Study of the Heteronuclear Luminescent [Pt(2)Au(2)(dmb)(2)(PPh(3))(4)](PF(6))(2) Cluster (dmb = 1,8-Diisocyano-p-menthane). A Cluster with a Formal Au(0)-Au(0) Bond Encapsulated inside a "Pt(2)(dmb)(2)(2+) " Fragment.

PubMed

Zhang, Tianle; Drouin, Marc; Harvey, Pierre D.

1999-11-01

The title compound is prepared from the direct reaction of Pt(2)(dba)(3) (dba = dibenzylideneacetone) and [Au(PPh(3))(2)](PF(6)) in the presence of 1,8-diisocyano-p-methane (dmb), with Pt(2)(dmb)(2)Cl(2), [Pt(4)(dmb)(4)(PPh(3))(2)](PF(6))(2), and (PPh(3))AuCl being formed as parallel products. X-ray crystallography reveals the presence of a quasi-linear PPh(3)Au-AuPPh(3) fragment encapsulated inside a "Pt(2)(dmb)(2)(2+)" ring which is axially coordinated with two PPh(3) ligands. The d(AuAu) is 2.5977(6) Å and is indicative of a strong Au-Au single bond. The IR nu(CN) data reveal that the Pt oxidation state is I, which places the Au oxidation state at 0. The PtAu distances are 2.8422(5) and 2.8082(5) Å. The Raman-active nu(Au(2)), nu(PtAu) (b(2g) + a(g)), nu(PtP), nu(AuP), and nu(PtC) are found at 121.2, approximately 100, 85.5, 162.1, 183.1, and 457.2, and 440.9 cm(-)(1), respectively. The PtAu (0.67 mdyn Å(-)(1)) and Au(2) (1.21 mdyn Å(-)(1)) force constants (F) confirm the presence of medium PtAu and strong Au(2) bonding interactions. The absorption spectra are characterized by strong bands at lambda(max) (epsilon, M(-1) cm(-1)) at 316 (32 300), 366 (37 800), and 418 nm (21 500) and lower intensity features at 516 (2860) and 655 nm (834). The cluster is luminescent at low temperatures (solid and frozen glasses), and in the solid state at room temperature, and exhibits an emission band at approximately 875 nm, and an emission lifetime, tau(e), of 4.4 +/- 0.4 ns (solvent = butyronitrile, T = 77 K).

Enhanced electrocatalytic activity of graphene-gold nanoparticles hybrids for peroxynitrite electrochemical detection on hemin-based electrode.

PubMed

Wang, Beibei; Ji, Xueping; Ren, Jujie; Ni, Ruixing; Wang, Lin

2017-12-01

A simple, ultrasensitive peroxynitrite anion (ONOO - ) electrochemical sensing platform was developed by immobilizing hemin on a density controllable electrochemically reduced graphene oxide-Au nanoparticles (ERGO-AuNPs) nanohybrids. The ERGO-AuNPs in situ nanohybrids were produced onto a glass carbon electrode (GCE) by one-step electrodeposition, the density of which could be easily controlled by electrodeposited time. The morphology of ERGO-AuNPs nanohybrids was characterized by a scanning electron microscope (SEM). The ERGO-AuNPs nanohybrids showed a high electrocatalytic activity for immobilized-hemin, because the nanostructures hybrids could effectively promote electron transfer rate between hemin and the electrode. Due to nanohybrids-enhanced catalytic effect for hemin, they were firstly selected for use as a highly sensitive electrochemical platform for ONOO - detection. The resulted sensor showed a high electrocatalytic activity toward ONOO - oxidation, being free from the electroactive interferents, including nitrite, nitrate, dopamine and uric acid at an applied potential of 0.7V. The sensor exhibited a high sensitivity of 123.1nAμM -1 and a lower detection limit of 0.1μM, and a wide linear range of 2.4×10 -6 to 5.5×10 -5 M, which could be attributed to the synergy between ERGO and AuNPs in hybrids. The nanohybrids in situ preparation and ONOO - detection methods would be beneficial to developing other sensing interface and have promising applications in biological molecules analysis and clinical diagnostic. Copyright © 2017 Elsevier B.V. All rights reserved.

Thermal neutron capture and resonance integral cross sections of 45Sc

NASA Astrophysics Data System (ADS)

Van Do, Nguyen; Duc Khue, Pham; Tien Thanh, Kim; Thi Hien, Nguyen; Kim, Guinyun; Kim, Kwangsoo; Shin, Sung-Gyun; Cho, Moo-Hyun; Lee, Manwoo

2015-11-01

The thermal neutron cross section (σ0) and resonance integral (I0) of the 45Sc(n,γ)46Sc reaction have been measured relative to that of the 197Au(n,γ)198Au reaction by means of the activation method. High-purity natural scandium and gold foils without and with a cadmium cover of 0.5 mm thickness were irradiated with moderated pulsed neutrons produced from the Pohang Neutron Facility (PNF). The induced activities in the activated foils were measured with a high purity germanium (HPGe) detector. In order to improve the accuracy of the experimental results the counting losses caused by the thermal (Gth) and resonance (Gepi) neutron self-shielding, the γ-ray attenuation (Fg) and the true γ-ray coincidence summing effects were made. In addition, the effect of non-ideal epithermal spectrum was also taken into account by determining the neutron spectrum shape factor (α). The thermal neutron cross-section and resonance integral of the 45Sc(n,γ)46Sc reaction have been determined relative to the reference values of the 197Au(n,γ)198Au reaction, with σo,Au = 98.65 ± 0.09 barn and Io,Au = 1550 ± 28 barn. The present thermal neutron cross section has been determined to be σo,Sc = 27.5 ± 0.8 barn. According to the definition of cadmium cut-off energy at 0.55 eV, the present resonance integral cross section has been determined to be Io,Sc = 12.4 ± 0.7 barn. The present results are compared with literature values and discussed.

Natural gold particles in Eucalyptus leaves and their relevance to exploration for buried gold deposits

PubMed Central

Lintern, Melvyn; Anand, Ravi; Ryan, Chris; Paterson, David

2013-01-01

Eucalyptus trees may translocate Au from mineral deposits and support the use of vegetation (biogeochemical) sampling in mineral exploration, particularly where thick sediments dominate. However, biogeochemistry has not been routinely adopted partly because biotic mechanisms of Au migration are poorly understood. For example, although Au has been previously measured in plant samples, there has been doubt as to whether it was truly absorbed rather than merely adsorbed on the plant surface as aeolian contamination. Here we show the first evidence of particulate Au within natural specimens of living biological tissue (not from laboratory experimentation). This observation conclusively demonstrates active biogeochemical adsorption of Au and provides insight into its behaviour in natural samples. The confirmation of biogeochemical adsorption of Au, and of a link with abiotic processes, promotes confidence in an emerging technique that may lead to future exploration success and maintain continuity of supply. PMID:24149278

Mono and bimetallic nanoparticles of gold, silver and palladium-catalyzed NADH oxidation-coupled reduction of Eosin-Y

NASA Astrophysics Data System (ADS)

Santhanalakshmi, J.; Venkatesan, P.

2011-02-01

Mono metallic (Au, Ag, Pd) and bimetallic (Au-Ag, Ag-Pd, Au-Pd) with 1:1 mol stoichiometry, nanoparticles are synthesized using one-pot, temperature controlled chemical method using cetyltrimethylammonium bromide (CTAB) as the capping agent. The particle sizes (Au = 5.6, Ag = 5.0, Pd = 6.0, Au-Ag = 9.2, Ag-Pd = 9.6, Au-Pd = 9.4 nm) are characterized by UV-Vis, HRTEM, and XRD measurements, respectively. CTAB bindings onto mono and bimetallic nanoparticles are analyzed by FTIR spectra. The catalytic activities of mono and bimetallic nanoparticles are tested on the reaction between NADH oxidation and Eosin-Y reduction. The effects of base, pH, ionic strength, nature of mono and bimetallic catalysts are studied and the reaction conditions are optimized. Bimetallic nanoparticles exhibited better catalysis than the mono metallic nanoparticles, which may be due to the electronic effects of the core to shell metal atoms.

Gold@silver bimetal nanoparticles/pyramidal silicon 3D substrate with high reproducibility for high-performance SERS

NASA Astrophysics Data System (ADS)

Zhang, Chao; Jiang, Shou Zhen; Yang, Cheng; Li, Chong Hui; Huo, Yan Yan; Liu, Xiao Yun; Liu, Ai Hua; Wei, Qin; Gao, Sai Sai; Gao, Xing Guo; Man, Bao Yuan

2016-05-01

A novel and efficient surface enhanced Raman scattering (SERS) substrate has been presented based on Gold@silver/pyramidal silicon 3D substrate (Au@Ag/3D-Si). By combining the SERS activity of Ag, the chemical stability of Au and the large field enhancement of 3D-Si, the Au@Ag/3D-Si substrate possesses perfect sensitivity, homogeneity, reproducibility and chemical stability. Using R6G as probe molecule, the SERS results imply that the Au@Ag/3D-Si substrate is superior to the 3D-Si, Ag/3D-Si and Au/3D-Si substrate. We also confirmed these excellent behaviors in theory via a commercial COMSOL software. The corresponding experimental and theoretical results indicate that our proposed Au@Ag/3D-Si substrate is expected to develop new opportunities for label-free SERS detections in biological sensors, biomedical diagnostics and food safety.

