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Sample records for hyaluronan-modified magnetic nanoclusters

  1. Magnetic Ordering in Gold Nanoclusters

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    Agrachev, Mikhail; Antonello, Sabrina; Dainese, Tiziano; Ruzzi, Marco; Zoleo, Alfonso; Aprà, Edoardo; Govind, Niranjan; Fortunelli, Alessandro; Sementa, Luca; Maran, Flavio

    2017-06-12

    Several research groups have observed magnetism in monolayer-protected gold-cluster samples, but the results were often contradictory and thus a clear understanding of this phenomenon is still missing. We used Au25(SCH2CH2Ph)180, which is a paramagnetic cluster that can be prepared with atomic precision and whose structure is known precisely. Previous magnetometry studies only detected paramagnetism. We used samples representing a range of crystallographic orders and studied their magnetic behaviors by electron paramagnetic resonance (EPR). As a film, Au25(SCH2CH2Ph)180 displays paramagnetic behavior but, at low temperature, ferromagnetic interactions are detectable. One or few single crystals undergo physical reorientation with the applied field and display ferromagnetism, as detected through hysteresis experiments. A large collection of microcrystals is magnetic even at room temperature and shows distinct paramagnetic, superparamagnetic, and ferromagnetic behaviors. Simulation of the EPR spectra shows that both spin-orbit coupling and crystal distortion are important to determine the observed magnetic behaviors. DFT calculations carried out on single cluster and periodic models predict values of spin6orbit coupling and crystal6splitting effects in agreement with the EPR derived quantities. Magnetism in gold nanoclusters is thus demonstrated to be the outcome of a very delicate balance of factors. To obtain reproducible results, the samples must be (i) controlled for composition and thus be monodispersed with atomic precision, (ii) of known charge state, and (iii) well defined also in terms of crystallinity and experimental conditions. This study highlights the efficacy of EPR spectroscopy to provide a molecular understanding of these phenomena

  2. Magnetic behavior of Pd nanoclusters

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    Aguilera-Granja, F. [Instituto de Fisica ' Manuel Sandoval Vallarta' , Universidad Autonoma de San Luis Potosi, Alvaro Obregon 64, 78000 San Luis Potosi, S.L.P. (Mexico)]. E-mail: faustino@dec1.ifisica.uaslp.mx; Montejano-Carrizales, J.M. [Instituto de Fisica ' Manuel Sandoval Vallarta' , Universidad Autonoma de San Luis Potosi, Alvaro Obregon 64, 78000 San Luis Potosi, S.L.P. (Mexico); Berlanga-Ramirez, E.O. [Instituto de Fisica ' Manuel Sandoval Vallarta' , Universidad Autonoma de San Luis Potosi, Alvaro Obregon 64, 78000 San Luis Potosi, S.L.P. (Mexico); Vega, A. [Departamento de Fisica Teorica, Atomica, Nuclear y Optica, Universidad de Valladolid, E-47011 Valladolid (Spain)

    2004-12-31

    We study the magnetic properties of free-standing Pd clusters of some selected sizes with icosahedral structures which are obtained as the most stable ones using the Embedded Atom Method from an uniform relaxation of different geometrical configurations. The spin-polarized electronic structure and related magnetic properties of those optimized geometries were calculated by solving self-consistently a spd tight-binding Hamiltonian. The magnetic moments obtained in our calculations present a step-like dependence as a function of the exchange parameter in the case of small cluster sizes and a more complex dependence for larger cluster sizes is found. We discuss the results in comparison with previous calculations for FCC Pd clusters and with recent experimental findings. We also study the dependence of the magnetic moments distribution within the clusters with some geometrical effects such as hydrostatic deformations and twining.

  3. Nonextensivity in Magnetic Nanocluster Ensembles

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    Binek, Christian; Polisetty, Srinivas; He, Xi; Mukherjee, Tathagata; Rajasekeran, Rajesh; Redepenning, Jody

    2006-03-01

    We study the scaling behavior of dipolar interacting nanoparticles in 3D samples of various sizes but constant particle density. Ferromagnetic γ-Fe2O3 clusters embedded in a polystyrene matrix are fabricated by thermal decomposition of metal carbonyls. Transmission electron microscopy reveals a narrow size distribution of 12 nm clusters. They are randomly dispersed in the matrix with an average separation of 80 nm. Magnetization isotherms of these single domain particle ensembles are measured by SQUID magnetometry above the blocking temperature TB =115K where non-equilibrium effects are avoided. After demagnetization corrections which convert the applied magnetic fields into internal fields, H, a data collapse is achieved when scaling the magnetic moment, m, and H by appropriate factors. The latter are theoretically predicted functions of the number of particles and determined here numerically. Scaling of H takes into account the nonextensive (NE) behavior of dipolar interacting particles. In the case of long range interactions a scaling schema has been proposed by Tsallis and confirmed by simulations. The controversial field of NE thermodynamics requires however experimental evidence provided here.

  4. Magnetic properties of colloidal cobalt nanoclusters

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    Torchio, R; Meneghini, C; Mobilio, S; Capellini, G [Dipartimento di Fisica ' E. Amaldi' , Universita di Roma Tre, via della Vasca Navale 84, I-00146 Roma (Italy); Prieto, A Garcia; Alonso, J; Fdez-Gubieda, M L [Departamento de Electricidad y Electronica y Fisica Aplicada I, Universidad del PaIs Vasco (Spain); Liveri, V Turco; Ruggirello, A M [Dipartimento di Chimica Fisica ' F. Accascina' , Universita di Palermo, Viale delle Scienze, Parco d' Orleans II, Edificio 17, 90128 Palermo (Italy); Longo, A [ISMN, Istituto per lo Studio dei Materiali Nanostrutturati, CNR, Via U. La Malfa 153, 90146 Palermo (Italy); Neisius, T, E-mail: torchio@fis.uniroma3.i [Universite Paul CEZANNE, Faculte des Sciences et Techniques, Marseille (France)

    2010-01-01

    Co nanoclusters were synthesized by an inverse-micelle chemical route. The magnetic and microstructural properties of the nanoparticles have been analyzed as a function of the surfactant (AOT and DEHP) and the drying method. Microstructural analysis has been performed by TEM and XANES; magnetic properties have been studied by hysteresis loops and zero-field cooling - field cooling (ZFC-FC) curves. TEM images show 2 to 4 nm sized particles spherical in shape. XANES measurements point out a significant presence of Co{sub 3}O{sub 4}with metallic Co and some Co{sup 2+} bound to the surfactant. The presence of antiferromagnetic Co{sub 3}O{sub 4} explains the magnetic transition observed at low T in both ZFC-FC measurements and hysteresis loops. Finally, the presence of magnetic interactions explains the bigger effective cluster size obtained from hysteresis loops fits (6-10 nm) compared to the sizes observed by TEM (2-4 nm).