A plasmonic nanosensor for lipase activity based on enzyme-controlled gold nanoparticles growth in situ

NASA Astrophysics Data System (ADS)

Tang, Yan; Zhang, Wei; Liu, Jia; Zhang, Lei; Huang, Wei; Huo, Fengwei; Tian, Danbi

2015-03-01

A plasmonic nanosensor for lipase activity was developed based on one-pot nanoparticle growth. Tween 80 was selected not only as the substrate for lipase recognition but also as the reducing and stabilizing agent for the sensor fabrication. The different molecular groups in Tween 80 could have different roles in the fabrication procedure; the H2O2 produced by the autoxidation of the ethylene oxide subunits in Tween 80 could reduce the AuCl4- ions to Au atoms, meanwhile, the lipase could hydrolyze its carboxyl ester bond, which could, in turn, control the rate of nucleation of the gold nanoparticles (AuNPs) and tailor the localized surface plasmon resonance (LSPR) of the AuNP transducers. The color changes, which depend on the absence or presence of the lipase, could be used to sense the lipase activity. A linear response ranging from 0.025 to 4 mg mL-1 and a detection limit of the lipase as low as 3.47 μg mL-1 were achieved. This strategy circumvents the problems encountered by general enzyme assays that require sophisticated instruments and complicated assembling steps. The methodology can benefit the assays of heterogeneous-catalyzed enzymes.A plasmonic nanosensor for lipase activity was developed based on one-pot nanoparticle growth. Tween 80 was selected not only as the substrate for lipase recognition but also as the reducing and stabilizing agent for the sensor fabrication. The different molecular groups in Tween 80 could have different roles in the fabrication procedure; the H2O2 produced by the autoxidation of the ethylene oxide subunits in Tween 80 could reduce the AuCl4- ions to Au atoms, meanwhile, the lipase could hydrolyze its carboxyl ester bond, which could, in turn, control the rate of nucleation of the gold nanoparticles (AuNPs) and tailor the localized surface plasmon resonance (LSPR) of the AuNP transducers. The color changes, which depend on the absence or presence of the lipase, could be used to sense the lipase activity. A linear response ranging from 0.025 to 4 mg mL-1 and a detection limit of the lipase as low as 3.47 μg mL-1 were achieved. This strategy circumvents the problems encountered by general enzyme assays that require sophisticated instruments and complicated assembling steps. The methodology can benefit the assays of heterogeneous-catalyzed enzymes. Electronic supplementary information (ESI) available: Zeta potential measurements, optimization of assay conditions, pH-stat method. See DOI: 10.1039/c4nr07579j

Biosynthesis of gold nanoparticles by the extreme bacterium Deinococcus radiodurans and an evaluation of their antibacterial properties.

PubMed

Li, Jiulong; Li, Qinghao; Ma, Xiaoqiong; Tian, Bing; Li, Tao; Yu, Jiangliu; Dai, Shang; Weng, Yulan; Hua, Yuejin

Deinococcus radiodurans is an extreme bacterium known for its high resistance to stresses including radiation and oxidants. The ability of D. radiodurans to reduce Au(III) and biosynthesize gold nanoparticles (AuNPs) was investigated in aqueous solution by ultraviolet and visible (UV/Vis) absorption spectroscopy, electron microscopy, X-ray diffraction (XRD), dynamic light scattering (DLS), Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). D. radiodurans efficiently synthesized AuNPs from 1 mM Au(III) solution in 8 h. The AuNPs were of spherical, triangular and irregular shapes with an average size of 43.75 nm and a polydispersity index of 0.23 as measured by DLS. AuNPs were distributed in the cell envelope, across the cytosol and in the extracellular space. XRD analysis confirmed the crystallite nature of the AuNPs from the cell supernatant. Data from the FTIR and XPS showed that upon binding to proteins or compounds through interactions with carboxyl, amine, phospho and hydroxyl groups, Au(III) may be reduced to Au(I), and further reduced to Au(0) with the capping groups to stabilize the AuNPs. Biosynthesis of AuNPs was optimized with respect to the initial concentration of gold salt, bacterial growth period, solution pH and temperature. The purified AuNPs exhibited significant antibacterial activity against both Gram-negative ( Escherichia coli ) and Gram-positive ( Staphylococcus aureus ) bacteria by damaging their cytoplasmic membrane. Therefore, the extreme bacterium D. radiodurans can be used as a novel bacterial candidate for efficient biosynthesis of AuNPs, which exhibited potential in biomedical application as an antibacterial agent.

Activation of Noble Metals on Metal-Carbide Surfaces: Novel Catalysts for CO Oxidation, Desulfurization and Hydrogenation Reactions

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

Rodriguez J. A.; Illas, F.

2012-01-01

This perspective article focuses on the physical and chemical properties of highly active catalysts for CO oxidation, desulfurization and hydrogenation reactions generated by depositing noble metals on metal-carbide surfaces. To rationalize structure-reactivity relationships for these novel catalysts, well-defined systems are required. High-resolution photoemission, scanning tunneling microscopy (STM) and first-principles periodic density-functional (DF) calculations have been used to study the interaction of metals of Groups 9, 10 and 11 with MC(001) (M = Ti, Zr, V, Mo) surfaces. DF calculations give adsorption energies that range from 2 eV (Cu, Ag, Au) to 6 eV (Co, Rh, Ir). STM images show thatmore » Au, Cu, Ni and Pt grow on the carbide substrates forming two-dimensional islands at very low coverage, and three-dimensional islands at medium and large coverages. In many systems, the results of DF calculations point to the preferential formation of admetal-C bonds with significant electronic perturbations in the admetal. TiC(001) and ZrC(001) transfer some electron density to the admetals facilitating bonding of the adatom with electron-acceptor molecules (CO, O{sub 2}, C{sub 2}H{sub 4}, SO{sub 2}, thiophene, etc.). For example, the Cu/TiC(001) and Au/TiC(001) systems are able to cleave both S-O bonds of SO{sub 2} at a temperature as low as 150 K, displaying a reactivity much larger than that of TiC(001) or extended surfaces of bulk copper and gold. At temperatures below 200 K, Au/TiC is able to dissociate O{sub 2} and perform the 2CO + O{sub 2} {yields} 2CO{sub 2} reaction. Furthermore, in spite of the very poor hydrodesulfurization performance of TiC(001) or Au(111), a Au/TiC(001) surface displays an activity for the hydrodesulfurization of thiophene higher than that of conventional Ni/MoS{sub x} catalysts. In general, the Au/TiC system is more chemically active than systems generated by depositing Au nanoparticles on oxide surfaces. Thus, metal carbides are excellent supports for enhancing the chemical reactivity of noble metals.« less

Multifunctional two-photon active silica-coated Au@MnO Janus particles for selective dual functionalization and imaging.

PubMed

Schick, Isabel; Lorenz, Steffen; Gehrig, Dominik; Schilmann, Anna-Maria; Bauer, Heiko; Panthöfer, Martin; Fischer, Karl; Strand, Dennis; Laquai, Frédéric; Tremel, Wolfgang

2014-02-12

Monodisperse multifunctional and nontoxic Au@MnO Janus particles with different sizes and morphologies were prepared by a seed-mediated nucleation and growth technique with precise control over domain sizes, surface functionalization, and dye labeling. The metal oxide domain could be coated selectively with a thin silica layer, leaving the metal domain untouched. In particular, size and morphology of the individual (metal and metal oxide) domains could be controlled by adjustment of the synthetic parameters. The SiO2 coating of the oxide domain allows biomolecule conjugation (e.g., antibodies, proteins) in a single step for converting the photoluminescent and superparamagnetic Janus nanoparticles into multifunctional efficient vehicles for theranostics. The Au@MnO@SiO2 Janus particles were characterized using high-resolution transmission electron microscopy (HR-)TEM, powder X-ray diffraction (PXRD), optical (UV-vis) spectroscopy, confocal laser fluorescence scanning microscopy (CLSM), and dynamic light scattering (DLS). The functionalized nanoparticles were stable in buffer solution or serum, showing no indication of aggregation. Biocompatibility and potential biomedical applications of the Au@MnO@SiO2 Janus particles were assayed by a cell viability analysis by coincubating the Au@MnO@SiO2 Janus particles with Caki 1 and HeLa cells. Time-resolved fluorescence spectroscopy in combination with CLSM revealed the silica-coated Au@MnO@SiO2 Janus particles to be highly two-photon active; no indication for an electronic interaction between the dye molecules incorporated in the silica shell surrounding the MnO domains and the attached Au domains was found; fluorescence quenching was observed when dye molecules were bound directly to the Au domains.

Solvent-driven reductive activation of carbon dioxide by gold anions.

PubMed

Knurr, Benjamin J; Weber, J Mathias

2012-11-14

Catalytic activation and electrochemical reduction of CO(2) for the formation of chemically usable feedstock and fuel are central goals for establishing a carbon neutral fuel cycle. The role of solvent molecules in catalytic processes is little understood, although solvent-solute interactions can strongly influence activated intermediate species. We use vibrational spectroscopy of mass-selected Au(CO(2))(n)(-) cluster ions to probe the solvation of AuCO(2)(-) as a model for a reactive intermediate in the reductive activation of a CO(2) ligand by a single-atom catalyst. For the first few solvent molecules, solvation of the complex preferentially occurs at the CO(2) moiety, enhancing reductive activation through polarization of the excess charge onto the partially reduced ligand. At higher levels of solvation, direct interaction of additional solvent molecules with the Au atom diminishes reduction. The results show how the solvation environment can enhance or diminish the effects of a catalyst, offering design criteria for single-atom catalyst engineering.

Value added cleaning and disinfection of the root canal: laser-activated irrigation and laser-induced photoporation

NASA Astrophysics Data System (ADS)

De Moor, Roeland J. G.; Meire, Maarten A.

2016-03-01

Among present-day marketed systems ultrasonic activation appears to be the best way to activate and potentiate endodontic irrigants. An alternative for ultrasonic activation of irrigants is laser activated irrigation (LAI) or photoninitiated acoustic streaming. Based on present-day research it appears that LAI (especially with Erbium lasers) can be more efficient for debris removal out of root canals and interaction with the endodontic biofilms thanks to the induction of specific cavitation phenomena and acoustic streaming. Other wavelengths are now explored to be used for LAI. Another way to interact with biofilms is to rely on laser-induced photoporation in combination with gold nanoparticles ( AuNPs). The latter is an alternative physical method for delivering macromolecules in cells. Nanosized membrane pores can be created upon pulsed laser illumination. Depending on the laser energy, pores are created through either direct heating of the AuNPs or by vapour nanobubbles that can emerge around the AuNPs.

Size- and time-dependent alteration in metabolic activities of human hepatic cytochrome P450 isozymes by gold nanoparticles via microsomal coincubations

NASA Astrophysics Data System (ADS)

Ye, Meiling; Tang, Ling; Luo, Mengjun; Zhou, Jing; Guo, Bin; Liu, Yangyuan; Chen, Bo

2014-11-01

Nano-sized particles are known to interfere with drug-metabolizing cytochrome P450 (CYP) enzymes, which can be anticipated to be a potential source of unintended adverse reactions, but the mechanisms underlying the inhibition are still not well understood. Herein we report a systematic investigation of the impacts of gold nanoparticles (AuNPs) on five major CYP isozymes under in vitro incubations of human liver microsomes (HLMs) with tannic acid (TA)-stabilized AuNPs in the size range of 5 to 100 nm. It is found that smaller AuNPs show more pronounced inhibitory effects on CYP2C9, CYP2C19, CYP2D6, and CYP3A4 in a dose-dependent manner, while 1A2 is the least susceptible to the AuNP inhibition. The size- and dose-dependent CYP-specific inhibition and the nonspecific drug-nanogold binding in the coincubation media can be significantly reduced by increasing the concentration ratio of microsomal proteins to AuNPs, probably via a noncompetitive mode. Remarkably, AuNPs are also found to exhibit a slow time-dependent inactivation of 2D6 and 3A4 in a β-nicotinamide adenine dinucleotide 2'-phosphate reduced tetrasodium salt hydrate (NADPH)-independent manner. During microsomal incubations, UV-vis spectroscopy, dynamic light scattering, and zeta-potential measurements were used to monitor the changes in particle properties under the miscellaneous AuNP/HLM/CYP dispersion system. An improved stability of AuNPs by mixing HLM with the gold nanocolloid reveals that the stabilization via AuNP-HLM interactions may occur on a faster time scale than the salt-induced nanoaggregation by incubation in phosphate buffer. The results suggest that the AuNP induced CYP inhibition can be partially attributed to its adhesion onto the enzymes to alter their structural conformations or onto the HLM membrane therefore impairing the integral membrane proteins. Additionally, AuNPs likely block the substrate pocket on the CYP surface, depending on both the particle characteristics and the structural diversity of the isozymes. These findings may represent additional mechanisms for the differential inhibitory effects arising from the coincubated AuNPs on the metabolic activities of the hepatic CYP isozymes.

Enhanced activity of gold-supported cobalt oxide for the electrochemical evolution of oxygen.

PubMed

Yeo, Boon Siang; Bell, Alexis T

2011-04-13

Scanning electron microscopy, linear sweep voltammetry, chronoamperometry, and in situ surface-enhanced Raman spectroscopy were used to investigate the electrochemical oxygen evolution reaction (OER) occurring on cobalt oxide films deposited on Au and other metal substrates. All experiments were carried out in 0.1 M KOH. A remarkable finding is that the turnover frequency for the OER exhibited by ∼0.4 ML of cobalt oxide deposited on Au is 40 times higher than that of bulk cobalt oxide. The activity of small amounts of cobalt oxide deposited on Pt, Pd, Cu, and Co decreased monotonically in the order Au > Pt > Pd > Cu > Co, paralleling the decreasing electronegativity of the substrate metal. Another notable finding is that the OER turnover frequency for ∼0.4 ML of cobalt oxide deposited on Au is nearly three times higher than that for bulk Ir. Raman spectroscopy revealed that the as-deposited cobalt oxide is present as Co(3)O(4) but undergoes progressive oxidation to CoO(OH) with increasing anodic potential. The higher OER activity of cobalt oxide deposited on Au is attributed to an increase in fraction of the Co sites present as Co(IV) cations, a state of cobalt believed to be essential for OER to occur. A hypothesis for how Co(IV) cations contribute to OER is proposed and discussed. © 2011 American Chemical Society

M13 Virus-Incorporated Biotemplates on Electrode Surfaces To Nucleate Metal Nanostructures by Electrodeposition.

PubMed

Manivannan, Shanmugam; Kang, Inhak; Seo, Yeji; Jin, Hyo-Eon; Lee, Seung-Wuk; Kim, Kyuwon

2017-09-27

We report a virus-incorporated biological template (biotemplate) on electrode surfaces and its use in electrochemical nucleation of metal nanocomposites as an electrocatalytic material for energy applications. The biotemplate was developed with M13 virus (M13) incorporated in a silicate sol-gel matrix as a scaffold to nucleate Au-Pt alloy nanostructures by electrodeposition, together with reduced graphene oxide (rGO). The phage when engineered with Y3E peptides could nucleate Au-Pt alloy nanostructures, which ensured adequate packing density, simultaneous stabilization of rGO, and a significantly increased electrochemically active surface area. Investigation of the electrocatalytic activity of the resulting sol-gel composite catalyst toward methanol oxidation in an alkaline medium showed that this catalyst had mass activity greater than that of the biotemplate containing wild-type M13 and that of monometallic Pt and other Au-Pt nanostructures with different compositions and supports. M13 in the nanocomposite materials provided a close contact between the Au-Pt alloy nanostructures and rGO. In addition, it facilitated the availability of an OH - -rich environment to the catalyst. As a result, efficient electron transfer and a synergistic catalytic effect of the Au and Pt in the alloy nanostructures toward methanol oxidation were observed. Our nanocomposite synthesis on the novel biotemplate and its application might be useful for developing novel clean and green energy-generating and energy-storage materials.

Improved Power Conversion Efficiency of Inverted Organic Solar Cells by Incorporating Au Nanorods into Active Layer.

PubMed

He, Yeyuan; Liu, Chunyu; Li, Jinfeng; Zhang, Xinyuan; Li, Zhiqi; Shen, Liang; Guo, Wenbin; Ruan, Shengping

2015-07-29

This Research Article describes a cooperative plasmonic effect on improving the performance of organic solar cells. When Au nanorods(NRs) are incorporated into the active layers, the designed project shows superior enhanced light absorption behavior comparing with control devices, which leads to the realization of organic solar cell with power conversion efficiency of 6.83%, accounting for 18.9% improvement. Further investigations unravel the influence of plasmonic nanostructures on light trapping, exciton generation, dissociation, and charge recombination and transport inside the thin films devices. Moreover, the introduction of high-conductivity Au NRs improves electrical conductivity of the whole device, which contributes to the enhanced fill factor.

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

Dai, Sheng; Liu, Rui; Mahurin, Shannon Mark

A facile and versatile synthesis using dopamine as a carbon source gives hollow carbon spheres and yolk-shell Au{at}Carbon nanocomposites. The uniform nature of dopamine coatings and their high carbon yield endow the products with high structural integrity. The Au{at}C nanocomposites are catalytically active.

Ag@Au concave cuboctahedra: A unique probe for monitoring Au-catalyzed reduction and oxidation reactions by surface-enhanced Raman spectroscopy

DOE PAGES

Zhang, Jiawei; Winget, Sarah A.; Wu, Yiren; ...

2016-01-26

In this paper, we report a facile synthesis of Ag@Au concave cuboctahedra by titrating aqueous HAuCl4 into a suspension of Ag cuboctahedra in the presence of ascorbic acid (AA), NaOH, and poly(vinylpyrrolidone) (PVP) at room temperature. Initially, the Au atoms derived from the reduction of Au 3+ by AA are conformally deposited on the entire surface of a Ag cuboctahedron. Upon the formation of a complete Au shell, however, the subsequently formed Au atoms are preferentially deposited onto the Au{100} facets, resulting in the formation of a Ag@Au cuboctahedron with concave structures at the sites of {111} facets. The concavemore » cuboctahedra embrace excellent SERS activity that is more than 70-fold stronger than that of the original Ag cuboctahedra at an excitation wavelength of 785 nm. The concave cuboctahedra also exhibit remarkable stability in the presence of an oxidant such as H 2O 2 because of the protection by a complete Au shell. These two unique attributes enable in-situ SERS monitoring of the reduction of 4-nitrothiophenol (4-NTP) to 4-aminothiophenol (4-ATP) by NaBH4 through a 4,4'-dimercaptoazobenzene ( trans-DMAB) intermediate and the subsequent oxidation of 4-ATP back to trans-DMAB upon the introduction of H 2O 2.« less

Ag@Au concave cuboctahedra: A unique probe for monitoring Au-catalyzed reduction and oxidation reactions by surface-enhanced Raman spectroscopy

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

Zhang, Jiawei; Winget, Sarah A.; Wu, Yiren

In this paper, we report a facile synthesis of Ag@Au concave cuboctahedra by titrating aqueous HAuCl4 into a suspension of Ag cuboctahedra in the presence of ascorbic acid (AA), NaOH, and poly(vinylpyrrolidone) (PVP) at room temperature. Initially, the Au atoms derived from the reduction of Au 3+ by AA are conformally deposited on the entire surface of a Ag cuboctahedron. Upon the formation of a complete Au shell, however, the subsequently formed Au atoms are preferentially deposited onto the Au{100} facets, resulting in the formation of a Ag@Au cuboctahedron with concave structures at the sites of {111} facets. The concavemore » cuboctahedra embrace excellent SERS activity that is more than 70-fold stronger than that of the original Ag cuboctahedra at an excitation wavelength of 785 nm. The concave cuboctahedra also exhibit remarkable stability in the presence of an oxidant such as H 2O 2 because of the protection by a complete Au shell. These two unique attributes enable in-situ SERS monitoring of the reduction of 4-nitrothiophenol (4-NTP) to 4-aminothiophenol (4-ATP) by NaBH4 through a 4,4'-dimercaptoazobenzene ( trans-DMAB) intermediate and the subsequent oxidation of 4-ATP back to trans-DMAB upon the introduction of H 2O 2.« less

Microbial synthesis of core/shell gold/palladium nanoparticles for applications in green chemistry

PubMed Central

Deplanche, Kevin; Merroun, Mohamed L.; Casadesus, Merixtell; Tran, Dung T.; Mikheenko, Iryna P.; Bennett, James A.; Zhu, Ju; Jones, Ian P.; Attard, Gary A.; Wood, J.; Selenska-Pobell, Sonja; Macaskie, Lynne E.

2012-01-01

We report a novel biochemical method based on the sacrificial hydrogen strategy to synthesize bimetallic gold (Au)–palladium (Pd) nanoparticles (NPs) with a core/shell configuration. The ability of Escherichia coli cells supplied with H2 as electron donor to rapidly precipitate Pd(II) ions from solution is used to promote the reduction of soluble Au(III). Pre-coating cells with Pd(0) (bioPd) dramatically accelerated Au(III) reduction, with the Au(III) reduction rate being dependent upon the initial Pd loading by mass on the cells. Following Au(III) addition, the bioPd–Au(III) mixture rapidly turned purple, indicating the formation of colloidal gold. Mapping of bio-NPs by energy dispersive X-ray microanalysis suggested Au-dense core regions and peripheral Pd but only Au was detected by X-ray diffraction (XRD) analysis. However, surface analysis of cleaned NPs by cyclic voltammetry revealed large Pd surface sites, suggesting, since XRD shows no crystalline Pd component, that layers of Pd atoms surround Au NPs. Characterization of the bimetallic particles using X-ray absorption spectroscopy confirmed the existence of Au-rich core and Pd-rich shell type bimetallic biogenic NPs. These showed comparable catalytic activity to chemical counterparts with respect to the oxidation of benzyl alcohol, in air, and at a low temperature (90°C). PMID:22399790

Highly sensitive electrochemical detection of human telomerase activity based on bio-barcode method.