  5. Tailoring the magnetic properties of cobalt-ferrite nanoclusters

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    Vega, A. Estrada de la; Garza-Navarro, M. A., E-mail: marco.garzanr@uanl.edu.mx; Durán-Guerrero, J. G.; Moreno Cortez, I. E.; Lucio-Porto, R.; González-González, V. [Universidad Autónoma de Nuevo León, Facultad de Ingeniería Mecánica y Eléctrica (Mexico)

    2016-01-15

    In this contribution, we report on the tuning of magnetic properties of cobalt-ferrite nanoclusters. The cobalt-ferrite nanoclusters were synthesized from a two-step approach that consists of the synthesis of cobalt-ferrite nanoparticles in organic media, followed by their dispersion into aqueous dissolution to form an oil-in-water emulsion. These emulsions were prepared at three different concentrations of the cationic surfactant cetyltrimethylammonium bromide (CTAB), in order to control the size and clustering density of the nanoparticles in the nanoclusters. The synthesized samples were characterized by transmission electron microscopy and their related techniques, such as bright-field and Z-contrast imaging, electron diffraction and energy-dispersive X-ray spectrometry; as well as static magnetic measures. The experimental evidence indicates that the size, morphology, and nanoparticles clustering density in the nanoclusters is highly dependent of the cobalt-ferrite:CTAB molar ratio that is used in their synthesis. In addition, due to the clustering of the nanoparticles into the nanoclusters, their magnetic moments are blocked to relax cooperatively. Hence, the magnetic response of the nanoclusters can be tailored by controlling the size and nanoparticles clustering density.

  6. Efficiency of genomic DNA extraction dependent on the size of magnetic nanoclusters

    Science.gov (United States)

    Cho, Hyun Ah; Hyun Min, Ji; Hua Wu, Jun; Woo Jang, Jin; Lim, Chae-Seung; Keun Kim, Young

    2014-05-01

    We report the efficiency of genomic DNA extraction as a function of particle size and quantity. For DNA extraction, we synthesized magnetic nanoclusters of various sizes and coated the surface of these magnetic nanoclusters with meso-2,3-dimercaptosuccinic acid. We showed that the nanoclusters had a tight particle size distribution and high crystallinity. Furthermore, we observed that the three types of magnetic nanoclusters studied exhibited ferrimagnetic behavior and that larger nanoclusters showed larger saturation magnetization values. The resultant efficiency of DNA extraction is inversely proportional to particle size in the range of nanoclusters tested, due to the fact that the surface-to-volume ratio decreases as particle size increases.

  7. Magnetic and optoelectronic properties of gold nanocluster-thiophene assembly.

    Science.gov (United States)

    Qin, Wei; Lohrman, Jessica; Ren, Shenqiang

    2014-07-07

    Nanohybrids consisting of Au nanocluster and polythiophene nanowire assemblies exhibit unique thermal-responsive optical behaviors and charge-transfer controlled magnetic and optoelectronic properties. The ultrasmall Au nanocluster enhanced photoabsorption and conductivity effectively improves the photocurrent of nanohybrid based photovoltaics, leading to an increase of power conversion efficiency by 14 % under AM 1.5 illumination. In addition, nanohybrids exhibit electric field controlled spin resonance and magnetic field sensing behaviors, which open up the potential of charge-transfer complex system where the magnetism and optoelectronics interact.

  8. Hydrophilic magnetic nanoclusters with thermo-responsive properties and their drug controlled release

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    Meerod, Siraprapa [Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Naresuan University, Phitsanulok 65000 (Thailand); Rutnakornpituk, Boonjira; Wichai, Uthai [Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Naresuan University, Phitsanulok 65000 (Thailand); Center of Excellence in Biomaterials, Faculty of Science, Naresuan University, Phitsanulok 65000 Thailand (Thailand); Rutnakornpituk, Metha, E-mail: methar@nu.ac.th [Department of Chemistry and Center of Excellence for Innovation in Chemistry, Faculty of Science, Naresuan University, Phitsanulok 65000 (Thailand); Center of Excellence in Biomaterials, Faculty of Science, Naresuan University, Phitsanulok 65000 Thailand (Thailand)

    2015-10-15

    Synthesis and drug controlled release properties of thermo-responsive magnetic nanoclusters grafted with poly(N-isopropylacrylamide) (poly(NIPAAm)) and poly(NIPAAm-co-poly(ethylene glycol) methyl ether methacrylate) (PEGMA) copolymers were described. These magnetic nanoclusters were synthesized via an in situ radical polymerization in the presence of acrylamide-grafted magnetic nanoparticles (MNPs). Poly(NIPAAm) provided thermo-responsive properties, while PEGMA played a role in good water dispersibility to the nanoclusters. The ratios of PEGMA to NIPAAm in the (co)polymerization in the presence of the MNPs were fine-tuned such that the nanoclusters with good water dispersibility, good magnetic sensitivity and thermo responsiveness were obtained. The size of the nanoclusters was in the range of 50–100 nm in diameter with about 100–200 particles/cluster. The nanoclusters were well dispersible in water at room temperature and can be suddenly agglomerated when temperature was increased beyond the lower critical solution temperature (LCST) (32 °C). The release behavior of an indomethacin model drug from the nanoclusters was also investigated. These novel magnetic nanoclusters with good dispersibility in water and reversible thermo-responsive properties might be good candidates for the targeting drug controlled release applications. - Highlights: • Nanoclusters with good water dispersibility and magnetic response were prepared. • They were grafted with thermo-responsive poly(NIPAAm) and/or poly(PEGMA). • Poly(NIPAAm) provided thermo-responsive properties to the nanoclusters. • Poly(PEGMA) provided good water dispersibilityto the nanoclusters. • Accelerated and controllable releases of a drug from the nanoclusters were shown.