PubMed

Li, Ying; Liu, Bangwei; Li, Xia; Wei, Qingli

2010-07-15

In the present study, an electrochemical method for highly sensitive detection of human telomerase activity was developed based on bio-barcode amplification assay. Telomerase was extracted from HeLa cells, then the extract was mixed with telomerase substrate (TS) primer to perform extension reaction. The extension product was hybridized with the capture DNA immobilized on the Au electrode and then reacted with the signal DNA on Au nanoparticles to form a sandwich hybridization mode. Electrochemical signals were generated by chronocoulometric interrogation of [Ru(NH(3))(6)](3+) that quantitatively binds to the DNA on Au nanoparticles via electrostatic interaction. This method can detect the telomerase activity from as little as 10 cultured cancer cells without the polymerase chain reaction (PCR) amplification of telomerase extension product. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Americium alloys with gold and copper

NASA Astrophysics Data System (ADS)

Radchenko, V. M.; Ryabinin, M. A.; Chernakova, T. A.; Tomilin, S. V.

2010-03-01

Presented are results of the production and X-ray examination of micro-samples of americium-241 compounds with gold and copper produced by high-temperature condensation of metal americium vapor onto corresponding substrates. No mutual solubility of the investigated system components was revealed at room temperature. The following three intermetallic compounds were revealed in the Am-Au system: Au6Am with tetragonal lattice of the Au6Sm structural type, AuAm with orthorhombic lattice of the CuCe structural type and AuAm with cubic lattice. The Am-Cu system showed the intermetallic compound Cu5Am (Cu7Am) with a hexagonal lattice of the Cu5Ca(Cu7Tb) structure type. An effect of the 241Am nuclide alpha-activity on the crystal structure of the produced intermetallide was studied.

Highly active surface-enhanced Raman scattering (SERS) substrates based on gold nanoparticles infiltrated into SiO2 inverse opals

NASA Astrophysics Data System (ADS)

Ankudze, Bright; Philip, Anish; Pakkanen, Tuula T.; Matikainen, Antti; Vahimaa, Pasi

2016-11-01

SiO2 inverse opal (IO) films with embedded gold nanoparticles (AuNPs) for surface-enhanced Raman scattering (SERS) application are reported. SiO2 IO films were loaded with AuNPs by a simple infiltration in a single cycle to form Au-SiO2 IOs. The optical property and the morphology of the Au-SiO2 IO substrates were characterized; it was observed that they retained the Bragg diffraction of SiO2 IO and the localized surface plasmon resonance (LSPR) of AuNPs. The SERS property of the Au-SiO2 IO substrates were studied with methylene blue (MB) and 4-aminothiophenol (4-ATP). The SERS enhancement factors were 107 and 106 for 4-ATP and MB, respectively. A low detection limit of 10-10 M for 4-ATP was also obtained with the Au-SiO2 IO substrate. A relative standard deviation of 18.5% for the Raman signals intensity at 1077 cm-1 for 4-ATP shows that the Au-SiO2 IO substrates have good signal reproducibility. The results of this study indicate that the Au-SiO2 IO substrates can be used in sensing and SERS applications.

Important factors for cell-membrane permeabilization by gold nanoparticles activated by nanosecond-laser irradiation

PubMed Central

Yao, Cuiping; Rudnitzki, Florian; Hüttmann, Gereon; Zhang, Zhenxi; Rahmanzadeh, Ramtin

2017-01-01

Purpose Pulsed-laser irradiation of light-absorbing gold nanoparticles (AuNPs) attached to cells transiently increases cell membrane permeability for targeted molecule delivery. Here, we targeted EGFR on the ovarian carcinoma cell line OVCAR-3 with AuNPs. In order to optimize membrane permeability and to demonstrate molecule delivery into adherent OVCAR-3 cells, we systematically investigated different experimental conditions. Materials and methods AuNPs (30 nm) were functionalized by conjugation of the antibody cetuximab against EGFR. Selective binding of the particles was demonstrated by silver staining, multiphoton imaging, and fluorescence-lifetime imaging. After laser irradiation, membrane permeability of OVCAR-3 cells was studied under different conditions of AuNP concentration, cell-incubation medium, and cell–AuNP incubation time. Membrane permeability and cell viability were evaluated by flow cytometry, measuring propidium iodide and fluorescein isothiocyanate–dextran uptake. Results Adherently growing OVCAR-3 cells can be effectively targeted with EGFR-AuNP. Laser irradiation led to successful permeabilization, and 150 kDa dextran was successfully delivered into cells with about 70% efficiency. Conclusion Antibody-targeted and laser-irradiated AuNPs can be used to deliver molecules into adherent cells. Efficacy depends not only on laser parameters but also on AuNP:cell ratio, cell-incubation medium, and cell–AuNP incubation time. PMID:28848345

Theoretical study on the photocatalytic properties of graphene oxide with single Au atom adsorption

NASA Astrophysics Data System (ADS)

Ju, Lin; Dai, Ying; Wei, Wei; Li, Mengmeng; Jin, Cui; Huang, Baibiao

2018-03-01

The photocatalytic properties of graphene oxide (GO) with single Au atom adsorption are studied via the first-principles calculations based on the density functional theory. The present study addresses the origin of enhancement in photocatalytic efficiency of GO derived from single Au atom depositing. Compared with the clean one, the work function of the single Au atom adsorbed GO is lowered due to the charge transfer from Au to GO, indicating enhanced surface activity. The Au atom plays as an electron trapping center and a mediating role in charge transfer from photon excited GO to target species. The photogenerated electron-hole pairs can be separated effectively. For the GO configuration with atomic Au dispersion, there are some states introduced in the band gap, which are predominantly composed of Au 6s states. Through the in-gap state, the photo-generated electron transfer from the valence band of clean GO to the conductive band more easily. In addition, the reduction of the gap in the system is also presented in the current work, which indicates that the single Au atom adsorption improves light absorption for the GO based photocatalyst. These theoretical results are valuable for the future applications of GO materials as photocatalyst for water splitting.

Study of Colloidal Gold Synthesis Using Turkevich Method

NASA Astrophysics Data System (ADS)

Rohiman, Asep; Anshori, Isa; Surawijaya, Akhmadi; Idris, Irman

2011-12-01

The synthesis of colloidal gold or Au-nanoparticles (Au-NPs) by reduction of chloroauric acid (HAuCl4) with sodium citrate was done using Turkevich method. We prepare HAuCl4 solution by dissolving gold wires (99.99%) into aqua regia solution. To initiate the Au-NPs synthesis 0.17 ml of 1 % chloroauric acid solution was heated to the boiling point and then 10 ml of 1 % sodium citrate was added to the boiling solution with a constant stirring in order to maintain a homogenous solution. A color of faint gray was observed in the solution approximately one minute and in a period of 2-3 minutes later, it further darkened to deep wine and red color. It showed that the gold solution has reduced to Au-NPs. The effect of process temperature on the size of Au-NPs prepared by sodium citrate reduction has also been investigated. With increasing temperature of Au-NPs synthesis, smaller-size Au-NPs were obtained. The higher temperatures shorten the time needed to achieve activation energy for reduction process. The resulting Au-NPs has been characterized by scanning Electron Microscope (SEM), showing the size of Au-NPs average diameter is ˜20-27 nm. The resulting colloidal gold will be used as catalyst for Si nanowires growth using VLS method.

Kinetically controlled synthesis of Au102(SPh)44 nanoclusters and catalytic application.

PubMed

Chen, Yongdong; Wang, Jin; Liu, Chao; Li, Zhimin; Li, Gao

2016-05-21

We here explore a kinetically controlled synthetic protocol for preparing solvent-solvable Au102(SPh)44 nanoclusters which are isolated from polydispersed gold nanoclusters by solvent extraction and size exclusion chromatography (SEC). The as-obtained Au102(SPh)44 nanoclusters are determined by matrix-assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) mass spectrometry, in conjunction with UV-vis spectroscopy and thermogravimetric analysis (TGA). However, Au99(SPh)42, instead of Au102(SPh)44, is yielded when the polydispersed gold nanoclusters are etched in the presence of excess thiophenol under thermal conditions (e.g., 80 °C). Interestingly, the Au102(SPh)44 nanoclusters also can convert to Au99(SPh)42 with equivalent thiophenol ligands, evidenced by the analyses of UV-vis and MALDI mass spectrometry. Finally, the TiO2-supported Au102(SPh)44 nanocluster catalyst is investigated in the selective oxidation of sulfides into sulfoxides by the PhIO oxidant and gives rise to high catalytic activity (e.g., 80-99% conversion of R-S-R' sulfides with 96-99% selectivity for R-S([double bond, length as m-dash]O)-R' sulfoxides). The Au102(SPh)44/TiO2 catalyst also shows excellent recyclability in the sulfoxidation process.

Dual structural transition in small nanoparticles of Cu-Au alloy

NASA Astrophysics Data System (ADS)

Gafner, Yuri; Gafner, Svetlana; Redel, Larisa; Zamulin, Ivan

2018-02-01

Cu-Au alloy nanoparticles are known to be widely used in the catalysis of various chemical reactions as it was experimentally defined that in many cases the partial substitution of copper with gold increases catalytic activity. However, providing the reaction capacity of alloy nanoparticles the surface electronic structure strongly depends on their atomic ordering. Therefore, to theoretically determine catalytic properties, one needs to use a most real structural model complying with Cu-Au nanoparticles under various external influences. So, thermal stability limits were studied for the initial L12 phase in Cu3Au nanoalloy clusters up to 8.0 nm and Cu-Au clusters up to 3.0 nm at various degrees of Au atom concentration, with molecular dynamics method using a modified tight-binding TB-SMA potential. Dual structural transition L12 → FCC and further FCC → Ih is shown to be possible under the thermal factor in Cu3Au and Cu-Au clusters with the diameter up to 3.0 nm. The temperature of the structural transition FCC → Ih is established to decrease for small particles of Cu-Au alloy under the increase of Au atom concentration. For clusters with this structural transition, the melting point is found to be a linear increasing function of concentration, and for clusters without FCC → Ih structural transition, the melting point is a linear decreasing function of Au content. Thus, the article shows that doping Cu nanoclusters with Au atoms allows to control the forming structure as well as the melting point.

Morphological effects on the selectivity of intramolecular versus intermolecular catalytic reaction on Au nanoparticles.

PubMed

Wang, Dan; Sun, Yuanmiao; Sun, Yinghui; Huang, Jing; Liang, Zhiqiang; Li, Shuzhou; Jiang, Lin

2017-06-14

It is hard for metal nanoparticle catalysts to control the selectivity of a catalytic reaction in a simple process. In this work, we obtain active Au nanoparticle catalysts with high selectivity for the hydrogenation reaction of aromatic nitro compounds, by simply employing spine-like Au nanoparticles. The density functional theory (DFT) calculations further elucidate that the morphological effect on thermal selectivity control is an internal key parameter to modulate the nitro hydrogenation process on the surface of Au spines. These results show that controlled morphological effects may play an important role in catalysis reactions of noble metal NPs with high selectivity.

Enhanced photoelectric performance in self-powered UV detectors based on ZnO nanowires with plasmonic Au nanoparticles scattered electrolyte

NASA Astrophysics Data System (ADS)

Zeng, Yiyu; Ye, Zhizhen; Lu, Bin; Dai, Wei; Pan, Xinhua

2016-04-01

Vertically aligned ZnO nanowires (NWs) were grown on a fluorine-doped tin-oxide-coated glass substrate by a hydrothermal method. Au nanoparticles were well dispersed in the mixed solution of ethanol and deionized water. A simple self-powered ultraviolet detector based on solid-liquid heterojunction was fabricated, utilizing ZnO NWs as active photoanode and such prepared mixed solution as electrolyte. The introduction of Au nanoparticles results in considerable improvements in the responsivity and sensitivity of the device compared with the one using deionized water as electrolyte, which is attributed to the enhanced light harvesting by Au nanoparticles.

Surface tension estimation of high temperature melts of the binary alloys Ag-Au

NASA Astrophysics Data System (ADS)

Dogan, Ali; Arslan, Hüseyin

2017-11-01

Surface tension calculation of the binary alloys Ag-Au at the temperature of 1381 K, where Ag and Au have similar electronic structures and their atomic radii are comparable, are carried out in this study using several equations over entire composition range of Au. Apparently, the deviations from ideality of the bulk solutions, such as activities of Ag and Au are small and the maximum excess Gibbs free energy of mixing of the liquid phase is for instance -4500 J/mol at XAu = 0.5. Besides, the results obtained in Ag-Au alloys that at a constant temperature the surface tension increases with increasing composition while the surface tension decreases as the temperature increases for entire composition range of Au. Although data about surface tension of the Ag-Au alloy are limited, it was possible to make a comparison for the calculated results for the surface tension in this study with the available experimental data. Taken together, the average standard error analysis that especially the improved Guggenheim model in the other models gives the best agreement along with the experimental results at temperature 1383 K although almost all models are mutually in agreement with the other one.

Centaurs and Activity Beyond the Water Sublimation Zone

NASA Astrophysics Data System (ADS)

Jewitt, David

2017-08-01

Centaurs are icy objects in dynamical transition between the Kuiper belt, where they originate, and the Jupiter family comets. Water ice in inward drifting Centaurs should begin to sublimate measurably when their perihelion reaches the orbit of Jupiter (5 AU). Instead, a fraction of Centaurs become active (have a cometary appearance) even with perihelia at Saturn (10 AU). Of the many suggestions made for the origin of this distant activity, the current favorite and the one with the largest impact on cometary science is the crystallization of amorphous water ice. Amorphous ice is an excellent carrier of supervolatiles (e.g. CO, N2) which are released upon the exothermic transition to crystalline ice. If Centaur ice is amorphous, then so must be Kuiper belt ice, setting strong constraints on the internal temperature vs. time history of the Kuiper belt objects. If the crystallization hypothesis is correct, we should never find an active Centaur with a perihelion substantially beyond the so-called crystallization line at about 12 AU (because temperatures there are too low to trigger crystallization). We propose a simple search for distant activity in Centaurs with perihelia 15 to 20 AU, in which crystallization cannot occur, in order to challenge the crystallization hypothesis. The search is made possible by the tight and stable point spread function and sensitivity to near-nucleus coma of HST.

Highly Active Au/δ-MoC and Cu/δ-MoC Catalysts for the Conversion of CO2: The Metal/C Ratio as a Key Factor Defining Activity, Selectivity, and Stability.

PubMed

Posada-Pérez, Sergio; Ramírez, Pedro J; Evans, Jaime; Viñes, Francesc; Liu, Ping; Illas, Francesc; Rodriguez, José A

2016-07-06

The ever growing increase of CO2 concentration in the atmosphere is one of the main causes of global warming. Thus, CO2 activation and conversion toward valuable added compounds is a major scientific challenge. A new set of Au/δ-MoC and Cu/δ-MoC catalysts exhibits high activity, selectivity, and stability for the reduction of CO2 to CO with some subsequent selective hydrogenation toward methanol. Sophisticated experiments under controlled conditions and calculations based on density functional theory have been used to study the unique behavior of these systems. A detailed comparison of the behavior of Au/β-Mo2C and Au/δ-MoC catalysts provides evidence of the impact of the metal/carbon ratio in the carbide on the performance of the catalysts. The present results show that this ratio governs the chemical behavior of the carbide and the properties of the admetal, up to the point of being able to switch the rate and mechanism of the process for CO2 conversion. A control of the metal/carbon ratio paves the road for an efficient reutilization of this environmental harmful greenhouse gas.

Highly active Au/δ-MoC and Cu/δ-MoC catalysts for the conversion of CO 2: The metal/C ratio as a key factor defining activity, selectivity, and stability

DOE PAGES

Posada-Pérez, Sergio; Ramírez, Pedro J.; Evans, Jaime; ...

2016-06-16

The ever growing increase of CO 2 concentration in the atmosphere is one of the main causes of global warming. Thus, CO 2 activation and conversion toward valuable added compounds is a major scientific challenge. A new set of Au/δ-MoC and Cu/δ-MoC catalysts exhibits high activity, selectivity, and stability for the reduction of CO 2 to CO with some subsequent selective hydrogenation toward methanol. Sophisticated experiments under controlled conditions and calculations based on density functional theory have been used to study the unique behavior of these systems. A detailed comparison of the behavior of Au/β-Mo 2C and Au/δ-MoC catalysts providesmore » evidence of the impact of the metal/carbon ratio in the carbide on the performance of the catalysts. The present results show that this ratio governs the chemical behavior of the carbide and the properties of the admetal, up to the point of being able to switch the rate and mechanism of the process for CO 2 conversion. Here, a control of the metal/carbon ratio paves the road for an efficient reutilization of this environmental harmful greenhouse gas.« less

TS-1 supported highly dispersed sub-5 nm gold nanoparticles toward direct propylene epoxidation using H2 and O2

NASA Astrophysics Data System (ADS)

Li, Naixu; Chen, Yong; Shen, Quanhao; Yang, Bin; Liu, Ming; Wei, Lingfei; Tian, Wei; Zhou, Jiancheng

2018-05-01

We report a simple and efficient method for the preparation of highly dispersed Au nanoparticles (< 5 nm) on TS-1 substrate. The synthesis relies on the use of NaBH4 as a reductant for rapid Au atom generation, as well as PVA as a capping agent confining the particle size and dispersion. The samples were characterized by N2 physisorption, inductively coupled plasma mass spectrometry, power X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, CO pulse chemisorption and thermogravimetric analysis. The size of Au particles can be controlled in the range of 3-5 nm. The supported catalyst shows both good activity and selectivity for propylene oxide (PO) generation from direct propylene epoxidation. An optimal performance with PO formation rate of 102.94 gPO h-1 kg-1cat and selectivity of 84.83% is achieved over 2.0 wt% Au/TS-1 catalyst, which is prepared by controlling PVA/Au3+ mass ratio of 1.5/1 and NaBH4/Au3+ mole ratio of 5/1. After 50 h test at 200 °C, no significant decrement of both catalytic activity and PO selectivity can be observed, indicating the excellent thermally stability of the catalyst. Furthermore, a possible reaction mechanism is described on basis of the previous researches and our experimental results.

Colorimetric determination of glutathione in human serum and cell lines by exploiting the peroxidase-like activity of CuS-polydopamine-Au composite.

PubMed

Wang, Yanying; Liu, Yaqin; Ding, Fang; Zhu, Xiaoyan; Yang, Li; Zou, Ping; Rao, Hanbing; Zhao, Qingbiao; Wang, Xianxiang

2018-06-07

In this study, we developed a simple colorimetric approach to detect glutathione (GSH). The proposed approach is based on the ability of CuS-PDA-Au composite material to catalytically oxidize 3,3',5,5'-tetramethylbenzidine (TMB) to ox-TMB to induce a blue color with an absorption peak centered at 652 nm. However, the introduction of GSH can result in a decrease in oxidized TMB; similarly, it can combine with Au nanoparticles (Au NPs) on the surface of CuS-PDA-Au composite material. Both approaches can result in a fading blue color and a reduction of the absorbance at 652 nm. Based on this above, we proposed a technique to detect GSH quantitatively and qualitatively through UV-Vis spectroscopy and naked eye, respectively. This approach demonstrates a low detection limit of 0.42 μM with a broad detection range of 5 × 10 -7 -1 × 10 -4  M with the assistance of UV-Vis spectroscopy. More importantly, this approach is convenient and rapid. This method was successfully applied to GSH detection in human serum and cell lines. Graphical abstract A colorimetric approach has been developed by exploiting the peroxidase-like activity of CuS-polydopamine-Au composite for sensitive glutathione detection.

Phytosynthesis of stable Au, Ag and Au-Ag alloy nanoparticles using J. Sambac leaves extract, and their enhanced antimicrobial activity in presence of organic antimicrobials

NASA Astrophysics Data System (ADS)

Yallappa, S.; Manjanna, J.; Dhananjaya, B. L.

2015-02-01

A green chemistry approach for the synthesis of Au, Ag and Au-Ag alloy nanoparticles (NPs) using the corresponding metal precursors and Jasminum sambac leaves extract as both reducing and capping media, under microwave irradiation, is reported. During the formation, as expected, the reaction mixture shows marginal decrease in pH and an increase in solution potential. The formation of NPs is evident from their surface plasmon resonance (SPR) peak observed at ∼555 nm for Au, ∼435 nm for Ag and ∼510 nm for Au-Ag alloy. The XRD pattern shows fcc structure while the FTIR spectra indicate the presence of plant residues adsorbed on these NPs. Such a bio-capping of NPs is characterized by their weight loss, ∼35% due to thermal degradation of biomass, as observed in TG analysis. The colloidal dispersion of NPs is stable for about 6 weeks. The near spherical shape of NPs (ϕ20-50 nm) is observed by FE-SEM/TEM images and EDAX gives the expected elemental composition. Furthermore, these NPs showed enhanced antimicrobial activity (∼1-4-fold increase in zone of inhibition) in combination with antimicrobials against test strains. Thus, the phytosynthesized NPs could be used as effective growth inhibitors for various microorganisms.