  9. Magnetic endohedral transition-metal-doped semiconducting-nanoclusters.

    Science.gov (United States)

    Matxain, Jon M; Formoso, Elena; Mercero, Jose M; Piris, Mario; Lopez, Xabier; Ugalde, Jesus M

    2008-01-01

    Endohedral first-row transition-metal-doped TM@Zn(i)S(i) nanoclusters, in which TM stands for the first-row transition-metals from Sc to Zn, and i=12, 16, have been characterized. In these structures the dopant metals are trapped inside spheroidal hollow semiconducting nanoclusters. It is observed that some of the transition metals are trapped in the center of mass of the cluster, whereas others are found to be displaced from that center, leading to structures in which the transition metals display a complex dynamical behavior upon encapsulation. This fact was confirmed by quantum molecular dynamics calculations, which further confirmed the thermal stability of endohedral compounds. In the endohedrally-doped nanoclusters in which the transition-metal atom sits on the center of mass, the host hollow cluster structure remains undistorted after dopant encapsulation. Conversely, if the encapsulated transition-metal atom is displaced from the center of mass, the host hollow cluster structure suffers a very tiny distortion. Additionally, it is found that there is negligible charge transfer between the dopant transition-metal atom and its hollow cluster host and, after encapsulation, the spin densities remain localized on the transition-metal atom. This allows for the atomic-like behavior of the trapped transition-metal atom, which gives rise to their atomic-like magnetic properties. The encapsulation free energies are negative, suggesting that these compounds are thermodynamically stable.

  10. Computational Studies of Magnetically Doped Semiconductor Nanoclusters

    Science.gov (United States)

    Gutsev, Lavrenty Gennady

    Spin-polarized unrestricted density functional theory is used to calculate the molecular properties of magnetic semiconductor quantum dots doped with 3d-metal atoms. We calculate total energies of the low spin antiferromagnetically coupled states using a spin-flipping algorithm leading to the broken-symmetry states. Given the novel nature of the materials studied, we simulate experimental observables such as hyperfine couplings, ionization/ energies, electron affinities, first and second order polarizabilities, band gaps and exchange coupling constants. Specifically, we begin our investigation with pure clusters of (CdSe )16 and demonstrate the dependence of molecular observables on geometrical structures. We also show that the many isomers of this cluster are energetically quite closely spaced, and thus it would be necessary to employ a battery of tests to experimentally distinguish them. Next, we discuss Mn-doping into the cage (CdSe)9 cluster as well as the zinc-blende stacking type cluster (CdSe)36. We show that the local exchange coupling mechanism is ligand-mediated superexchange and simulate the isotropic hyperfine constants. Finally, we discuss a novel study where (CdSe)9 is doped with Mn or Fe up to a full replacement of all the Cd's and discuss the transition points for the magnetic behavior and specifically the greatly differing band-gap shifts. We also outline an unexpected pattern in the polarizability of the material as metals are added and compare our results with the results from theoretical studies of the bulk material.

  11. Magnetism of FePt Nanoclusters in Polyimide

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    Mircea Chipara

    2015-01-01

    Full Text Available FePt nanoclusters have been implanted onto polyimide films and subjected to thermal annealing in order to obtain a special magnetic phase (L10 dispersed within the polymer. SQUID measurements quantified the magnetic features of the as-prepared and annealed hybrid films. As-implanted FePt nanoparticles in polyimide films exhibited a blocking temperature of 70 ± 5 K. Thermal annealing in zero and 10 kOe applied magnetic field increased the magnetic anisotropy and coercivity of the samples. Wide Angle X-Ray Scattering confirmed the presence of FePt and L10 phase. All samples (as deposited and annealed exhibited electron spin resonance spectra consisting of two overlapping lines. The broad line was a ferromagnetic resonance originating from FePt nanoparticles. Its angular dependence indicated the magnetic anisotropy of FePt nanoparticles. SEM micrographs suggest a negligible coalescence of FePt nanoparticles, supporting that the enhancement of the magnetic properties is a consequence of the improvement of the L10 structure. The narrow ESR line was assigned to nonmagnetic (paramagnetic impurities within the samples consistent with graphite-like structures generated by the local degradation of the polymer during implantation and annealing. Raman spectroscopy confirmed the formation of graphitic structures in annealed KHN and in KHN-FePt.

  12. A colloidal assembly approach to synthesize magnetic porous composite nanoclusters for efficient protein adsorption

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    Yang, Qi; Lan, Fang; Yi, Qiangying; Wu, Yao; Gu, Zhongwei

    2015-10-01

    A combination strategy of the inverse emulsion crosslinking approach and the colloidal assembly technique is first proposed to synthesize Fe3O4/histidine composite nanoclusters as new-type magnetic porous nanomaterials. The nanoclusters possess uniform morphology, high magnetic content and excellent protein adsorption capacity, exhibiting their great potential for bio-separation.A combination strategy of the inverse emulsion crosslinking approach and the colloidal assembly technique is first proposed to synthesize Fe3O4/histidine composite nanoclusters as new-type magnetic porous nanomaterials. The nanoclusters possess uniform morphology, high magnetic content and excellent protein adsorption capacity, exhibiting their great potential for bio-separation. Electronic supplementary information (ESI) available: Experimental details. See DOI: 10.1039/c5nr05800g

  13. Collective electric and magnetic plasmonic resonances in spherical nanoclusters.

    Science.gov (United States)

    Vallecchi, Andrea; Albani, Matteo; Capolino, Filippo

    2011-01-31

    We report an investigation on the optical properties of three-dimensional nanoclusters (NCs) made by spherical constellations of metallic nanospheres arranged around a central dielectric sphere, which can be realized and assembled by current state-of-the-art nanochemistry techniques. This type of NCs supports collective plasmon modes among which the most relevant are those associated with the induced electric and magnetic resonances. Combining a single dipole approximation for each nanoparticle and the multipole spherical-wave expansion of the scattered field, we achieve an effective characterization of the optical response of individual NCs in terms of their scattering, absorption, and extinction efficiencies. By this approximate model we analyze a few sample NCs identifying the electric and magnetic resonance frequencies and their dependence on the size and number of the constituent nanoparticles. Furthermore, we discuss the effective electric and magnetic polarizabilities of the NCs, and their isotropic properties. A homogenization method based on an extension of the Maxwell Garnett model to account for interaction effects due to higher order multipoles in dense packed arrays is applied to a distribution of NCs showing the possibility of obtaining metamaterials with very large, small, and negative values of permittivity and permeability, and even negative index.