Gold Nanoparticles-enabled Efficient Dual Delivery of Anticancer Therapeutics to HeLa Cells

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

Farooq, Muhammad U.; Novosad, Valentyn; Rozhkova, Elena A.

Colloidal gold nanoparticles (AuNPs) are of interest as non-toxic carriers for drug delivery owing to their advanced properties, such as extensive surface-to-volume ratio and possibilities for tailoring their charge, hydrophilicity and functionality through surface chemistries. To date, various biocompatible polymers have been used for surface decoration of AuNPs to enhance their stability, payloads capacity and cellular uptake. This study describes a facile one-step method to synthesize stable AuNPs loaded with combination of two anticancer therapeutics, -bleomycin and doxorubicin. Anticancer activities, cytotoxicity, uptake and intracellular localization of the AuNPs were demonstrated in HeLa cells. We show that the therapeutic efficacy ofmore » the nanohybrid drug was strongly enhanced by the active targeting by the nanoscale delivery system to HeLa cells with a significant decrease of the half-maximal effective drug concentration, through blockage of HeLa cancer cell cycle. These results provide rationale for further progress of AuNPs-assisted combination chemotherapy using two drugs at optimized effective concentrations which act via different mechanisms thus decreasing possibilities of development of the cancer drug resistance, reduction of systemic drug toxicity and improvement of outcomes of chemotherapy.« less

Microfluidic Platform for High-throughput Screening of Leach Chemistry.

PubMed

Yang, Die; Priest, Craig

2018-06-20

We demonstrate an optofluidic screening platform for studying thiosulfate leaching of Au in a transparent microchannel. The approach permits in situ (optical) monitoring of Au thickness, reduced reagent use, rapid optimization of reagent chem-istry, screening of temperature, and determination of the activation energy. The results demonstrate the critical importance of the (1) preparation and storage of the leach solution, (2) deposition and annealing of the Au film, and (3) lixiviant chem-istry. The density of sputter deposited Au films decreased with depth resulting in accelerating leach rates during experiments. Atomic leach rates were determined and were constant throughout each experiment. Annealing above 270 °C was found to prevent leaching, which can be attributed to diffusion of the chromium adhesion layer into the Au film. The optofluidic analysis revealed leach rates that are sensitive to the stoichiometric ratio of thiosulphate, ammonia and copper in the leach solution, and optimized for 10 mM CuSO 4 , 1 M Na 2 S 2 O 3 and 1 M NH 4 OH. The temperature dependence of the leach rate gave an apparent activation energy of ~ 40 kJ.mol -1 , based on Arrhenius' relationship.

Gold Nanoparticles-enabled Efficient Dual Delivery of Anticancer Therapeutics to HeLa Cells

DOE PAGES

Farooq, Muhammad U.; Novosad, Valentyn; Rozhkova, Elena A.; ...

2018-02-13

Colloidal gold nanoparticles (AuNPs) are of interest as non-toxic carriers for drug delivery owing to their advanced properties, such as extensive surface-to-volume ratio and possibilities for tailoring their charge, hydrophilicity and functionality through surface chemistries. To date, various biocompatible polymers have been used for surface decoration of AuNPs to enhance their stability, payloads capacity and cellular uptake. This study describes a facile one-step method to synthesize stable AuNPs loaded with combination of two anticancer therapeutics, -bleomycin and doxorubicin. Anticancer activities, cytotoxicity, uptake and intracellular localization of the AuNPs were demonstrated in HeLa cells. We show that the therapeutic efficacy ofmore » the nanohybrid drug was strongly enhanced by the active targeting by the nanoscale delivery system to HeLa cells with a significant decrease of the half-maximal effective drug concentration, through blockage of HeLa cancer cell cycle. These results provide rationale for further progress of AuNPs-assisted combination chemotherapy using two drugs at optimized effective concentrations which act via different mechanisms thus decreasing possibilities of development of the cancer drug resistance, reduction of systemic drug toxicity and improvement of outcomes of chemotherapy.« less

Gold nanorods-enhanced rhodamine B-permanganate chemiluminescence and its analytical application.

PubMed

Hassanzadeh, Javad; Amjadi, Mohammad; Manzoori, Jamshid L; Sorouraddin, Mohammad Hossein

2013-04-15

A novel enhanced chemiluminescence system was developed by applying gold nanorods (Au NRs) as catalysts in rhodamine B-permanganate reaction. Au NRs with three different aspect ratios were synthesized by seed mediated growth method and characterized by UV-Vis spectra and transmission electron microscopy. It was demonstrated that Au NRs have much higher catalytic effect than spherical nanoparticles on rhodamine B-permanganate chemiluminescence reaction. Among various sizes of Au NRs, those with average aspect ratio of 3.0 were found to have the most remarkable catalytic activity. As an analytical application of the new chemiluminescence system, albumin as a model protein was quantified based on its interaction with NRs. Albumin binds to Au NRs active surfaces and inhibits their catalytic action and therefore decreases the intensity of chemiluminescence. This diminution effect is linearly related to the concentration of the human and bovine serum albumin over the ranges of 0.45-90 and 0.75-123 nmol L(-1), respectively with the corresponding limits of detection of 0.18 and 0.30 nmol L(-1). The method was successfully applied to the determination of albumin in human and bovine serum samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Nanomolar electrochemical detection of caffeic acid in fortified wine samples based on gold/palladium nanoparticles decorated graphene flakes.

PubMed

Thangavelu, Kokulnathan; Raja, Nehru; Chen, Shen-Ming; Liao, Wei-Cheng

2017-09-01

Amalgamation of noble metal nanomaterials on graphene flakes potentially paves one way to improve their physicochemical properties. This paper deals with the simultaneous electrochemical deposition of gold and palladium nanoparticles on graphene flakes (Au/PdNPs-GRF) for the sensitive determination of caffeic acid (CA). The physiochemical properties of the prepared Au/PdNPs-GRF was characterized by using numerous analytical techniques such as scanning electron microscopy, electron dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, X-ray powder diffraction, Raman spectroscopy and electrochemical impedance spectroscopy. The enhanced electrochemical determination of CA at Au/PdNPs deposition on GRF were studied by using cyclic voltammetry and differential pulse voltammetry. In results, Au/PdNPs-GRF electrode exhibited an excellent electrocatalytic activity towards CA with wide linear range and low limit of detection of 0.03-938.97µM and 6nM, respectively. Eventually, the Au/PdNPs-GRF was found as a selective and stable active material for the sensing of CA. In addition, the proposed sensor showed the adequate results in real sample analysis. Copyright © 2017 Elsevier Inc. All rights reserved.

Highly efficient visible-light driven photocatalytic hydrogen production from a novel Z-scheme Er3+:YAlO3/Ta2O5-V5+||Fe3+-TiO2/Au coated composite

NASA Astrophysics Data System (ADS)

Wang, Guowei; Ma, Xue; Wei, Shengnan; Li, Siyi; Qiao, Jing; Wang, Jun; Song, Youtao

2018-01-01

In this work, the preparation of a novel Z-scheme photocatalyst, Er3+:YAlO3/Ta2O5-V5+||Fe3+-TiO2/Au coated composite, for visible-light photocatalytic hydrogen production is reported for the first time. In this photocatalyst, Au nanoparticles as conduction band co-catalyst provide more active sites to enrich electrons. Ta2O5-V5+||Fe3+-TiO2 as composite redox cycle system thoroughly separates the photo-generated electrons and holes. In addition, Er3+:YAlO3 as up-conversion luminescence agent (from visible-light to ultraviolet-light) provides enough ultraviolet-light for satisfying the energy demand of wide band-gap semiconductors (TiO2 and Ta2O5). The photocatalytic hydrogen production can be achieved from methanol as sacrificial agent (electron donor) under visible-light irradiation. The main influence factors such as initial solution pH and molar ratio of TiO2 and Ta2O5 on visible-light photocatalytic hydrogen production activity of Er3+:YAlO3/Ta2O5-V5+||Fe3+-TiO2/Au coated composite are discussed in detail. The results show that the Er3+:YAlO3/Ta2O5-V5+||Fe3+-TiO2/Au coated composite with 1.0:0.5 M ratio of TiO2 and Ta2O5 in methanol aqueous solution at pH = 6.50 displays the highest photocatalytic hydrogen production activity. Furthermore, a high level of photocatalytic activity can be still maintained within three cycles under the same conditions. It implies that the prepared Z-scheme Er3+:YAlO3/Ta2O5-V5+||Fe3+-TiO2/Au coated composite may be a promising photocatalyst utilizing solar energy for hydrogen production.

Enhanced photocatalytic CO2 reduction to CH4 over separated dual co-catalysts Au and RuO2

NASA Astrophysics Data System (ADS)

Dong, Chunyang; Hu, Songchang; Xing, Mingyang; Zhang, Jinlong

2018-04-01

A spatially separated, dual co-catalyst photocatalytic system was constructed by the stepwise introduction of RuO2 and Au nanoparticles (NPs) at the internal and external surfaces of a three dimensional, hierarchically ordered TiO2-SiO2 (HTSO) framework (the final photocatalyst was denoted as Au/HRTSO). Characterization by HR-TEM, EDS-mapping, XRD and XPS confirmed the existence and spatially separated locations of Au and RuO2. In CO2 photocatalytic reduction (CO2PR), Au/HRTSO (0.8%) shows the optimal performance in both the activity and selectivity towards CH4; the CH4 yield is almost twice that of the singular Au/HTSO or HRTSO (0.8%, weight percentage of RuO2) counterparts. Generally, Au NPs at the external surface act as electron trapping agents and RuO2 NPs at the inner surface act as hole collectors. This advanced spatial configuration could promote charge separation and transfer efficiency, leading to enhanced CO2PR performance in both the yield and selectivity toward CH4 under simulated solar light irradiation.

Highly reproducible surface-enhanced Raman scattering-active Au nanostructures prepared by simple electrodeposition: origin of surface-enhanced Raman scattering activity and applications as electrochemical substrates.