  14. Polymer stabilized Ni-Ag and Ni-Fe alloy nanoclusters: Structural and magnetic properties

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    Kabir, L.; Mandal, A.R. [Department of Physics, Visva-Bharati, Santiniketan-731 235 (India); Mandal, S.K., E-mail: sk_mandal@hotmail.co [Department of Physics, Visva-Bharati, Santiniketan-731 235 (India)

    2010-04-15

    We report here the structural and magnetic behaviors of nickel-silver (Ni-Ag) and nickel-iron (Ni-Fe) nanoclusters stabilized with polymer (polypyrrole). High resolution transmission electron microscopy (HRTEM) indicates Ni-Ag nanoclusters to stabilize in core-shell configuration while that of Ni-Fe nanoclusters in a mixed type of geometry. Structural characterizations by X-ray diffraction (XRD) reveal the possibility of alloying in such bimetallic nanoclusters to some extent even at temperatures much lower than that of bulk alloying. Electron paramagnetic resonance (EPR) spectra clearly reveal two different absorption behaviors: one is ascribed to non-isolated Ni{sup 2+} clusters surrounded by either silver or iron giving rise to a broad signal, other (very narrow signal) being due to the isolated superparamagnetic Ni{sup 2+} clusters or bimetallic alloy nanoclusters. Results obtained for Ni-Ag and Ni-Fe nanoclusters have been further compared with the behavior exhibited by pure Ni nanoclusters in polypyrrole host. Temperature dependent studies (at 300 and 77 K) of EPR parameters, e.g. linewidth, g-value, line shape and signal intensity indicating the significant influence of surrounding paramagnetic silver or ferromagnetic iron within polymer host on the EPR spectra have been presented.

  15. Controlled nanoclustering of magnetic nanoparticles using telechelic polysiloxane and disiloxane

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    Thong-On, Bandit; Rutnakornpituk, Boonjira; Wichai, Uthai; Rutnakornpituk, Metha, E-mail: methar@nu.ac.th [Naresuan University, Department of Chemistry, Faculty of Science (Thailand)

    2015-06-15

    Diacrylate-terminated polydimethylsiloxane (PDMS) and disiloxane were synthesized and used for controlling degree of nanoclustering of magnetite nanoparticles (MNPs). PDMS was synthesized via a ring-opening polymerization of octamethylcyclotetrasiloxane (D{sub 4}), followed by end functionalization with diacrylate groups. Diacrylate-terminated disiloxane was separately synthesized in a similar fashion without the use of D{sub 4} in the reaction. They were then reacted with amino-coated MNPs to obtain MNP-embedded siloxane nanoclusters. Transmission electron microscopy showed the formation of MNP-siloxane nanoclusters with the size of 70–200 nm. Degree of MNP nanoclustering can be adjusted by varying the MNP-to-siloxane ratio to obtain hydrodynamic size ranging from 200 to 2400 nm. Using the same ratio of MNPs to the siloxanes, PDMS resulted in the nanoclusters with smaller D{sub h} and more stable in toluene than those coated with disiloxane. These novel nanoclusters with controllable size might be ideal candidates for biomedical and other advanced applications after suitable surface modification.

  16. Magnetic properties of transition-metal nanoclusters on a biological substrate

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    Herrmannsdoeerfer, T. [Institut Hochfeld-Magnetlabor Dresden (HLD), Forschungszentrum Dresden-Rossendorf, P.O. Box 510119, D-01314 Dresden (Germany)]. E-mail: T.Herrmannsdoerfer@fz-rossendorf.de; Bianchi, A.D. [Institut Hochfeld-Magnetlabor Dresden (HLD), Forschungszentrum Dresden-Rossendorf, P.O. Box 510119, D-01314 Dresden (Germany); Papageorgiou, T.P. [Institut Hochfeld-Magnetlabor Dresden (HLD), Forschungszentrum Dresden-Rossendorf, P.O. Box 510119, D-01314 Dresden (Germany); Pobell, F. [Institut Hochfeld-Magnetlabor Dresden (HLD), Forschungszentrum Dresden-Rossendorf, P.O. Box 510119, D-01314 Dresden (Germany); Wosnitza, J. [Institut Hochfeld-Magnetlabor Dresden (HLD), Forschungszentrum Dresden-Rossendorf, P.O. Box 510119, D-01314 Dresden (Germany); Pollmann, K. [Institut fuer Radiochemie, Forschungszentrum Dresden-Rossendorf, P.O. Box 510119, D-01314 Dresden (Germany); Merroun, M. [Institut fuer Radiochemie, Forschungszentrum Dresden-Rossendorf, P.O. Box 510119, D-01314 Dresden (Germany); Raff, J. [Institut fuer Radiochemie, Forschungszentrum Dresden-Rossendorf, P.O. Box 510119, D-01314 Dresden (Germany); Selenska-Pobell, S. [Institut fuer Radiochemie, Forschungszentrum Dresden-Rossendorf, P.O. Box 510119, D-01314 Dresden (Germany)

    2007-03-15

    We have investigated the magnetic properties of transition-metal clusters with a single grain size of about 1 nm. These metallic nanoclusters have been deposed on a biological substrate. This substrate is a purified self-assembling paracrystalline surface layer (S-layer) of the Bacillus sphaericus strain JG-A12, which exhibits square symmetry and is composed of identical protein monomers. First data of the magnetic susceptibility, taken in a SQUID magnetometer at 0magnetic properties. The Stoner enhancement factor of the d conduction-electron susceptibility in the Pd and Pt nanoclusters is dramatically reduced compared to the one of the corresponding bulk transition metals. The weakened magnetism of the 5d electrons is considered to play a crucial role for the occurrence of superconductivity in microgranular Pt by adjusting the balance between electron-phonon interactions and competing magnetic interactions.