PubMed

Choi, Suhee; Ahn, Miri; Kim, Jongwon

2013-05-24

The fabrication of effective surface-enhanced Raman scattering (SERS) substrates has been the subject of intensive research because of their useful applications. In this paper, dendritic gold (Au) rod (DAR) structures prepared by simple one-step electrodeposition in a short time were examined as an effective SERS-active substrate. The SERS activity of the DAR surfaces was compared to that of other nanostructured Au surfaces with different morphologies, and its dependence on the structural variation of DAR structures was examined. These comparisonal investigations revealed that highly faceted sharp edge sites present on the DAR surfaces play a critical role in inducing a high SERS activity. The SERS enhancement factor was estimated to be greater than 10(5), and the detection limit of rhodamine 6G at DAR surfaces was 10(-8)M. The DAR surfaces exhibit excellent spot-to-spot and substrate-to-substrate SERS enhancement reproducibility, and their long-term stability is very good. It was also demonstrated that the DAR surfaces can be effectively utilized in electrochemical SERS systems, wherein a reversible SERS behavior was obtained during the cycling to cathodic potential regions. Considering the straightforward preparation of DAR substrates and the clean nature of SERS-active Au surfaces prepared in the absence of additives, we expect that DAR surfaces can be used as cost-effective SERS substrates in analytical and electrochemical applications. Copyright © 2013 Elsevier B.V. All rights reserved.

Non-covalent binding of nucleic acids with gold nanoparticles provides their stability and effective desorption in environment mimicking biological media.

PubMed

Epanchintseva, Anna; Dolodoev, Anton; Grigor'eva, Alina; Chelobanov, Boris; Pyshnyi, Dmitrii; Ryabchikova, Elena; Pyshnaya, Inna

2018-08-31

The ability of gold nanoparticles to bind different substances has resulted in the high interest of researchers determining their usage as a promising carrier of various biological substances including nucleic acids (NAs) for therapeutic applications. Most publications report covalent binding (conjugation) of an NA to spherical AuNPs via the Au-S bond. In this work, we obtained non-covalent associates of different ssDNA, ssRNA and siRNAs with spherical gold nanoparticles (AuNPs) and examined their physico-chemical properties and stability in media mimicking intracellular space (bacterial 'cytosol') and cell culture media (10% FBS in DMEM). The 'cytosol' was obtained from E. coli and possessed nuclease activity. For the first time, we used the phosphoryl guanidine (dimethylimidazolidin-2-imine, Dmi) group for modification of 3'-ends to enhance the stability of ssRNAs and siRNAs against nuclease destruction. Trying to evaluate the material balance, we analyzed the whole nucleotide species obtained after incubation of NA-AuNPs associates in 'cytosol' and FBS and evaluated the degree of NAs destruction, a share of full-size NAs remained on the surface of the AuNPs and in the solution. Native ss- and siRNAs, both free and in composition of non-covalent associates with AuNPs, were less resistant to degrading factors than ssDNA. The introduction of two Dmi-groups into the ssDNA increased its stability in 'cytosol' three times within 2.5 h. Dmi-modified siRNAs in non-covalent associates with AuNPs were two times more stable than unmodified siRNA within 4 h. We showed that non-covalent siRNA-AuNPs associates serve as a kind of storage for full-size NAs and thereby prolong their presence in nuclease-active media. Our study showed that non-covalent binding of siRNAs with a surface of AuNPs provides desorption of both strands, which is necessary for siRNA functioning in living cells, and could be considered as an important way to construct siRNA and ssDNA delivery systems based on AuNPs.

Au/Ti resistors used for Nb/Pb-alloy Josephson junctions. II. Thermal stability

NASA Astrophysics Data System (ADS)

Murakami, Masanori; Kim, K. K.

1984-10-01

In the preceding paper bilayered Au/Ti resistors were found to have excellent electrical stability during storage at room temperature after preannealing at an elevated temperature, which is essential to design logic and memory circuits of Nb/Pb-alloy Josephson junction devices. The resistors could contact directly with the Pb-alloy control lines in which Pb and In atoms which are known to intermix easily with Au atoms are contained. Since Pb and In atoms in the control lines are separated from Au atoms of the resistors by thin Ti layers, thermal stability at the contacts is a major concern for use of the Au/Ti resistor material in the Josephson devices. In the present study, surface morphology change and diffusion mechanism at the resistor/control-line contacts were studied using x-ray diffraction and scanning electron microscopy for square-shaped Au/Ti resistors covered by Pb-In layers. The samples were isothermally annealed at temperatures ranging from 353 to 423 K. The diffusion did not occur immediately after annealing at these temperatures. After the incubation period, the interdiffusion was observed to initiate at the edges of the resistors facing to the center of the cathode. Significant amounts of the In atoms in the Pb-In layers were observed to diffuse into the Au layers of the resistors, forming AuIn2 compounds under the Ti layers. By measuring growth rates of the AuIn2 layers, the diffusion coefficients and the activation energy for the layer growth were determined. Also, by analyzing changes in the In concentration in the Pb-In layers during annealing, interdiffusion coefficients of In atoms in the Pb-In layers were determined using a computer simulation technique. The activation energy was about 1.1 eV. Since these diffusion coefficients were found to be very close to those determined previously in bulk materials, the diffusion kinetics is believed to be controlled by the lattice diffusion. Based on the present results, several methods to reduce the interdiffusion between Pb-alloy and Au/Ti resistors were proposed.

Toxicity of PAMAM-coated gold nanoparticles in different unicellular models.

PubMed

Perreault, François; Melegari, Silvia Pedroso; Fuzinatto, Cristiane Funghetto; Bogdan, Nicoleta; Morin, Mario; Popovic, Radovan; Matias, William Gerson

2014-03-01

Polyamidoamine (PAMAM) dendrimers are used for many pharmaceutical and biomedical applications. However, the toxicological risks of several PAMAM-based compounds are still not fully evaluated, despite evidences of PAMAM deleterious effects on biological membranes, leading to toxicity. In this report, we investigated the toxicity of generation 0 PAMAM-coated gold nanoparticles (AuG0 NPs) in four different models to determine how different cellular systems are affected by PAMAM-coated NPs. Toxicity was evaluated in two mammalian cell lines, Neuro 2A and Vero, in the green alga Chlamydomonas reinhardtii and the bacteria Vibrio fischeri. AuG0 NP treatments reduced cell metabolic activity in algal and bacterial cells, measured by esterase enzymatic activity (C. reinhardtii) and luminescence emission (V. fischeri). EC50 value after 30 min of treatment was similar in both organisms, with 0.114 and 0.167 mg mL(-1) for C. reinhardtii and V. fischeri, respectively. On the other hand, AuG0 NPs induced no change of mitochondrial activity in mammalian cells after 24 h of treatment to up to 0.4 mg mL(-1) AuG0 NPs. Change in the absorption spectra of AuG0 NP in the mammalian cell culture media may indicate an alteration of NP properties that contributed to the low toxicity of AuG0 NPs in mammalian cells. For a safe development of PAMAM-based nanomaterials, the difference of sensitivity between mammalian and microbial cells, as well as the modulation of NPs toxicity by medium properties, should be taken into account when designing PAMAM NPs for applications that may lead to their introduction in the environment. Copyright © 2012 Wiley Periodicals, Inc.

Biosynthesis, Characterization, and Bioactivities Evaluation of Silver and Gold Nanoparticles Mediated by the Roots of Chinese Herbal Angelica pubescens Maxim

NASA Astrophysics Data System (ADS)

Markus, Josua; Wang, Dandan; Kim, Yeon-Ju; Ahn, Sungeun; Mathiyalagan, Ramya; Wang, Chao; Yang, Deok Chun

2017-01-01

A facile synthesis and biological applications of silver (DH-AgNps) and gold nanoparticles (DH-AuNps) mediated by the aqueous extract of Angelicae Pubescentis Radix (Du Huo) are explored. Du Huo is a medicinal root belonging to Angelica pubescens Maxim which possesses anti-inflammatory, analgesic, and antioxidant properties. The absorption spectra of nanoparticles in varying root extract and metal ion concentration, pH, reaction temperatures, and time were recorded by ultraviolet-visible (UV-Vis) spectroscopy. The presence of DH-AgNps and DH-AuNps was confirmed from the surface plasmon resonance intensified at 414 and 540 nm, respectively. Field emission transmission electron micrograph (FE-TEM) analysis revealed the formation of quasi-spherical DH-AgNps and spherical icosahedral DH-AuNps. These novel DH-AgNps and DH-AuNps maintained an average crystallite size of 12.48 and 7.44 nm, respectively. The biosynthesized DH-AgNps and DH-AuNps exhibited antioxidant activity against 2,2-diphenyl-1-picrylhydrzyl (DPPH) radicals and the former exhibited antimicrobial activity against clinical pathogens including Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Salmonella enterica. The expected presence of flavonoids, sesquiterpenes, and phenols on the nanoparticle surface were conjectured to grant protection against aggregation and free radical scavenging activity. DH-AgNps and DH-AuNps were further investigated for their cytotoxic properties in RAW264.7 macrophages for their potential application as drug carriers to sites of inflammation. In conclusion, this green synthesis is favorable for the advancement of plant mediated nano-carriers in drug delivery systems, cancer diagnostic, and medical imaging.

Extracellular synthesis gold nanotriangles using biomass of Streptomyces microflavus.

PubMed

Soltani Nejad, Meysam; Khatami, Mehrdad; Shahidi Bonjar, Gholam Hosein

2016-02-01

Applications of nanotechnology and nano-science have ever-expanding breakthroughs in medicine, agriculture and industries in recent years; therefore, synthesis of metals nanoparticle (NP) has special significance. Synthesis of NPs by chemical methods are long, costly and hazardous for environment so biosynthesis has been developing interest for researchers. In this regard, the extracellular biosynthesis of gold nanotriangles (AuNTs) performed by use of the soil Streptomycetes. Streptomycetes isolated from rice fields of Guilan Province, Iran, showed biosynthetic activity for producing AuNTs via in vitro experiments. Among all 15 Streptomyces spp. isolates, isolate No. 5 showed high biosynthesis activity. To determine the bacterium taxonomical identity at genus level, its colonies characterised morphologically by use of scanning electron microscope. The polymerase chain reaction (PCR) molecular analysis of active isolate represented its identity partially. In this regard, 16S rRNA gene of the isolate was amplified using universal bacterial primers FD1 and RP2. The PCR products were purified and sequenced. Sequence analysis of 16S rDNA was then conducted using National Center for Biotechnology Information Basic Local Alignment Search Tool method. The AuNTs obtained were characterised by ultraviolet-visible spectroscopy, atomic force microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction spectroscopy analyses. The authors results indicated that Streptomyces microflavus isolate 5 bio-synthesises extracellular AuNTs in the range of 10-100 nm. Synthesised SNPs size ranged from 10 to 100 nm. In comparison with chemical methods for synthesis of metal NPs, the biosynthesis of AuNTs by Streptomyces source is a fast, simple and eco-friendly method. The isolate is a good candidate for further investigations to optimise its production efficacy for further industrial goals in biosynthesis of AuNTs.