  17. Surface induced magnetization reversal of MnP nanoclusters embedded in GaP

    Science.gov (United States)

    Lacroix, Christian; Lambert-Milot, Samuel; Desjardins, Patrick; Masut, Remo A.; Ménard, David

    2016-03-01

    We investigate the quasi-static magnetic behavior of ensembles of ferromagnetic nanoparticles consisting of MnP nanoclusters embedded in GaP(001) epilayers grown at 600, 650, and 700 °C. We use a phenomenological model, in which surface effects are included, to reproduce the experimental hysteresis curves measured as a function of temperature (120-260 K) and direction of the applied field. The slope of the hysteresis curve during magnetization reversal is determined by the MnP nanoclusters size distribution, which is a function of the growth temperature. Our results show that the coercive field is very sensitive to the strength of the surface anisotropy, which reduces the energy barrier between the two states of opposite magnetization. Notably, this reduction in the energy barrier increases by a factor of 3 as the sample temperature is lowered from 260 to 120 K.

  18. Size and property bimodality in magnetic nanoparticle dispersions: single domain particles vs. strongly coupled nanoclusters.

    Science.gov (United States)

    Wetterskog, E; Castro, A; Zeng, L; Petronis, S; Heinke, D; Olsson, E; Nilsson, L; Gehrke, N; Svedlindh, P

    2017-03-23

    The widespread use of magnetic nanoparticles in the biotechnical sector puts new demands on fast and quantitative characterization techniques for nanoparticle dispersions. In this work, we report the use of asymmetric flow field-flow fractionation (AF4) and ferromagnetic resonance (FMR) to study the properties of a commercial magnetic nanoparticle dispersion. We demonstrate the effectiveness of both techniques when subjected to a dispersion with a bimodal size/magnetic property distribution: i.e., a small superparamagnetic fraction, and a larger blocked fraction of strongly coupled colloidal nanoclusters. We show that the oriented attachment of primary nanocrystals into colloidal nanoclusters drastically alters their static, dynamic, and magnetic resonance properties. Finally, we show how the FMR spectra are influenced by dynamical effects; agglomeration of the superparamagnetic fraction leads to reversible line-broadening; rotational alignment of the suspended nanoclusters results in shape-dependent resonance shifts. The AF4 and FMR measurements described herein are fast and simple, and therefore suitable for quality control procedures in commercial production of magnetic nanoparticles.

  19. Modulation of magnetic anisotropy through self-assembled surface nanoclusters: Evolution of morphology and magnetism in Co-Pd alloy films

    Science.gov (United States)

    Hsu, Chuan-Che; Chiu, Hsiang-Chih; Mudinepalli, Venkata Ramana; Chen, Yu-Chuan; Chang, Po-Chun; Wu, Chun-Te; Yen, Hung-Wei; Lin, Wen-Chin

    2017-09-01

    In this study, the self-assembly of surface nanoclusters on 10-20-nm-thick Co50Pd50 (Co-Pd) alloy thin films deposited on the Al2O3(0001) substrate was systematically investigated. The time-dependent evolution of the nanocluster size and magnetic properties was monitored using an atomic force microscope (AFM) and the magneto-optical Kerr effect. When the Co-Pd alloy films were stored in an ambient environment, small nanodots gradually gathered to form large nanoclusters. Approximately 30 days after growth, a nanocluster array formed with an average lateral size of 100 ± 20 nm and average height of 10 ± 3 nm. After 100 days, the average lateral size and average height had increased to 140 ± 20 and 25 ± 5 nm, respectively. The AFM phase image exhibited a structured contrast on the nanocluster surface, indicating the nonuniform stiffness distribution of the nanoclusters. A microscopic Auger spectroscopy measurement suggested that in contrast to the Pd-rich signal in the flat area, the nanoclusters were cobalt- and oxygen-rich areas. Cross-sectional investigation through transmission electron microscopy coupled with energy dispersive spectroscopy showed that the nanoclusters were mostly composed of Co oxide. A uniform Pd-rich underlayer had been maintained underneath the self-assembled Co-oxide nanoclusters. With the formation of a Co-oxide nanocluster array and Pd-rich underlayer, the magnetic easy axis of the Co-Pd film gradually altered its direction from the pristine perpendicular to in-plane direction. Because of the change in the magnetic easy axis, the hydrogenation-induced spin-reorientation transition was suppressed with the evolution of the surface Co-oxide nanoclusters.

  20. Magnetic properties of novel superparamagnetic iron oxide nanoclusters and their peculiarity under annealing treatment

    Science.gov (United States)

    Tadic, Marin; Kralj, Slavko; Jagodic, Marko; Hanzel, Darko; Makovec, Darko

    2014-12-01

    The aim of this work is to present the magnetic properties of novel superparamagnetic iNANOvative™|silica nanoparticle clusters. A TEM analysis showed that these nanoparticle clusters, approximately 80 nm in size, contained an assembly of maghemite nanoparticles in the core and an amorphous silica shell. The maghemite nanoparticles in the core were approximately 10 nm in size, whereas the uniform silica shell was approximately 15-nm thick. The number of magnetic nanoparticles that were densely packed in the core of the single nanocluster was estimated to be approximately 67, resulting in a high magnetic moment for the single nanocluster of mnc ∼ 1.2 × 106μB. This magnetic property of the nanoparticle cluster is advantageous for its easy manipulation using an external magnetic field, for example, in biomedical applications, such as drug delivery, or for magnetic separation in biotechnology. The magnetic properties of the iNANOvative™|silica nanoparticle clusters were systematically studied, with a special focus on the influence of the magnetic interactions between the nanoparticles in the core. For comparison, the nanoparticle clusters were annealed for 3 h at 300 °C in air. The annealing had no influence on the nanoparticles' size and phase; however, it had a unique effect on the magnetic properties, i.e., a decrease of the blocking temperature and a weakening of the inter-particle interactions. We believe that this surprising observation is related to the thermal decomposition of the organic surfactant on the surfaces of the nanoparticles' at the high annealing temperatures, which resulted in the formation of amorphous carbon inside the nanocluster.

  1. Magnetic properties of novel superparamagnetic iron oxide nanoclusters and their peculiarity under annealing treatment

    Energy Technology Data Exchange (ETDEWEB)

    Tadic, Marin, E-mail: marint@vinca.rs [Condensed Matter Physics Laboratory, Vinca Institute of Nuclear Sciences, University of Belgrade, POB 522, 11001 Belgrade (Serbia); Kralj, Slavko [Department for Materials Synthesis, Jožef Stefan Institute, Ljubljana SI-1000 (Slovenia); Nanos Scientificae d.o.o. (Nanos Sci.), Teslova 30, Ljubljana (Slovenia); Jagodic, Marko [Institute of Mathematics, Physics and Mechanics, 1000 Ljubljana (Slovenia); Hanzel, Darko [Jozef Stefan Institute, Jamova 39, Ljubljana (Slovenia); Makovec, Darko [Department for Materials Synthesis, Jožef Stefan Institute, Ljubljana SI-1000 (Slovenia)

    2014-12-15

    Graphical abstract: - Highlights: • Magnetic properties of γ-Fe{sub 2}O{sub 3} nanoclusters and their thermal decomposition. • SPION clusters show superparamagnetism and high magnetic moments m{sub nc} ∼ 1.2 × 10{sup 6}μ{sub B.} • The TEM shows maghemite nanoparticles in a core and an amorphous silica shell. • The annealing treatment produces weakening the inter-particle interactions. - Abstract: The aim of this work is to present the magnetic properties of novel superparamagnetic iNANOvative™|silica nanoparticle clusters. A TEM analysis showed that these nanoparticle clusters, approximately 80 nm in size, contained an assembly of maghemite nanoparticles in the core and an amorphous silica shell. The maghemite nanoparticles in the core were approximately 10 nm in size, whereas the uniform silica shell was approximately 15-nm thick. The number of magnetic nanoparticles that were densely packed in the core of the single nanocluster was estimated to be approximately 67, resulting in a high magnetic moment for the single nanocluster of m{sub nc} ∼ 1.2 × 10{sup 6}μ{sub B}. This magnetic property of the nanoparticle cluster is advantageous for its easy manipulation using an external magnetic field, for example, in biomedical applications, such as drug delivery, or for magnetic separation in biotechnology. The magnetic properties of the iNANOvative™|silica nanoparticle clusters were systematically studied, with a special focus on the influence of the magnetic interactions between the nanoparticles in the core. For comparison, the nanoparticle clusters were annealed for 3 h at 300 °C in air. The annealing had no influence on the nanoparticles’ size and phase; however, it had a unique effect on the magnetic properties, i.e., a decrease of the blocking temperature and a weakening of the inter-particle interactions. We believe that this surprising observation is related to the thermal decomposition of the organic surfactant on the surfaces of the

  2. Microstructure and magnetic properties of colloidal cobalt nano-clusters

    Energy Technology Data Exchange (ETDEWEB)

    Torchio, R. [Dipartimento di Fisica ' E. Amaldi' , Universita di Roma Tre, via della Vasca Navale 84, I-00146 Roma (Italy); CNR-TASC c/o GILDA-ESRF Grenoble (France); European Synchrotron Radiation Facility, 6 Rue Jules Horowitz, BP220, 38043 Grenoble Cedex (France); Meneghini, C., E-mail: meneghini@fis.uniroma3.i [Dipartimento di Fisica ' E. Amaldi' , Universita di Roma Tre, via della Vasca Navale 84, I-00146 Roma (Italy); CNR-TASC c/o GILDA-ESRF Grenoble (France); Mobilio, S. [Dipartimento di Fisica ' E. Amaldi' , Universita di Roma Tre, via della Vasca Navale 84, I-00146 Roma (Italy); CNR-TASC c/o GILDA-ESRF Grenoble (France); Laboratori Nazionali di Frascati INFN, via E. Fermi 40, I-00044 Frascati, Roma (Italy); Capellini, G. [Dipartimento di Fisica ' E. Amaldi' , Universita di Roma Tre, via della Vasca Navale 84, I-00146 Roma (Italy); Garcia Prieto, A. [Departamento de Fisica Aplicada I, Universidad del Pais Vasco (Spain); Alonso, J.; Fdez-Gubieda, M.L. [Departamento de Electricidad y Electronica, Universidad del Pais Vasco (Spain); Turco Liveri, V. [Dipartimento di Chimica Fisica ' F. Accascina' , Universita di Palermo, Viale delle Scienze, Parco d' Orleans II, Edificio 17, 90128 Palermo (Italy); Longo, A. [ISMN, Istituto per lo Studio dei Materiali Nanostrutturati, CNR, Via U. La Malfa 153, 90146 Palermo (Italy); Ruggirello, A.M. [Dipartimento di Chimica Fisica ' F. Accascina' , Universita di Palermo, Viale delle Scienze, Parco d' Orleans II, Edificio 17, 90128 Palermo (Italy); Neisius, T. [Federation des Sciences Chimiques de Marseille, Universite Paul Cezanne, Faculte des Sciences et Techniques Campus de Saint Jerome av. Escadrille Normandie Niemen 13397 Marseille Cedex (France)

    2010-11-15

    The magnetic response of nanometer sized Co nanoparticles (NP) prepared using reverse micelle solutions are presented. The use of complementary structural and morphological probes (like transmission electron microscopy, high resolution electron microscopy, X-ray absorption spectroscopy) allowed to relate the magnetic properties to the size, morphology, composition and atomic structure of the nanoparticles. All data agree on the presence of a core-shell structure of NPs made of a metallic Co core surrounded by a thin Co-oxide layer. The core-shell microstructure of NPs affects its magnetic response mainly raising the anisotropy constant.