Some current methods to represent the heterogeneity of natural media in hydrogeology

NASA Astrophysics Data System (ADS)

de Marsily, G.; Delay, F.; Teles, V.; Schafmeister, M. T.

We have known for a long time that the material properties of the subsurface are highly variable in space. We have learned that this variability is due to the extreme complexity and variation with time of processes responsible for the formation of the earth's crust, from plate tectonics to erosion, sediment transport, and deposition, as well as to mechanical, climatic, and diagenetic effects. As geologists, we learned how to "read" this complex history in the rocks and how to try to extrapolate in space what we have understood. As physicists, we then learned that to study flow processes in such media we must apply the laws of continuum mechanics. As mathematicians using analytical methods, we learned that we must simplify by dividing this complex continuum into a small number of units, such as aquifers and aquitards, and describe their properties by (constant) equivalent values. In recent years, as numerical modelers, we learned that we now have the freedom to "discretize" this complex reality and describe it as an ensemble of small homogeneous boxes of continuous media, each of which can have different properties. How do we use this freedom? Is there a need for it? If the answer is "yes," how can we assign different rock-property values to thousands or even millions of such little boxes in our models, to best represent reality, and include confidence levels for each selected rock property? As a tribute to Professor Eugene S. Simpson, with whom the first author of this paper often discussed these questions, we present an overview of three techniques that focus on one property, the rock permeability. We explain the motivation for describing spatial variability and illustrate how to do so by the geostatistical method, the Boolean method, and the genetic method. We discuss their advantages and disadvantages and indicate their present state of development. This is an active field of research and space is limited, so the review is certain to be incomplete, but we hope that it will encourage the development of new ideas and approaches. Résumé On sait depuis longtemps que les propriétés des roches en profondeur sont éminemment variables dans l'espace. On sait que cette variabilité est due à la complexité extrême et à la variation au cours du temps des processus responsables de la formation de la croûte terrestre, de la tectonique des plaques à l'érosion, au transport sédimentaire et au dépôt, sans oublier les effets mécaniques, climatiques et de diagenèse. En tant que géologues, nous avons appris a "lire" cette histoire complexe au sein des roches, et à tenter d'extrapoler dans l'espace notre compréhension. En tant que physiciens, nous avons ensuite appris que pour étudier les écoulements dans de tels milieux, nous devions appliquer les concepts de la mécanique des milieux continus. En tant que mathématiciens utilisant des méthodes analytiques pour résoudre les problèmes d'écoulement, nous avons de plus appris que nous devions simplifier cette réalité complexe en un très petit nombre d'unités, tels que les aquifères et les aquitards, dont chacune est décrite par des propriétés équivalentes constantes. Enfin, dans les années récentes, en tant que numériciens, nous avons appris que nous avions désormais la liberté de "discrétiser" cette réalité complexe, et de la décrire comme un ensemble de petites "boîtes" homogènes de milieu continu, chacune d'entre elles pouvant avoir des propriétés différentes. Comment utilisons nous cette liberté nouvellement acquise? En avons-nous réellement besoin? Si la réponse est "oui", comment pouvons nous attribuer des propriétés différentes aux roches des milliers ou même millions de petites "boîtes" dans nos modèles, pour représenter au mieux la réalité, et comment déterminer les intervalles de confiance des propriétés choisies pour chaque roche? En hommage au Professeur Eugène S. Simpson, avec lequel le premier auteur de cet article a eu souvent l'occasion de discuter de ces questions, nous présentons ici un survol général de quelques techniques de génération de telles propriétés se focalisant sur une seule d'entre elles, la perméabilité des roches. Nous expliquons d'abord quels sont les raisons qui engagent à tenter de décrire la variabilité spatiale, puis nous illustrons trois méthodes pour le faire, la méthode géostatistique, la méthode Booléenne et la méthode génétique. Nous présentons leurs avantages et inconvénients respectifs, et donnons l'état actuel de leur développement. Ces méthodes constituant un domaine de recherche actif, et la place étant ici limitée, ce survol est nécessairement incomplet, mais nous espérons qu'il encouragera l'essor de nouvelles idées et de nouvelles approches. Resumen Sabemos desde hace tiempo que las propiedades del subsuelo son altamente variables espacialmente. Hemos aprendido que esta variabilidad es debida a la extrema complejidad y variabilidad temporal de los procesos responsables de la formación de la corteza terrestre, desde la tectónica de placas a la erosión, transporte de sedimentos y deposición, así como a efectos mecánicos, climáticos y diagenéticos. Como geólogos, hemos aprendido a "leer" esta compleja historia en las rocas y a cómo tratar de extrapolar en el espacio lo que ya sabemos. Como físicos, aprendimos después que para estudiar los procesos en este tipo de medios debemos aplicar las leyes de la mecánica de los medios continuos. Como matemáticos que usan métodos analíticos, hemos aprendido que debemos simplificar el medio dividiéndolo en un número menor de unidades, como serían los acuíferos y acuitardos, y describiendo sus propiedades mediante valores equivalentes (constantes). En los últimos años, como modelistas, también hemos aprendido que tenemos la libertad de "discretizar" esta realidad compleja y describirla como un conjunto de pequeñas cajas homogéneas de medio continuo, cada una con propiedades diferentes. ¿Cómo usamos esta libertad?¿Tenemos necesidad de ella? Si la respuesta es "sí", ¿cómo podemos asignar valores de las distintas propiedades de las rocas a miles e incluso millones de estas pequeñas cajas en nuestros modelos, con la pretensión de representar la realidad, y a la vez dar intervalos de confianza para cada propiedad seleccionada? Como un tributo al Profesor Eugene S. Simpson, con quien el autor de este artículo a menudo discutió sobre estas cuestiones, se presenta una recopilación de tres técnicas que se centran en una propiedad, la permeabilidad de la roca. Se explica la motivación para describir la variabilidad espacial y se ilustra cómo hacerlo mediante el método geoestadístico Booleano y mediante el método genético. Para cada método se discuten sus ventajas e inconvenientes y se indica su estado actual de desarrollo. Se trata éste de un campo activo de investigación y el espacio es limitado, por lo que la revisión es incompleta, pero esperamos que pueda servir para animar el desarrollo de nuevas ideas.

Mechanism of solid-state plasma-induced dewetting for formation of copper and gold nanoparticles.

PubMed

Kwon, Soon-Ho; Choe, Han Joo; Lee, Hyo-Chang; Chung, Chin-Wook; Lee, Jung-Joong

2013-09-01

Cu and Au nanoparticles were fabricated by plasma treatment on Cu and Au films at 653 K. The nanoparticles were formed by dewetting the metallic films using plasma. Scanning electron microscopy and transmission electron microscopy investigations showed that the plasma-induced dewetting of the Cu and Au films proceeded through heterogeneous hole nucleation and growth along the grain boundaries to lower the surface energy. The amount of energy transferred to surface atoms by one Ar ion was calculated to be 16.1 eV, which was sufficient for displacing Cu and Au atoms. Compared to thermally activated dewetting, more uniform particles could be obtained by plasma-induced dewetting because a much larger number of holes with smaller sizes was generated. The plasma dewetting process is less sensitive to the oxidation of metallic films compared to the annealing process. As a result, Cu nanoparticles could be fabricated at 653 K, whereas the thermally activated dewetting was not possible.

Morphological Control of Au Dendrite Electrocatalysts for CO2 Reduction

NASA Astrophysics Data System (ADS)

Nesbitt, Nathan T.; Ma, Ming; Carter, Brittany E.; D'Imperio, Luke A.; Naughton, Jeffrey R.; Courtney, Dave T.; Shepard, Steve; Burns, Michael J.; Smith, Wilson A.; Naughton, Michael J.

Au has demonstrated the highest catalytic selectivity, activity, and stability for CO2 reduction to CO of any metal, but the mechanism for this performance remains unclear. Studies of nanoparticle films have shown that higher index facets have improved performance, but the preeminent nanoparticle films, from oxide-derived Au, lack well-defined facets and morphological stability to illuminate their enabling mechanism. More recent work has shown Au needles with a sub 5 nm radius of curvature have excellent performance and stability, independent of crystal facet. The same studies, however, still show calculations expecting a facet dependance. Here we demonstrate a facile and novel dendrite fabrication process with tunable morphology. The dendrites show high catalytic selectivity, activity, and stability for CO2 reduction to CO, along with morphological stability after 18 hours of operation, allowing correlation between morphology and performance. The influence of exposed facets will be discussed. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under Grant No. (DGE-1258923).

Thermosensitive polymer stabilized core-shell AuNR@Ag nanostructures as "smart" recyclable catalyst

NASA Astrophysics Data System (ADS)

Li, Dongxiang; Liu, Na; Gao, Yuanyuan; Lin, Weihong; Li, Chunfang

2017-11-01

Core-shell AuNR@Ag nanostructures were synthesized and surface-grafted with thermosensitive poly( N-isopropylacrylamide) to enhance stability and endow stimuli-responsive property. The AuNR cores showed average dimensions of 8-nm diameter and 33-nm length, while the anisotropic silver shells displayed 1-2 nm thin side and maximal 8 nm fat side. The obtained polymer-stabilized AuNR@Ag nanostructures as catalysts showed normal Arrhenius change of apparent rate constant, k app, in catalyzed reaction between 20 and 30 °C, but displayed a decrease of k app with respect to the temperature increasing between 32.5-40 °C, showing self-inhibition of the observed catalytic activity. Such "smart" self-inhibition of catalytic activity at enhanced temperature can be attributed to the thermosensitive response of the grafted polymer molecules and should be significant to control the reaction rate and avoid superheat for exothermic reactions. Such polymer-stabilized nanocatalyst also could be recovered and reused in the catalytic system. [Figure not available: see fulltext.