  3. Gd doped Au nanoclusters: Molecular magnets with novel properties

    KAUST Repository

    Mokkath, Junais Habeeb

    2014-01-01

    The structural, magnetic, and optical properties of subnanometer Au N and AuN-1Gd1 gas phase clusters (N = 2 to 8) are systematically investigated in the framework of (time-dependent) density functional theory, using the B3LYP hybrid exchange correlation functional. The size dependent evolution of the gap between the highest occupied and lowest unoccupied molecular orbitals, the magnetism, and the absorption spectra are studied. The simultaneous appearance of large magnetic moments, significant band gaps, and plasmon resonances in the visible spectral region leads to novel multi-functional nanomaterials for applications in drug delivery, magnetic resonance imaging, and photo-responsive agents. © 2013 Elsevier B.V. All rights reserved.

  4. Theory of magnetic transition metal nanoclusters on surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Lounis, S.

    2007-04-17

    This thesis is motivated by the quest for the understanding and the exploration of complex magnetism provided by atomic scale magnetic clusters deposited on surfaces or embedded in the bulk. Use is made of the density functional theory (DFT). Acting within this framework, we have developed and implemented the treatment of non-collinear magnetism into the Juelich version of the full-potential Korringa-Kohn-Rostoker Green Function (KKR-GF) method. Firstly, the method was applied to 3d transition-metal clusters on different ferromagnetic surfaces. Different types of magnetic clusters where selected. In order to investigate magnetic frustration due to competing interactions within the ad-cluster we considered a (001) oriented surface of fcc metals, a topology which usually does not lead to non-collinear magnetism. We tuned the strength of the magnetic coupling between the ad-clusters and the ferromagnetic surface by varying the substrate from the case of Ni(001) with a rather weak hybridization of the Ni d-states with the adatom d-states to the case of Fe{sub 3ML}/Cu(001) with a much stronger hybridization due to the larger extend of the Fe wavefunctions. On Ni(001), the interaction between the Cr- as well as the Mn-dimer adatoms is of antiferromagnetic nature, which is in competition with the interaction with the substrate atoms. After performing total energy calculations we find that for Cr-dimer the ground state is collinear whereas the Mn-dimer prefers the non-collinear configuration as ground state. Bigger clusters are found to be magnetically collinear. These calculations were extended to 3d multimers on Fe{sub 3ML}/Cu(001). All neighboring Cr(Mn) moments in the compact tetramer are antiferromagnetically aligned in-plane, with the directions slightly tilted towards (outwards from) the substrate to gain some exchange interaction energy. The second type of frustration was investigated employing a Ni(111) surface, a surface with a triangular lattice of atoms, were

  5. Magnetism in segregated bimetallic CoRh nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Berlanga-Ramirez, E.O. [Instituto de Fisica, Universidad Autonoma de San Luis Potosi, 78000 San Luis Potosi, SLP (Mexico)]. E-mail: berlanga@dec1.ifisica.uaslp.mx; Aguilera-Granja, F. [Instituto de Fisica, Universidad Autonoma de San Luis Potosi, 78000 San Luis Potosi, SLP (Mexico); Montejano-Carrizales, J.M. [Instituto de Fisica, Universidad Autonoma de San Luis Potosi, 78000 San Luis Potosi, SLP (Mexico); Diaz-Ortiz, A. [Centro Nacional de Supercomputo, IPICyT, Apartado Postal 3-74 Tangamanga, 78231 San Luis Potosi, SLP (Mexico); Michaelian, K. [Instituto de Fisica, Universidad Nacional Autonoma de Mexico. 20-364, 01000 DF (Mexico); Vega, A. [Departamento de Fisica Teorica, Atomica y Optica, Universidad de Valladolid, E-47011 Valladolid (Spain)

    2004-12-31

    The magnetic properties of free-standing ConRhm clusters (N=n+m{approx}110 and n{approx}m) of three different symmetries: cubo-octahedral, icosahedral and HCP, were investigated in the segregated case. The initial geometrical structures constructed at Rh bulk distances were relaxed with a many-body Gupta potential to obtain the cluster geometries and energies. We find that the lowest energy is associated with the HCP structure. The relaxed interatomic distance for all the structures is slightly lower than the Rh bulk distance. The spin-polarized electronic structure and related magnetic properties of these optimized geometries were calculated by solving self-consistently a spd tight-binding Hamiltonian. The magnetic moment of the Rh atoms shows strong dependence on the position and environment, whereas the Co atoms show a smoother dependence. Results are compared with the experimental data and with other theoretical calculations available in the literature.

  6. Synthesis of Iron-ferrocyanide functionalized magnetic nanocluster for the removal of cesium

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Hee-Man; Jang, Sung-Chan; Lee, Kune Woo; Seo, Bum-Kyoung; Moon, Jei Kwon [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2014-10-15

    In the present study, magnetite nanocluster was synthesized by hydrothermal method, and coated with iron ferrocyanide for the adsorption of cesium in an aqueous solution through simple addition of iron ferrocyanide in acid condition. We describe the morphology, structure, and physical property of these nanoparticles. In addition, their ability to eliminate cesium from water was also evaluated. In this study, we fabricated Iron ferrocyanide immobilized magnetite nanocluster (IFC-MNC) using hydrothermal methods. The CIFC-MNC exhibited easy separation ability from water by an external magnet, and showed a high removal efficiency of cesium in aqueous solutions. Therefore, the IFC-MNC demonstrated good potential for the treatment of water contaminated with radioactive cesium. gnetic nanoadsorbents composed of a magnetic particles core and functional shell, which adsorb the contaminants, has attracted significant attention in environmental remediation owing to their high surface area and unique superparamagnetism. The nuclear accident at the Fukushima Daiichi nuclear power station in 2011 released a huge quantity of radioactive contaminants into the environment. Among these, cesium Cs-137 is the most problematic contaminant due to its long half-life (30.2 years), and high-energy gamma ray (γ-ray) emissions. Among various adsorbents to treat Cs-137 contaminated water, metal ferrocyanides were widely applied to remove the Cs-137 in water. For better separation of metal ferrocyanide from water, recently, our group reported the fabrication of copper ferrocyanide-functionalized magnetic nanoparticles (Cu-FC-EDA-MNPs) using alkoxysilanes, having ethylenediamine (EDA) group, modified Fe{sub 3}O{sub 4} nanoparticles (EDA-MNPs) for the fast and easy magnetic separation of metal ferrocyanide. However, the fabrication method was multistep procedure. Thus, a more simplified fabrication procedure is still desired.

  7. Synthesis, characterization, and cytotoxicity evaluation of high-magnetization multifunctional nanoclusters

    Science.gov (United States)

    Petran, Anca; Radu, Teodora; Nan, Alexandrina; Olteanu, Diana; Filip, Adriana; Clichici, Simona; Baldea, Ioana; Suciu, Maria; Turcu, Rodica

    2017-01-01

    The paper presents the synthesis, characterization, and in vitro cytotoxicity tests of Fe3O4 magnetic nanoclusters coated with ethylenediaminetetraacetic acid disodium salt (EDTA). Electron microscopy analysis (SEM) evidences that magnetite nanoparticles are closely packed into the clusters stabilized with EDTA with well-defined near spherical shapes and sizes in the range 100-200 nm. From XRD measurements, we determined the mean size of the crystallites inside the magnetic cluster about 36 nm. The saturation magnetization determined for the magnetic clusters stabilized with EDTA has high value, about 81.7 emu/g at 300 K. X-ray photoelectron spectroscopy has been used to determine both the elemental and chemical structure of the magnetic cluster surface. In vitro studies have shown that the magnetic clusters at low doses did not induce toxicity on human umbilical vein endothelial cells or lesions of the cell membrane. In contrast, at high doses, the magnetic clusters increased the lipid peroxidation and reduced the leakage of a cytoplasmic enzyme, lactate dehydrogenase (LDH), in parallel with increasing the antioxidant defense.

  8. Structural, electronic, and magnetic properties of single MnAs nanoclusters in GaAs

    Energy Technology Data Exchange (ETDEWEB)

    Smakman, E. P., E-mail: e.p.smakman@tue.nl; Mauger, S.; Koenraad, P. M. [Department of Applied Physics, Eindhoven University of Technology, Den Dolech 2, 5612 AZ Eindhoven (Netherlands); Rench, D. W.; Samarth, N. [Department of Physics and Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802 (United States)

    2014-12-08

    MnAs nanoclusters in GaAs were investigated with cross-sectional scanning tunneling microscopy. The topographic images reveal that the small clusters have the same zinc-blende crystal structure as the host material, while the larger clusters grow in a hexagonal crystal phase. The initial Mn concentration during molecular beam epitaxy growth has a strong influence on the size of the clusters that form during the annealing step. The local band structure of a single MnAs cluster is probed with scanning tunneling spectroscopy, revealing a Coulomb blockade effect that correlates with the size of the cluster. With a spin-sensitive tip, for the smaller clusters, superparamagnetic switching between two distinct states is observed at T = 77 K. The larger clusters do not change their magnetic state at this temperature, i.e., they are superferromagnetic, confirming that they are responsible for the ferromagnetic behavior of this material at room-temperature.

  9. Laser-assisted atom probe tomography investigation of magnetic FePt nanoclusters: First experiments

    Energy Technology Data Exchange (ETDEWEB)

    Folcke, E.; Larde, R. [Groupe de Physique des Materiaux, UMR CNRS 6634, Universite de Rouen, 76801 Saint Etienne du Rouvray (France); Le Breton, J.M., E-mail: jean-marie.lebreton@univ-rouen.fr [Groupe de Physique des Materiaux, UMR CNRS 6634, Universite de Rouen, 76801 Saint Etienne du Rouvray (France); Gruber, M.; Vurpillot, F. [Groupe de Physique des Materiaux, UMR CNRS 6634, Universite de Rouen, 76801 Saint Etienne du Rouvray (France); Shield, J.E.; Rui, X. [Department of Mechanical and Materials Engineering, Nebraska Center for Materials and Nanoscience, University of Nebraska, N104 WSEC, Lincoln, NE 68588 (United States); Patterson, M.M. [Department of Physics, University of Wisconsin-Stout, Menomonie, WI 54751 (United States)

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer FePt nanoclusters dispersed in a Cr matrix were studied by atom probe tomography. Black-Right-Pointing-Pointer Simulated experiments were conducted to study the artefacts of the analysis. Black-Right-Pointing-Pointer In FePt nanoclusters, Fe and Pt are present in equiatomic proportions. Black-Right-Pointing-Pointer FePt nanoclusters are homogeneous, no core-shell structure is observed. - Abstract: FePt nanoclusters dispersed in a Cr matrix have been investigated by laser-assisted atom probe tomography. The results were analysed according to simulated evaporation experiments. Three-dimensional (3D) reconstructions reveal the presence of nanoclusters roughly spherical in shape, with a size in good agreement with previous transmission electron microscopy observations. Some clusters appear to be broken up after the evaporation process due to the fact that the Cr matrix has a lower evaporation field than Fe and Pt. It is thus shown that the observed FePt nanoclusters are chemically homogeneous. They contain Fe and Pt in equiatomic proportions, with no core-shell structure observed.

  10. Room temperature observation by X-ray magnetic circular dichroism of the orbital momentum enhancement of Co nanoclusters grown on Au(110)

    Energy Technology Data Exchange (ETDEWEB)

    Roa, Daniel Bretas; Reis, Diogo Duarte; Coelho Neto, Paula Mariel; Simoes, Wendell; Siervo, Abner de; Magalhaes-Paniago, Rogerio [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil)

    2012-07-01

    Full text: Increase in magnetic storage capabilities inevitably requires miniaturization of magnetic bits. Two solutions for this problem have been proposed: the assembly of magnetic vortexes, where the competition between exchange and dipolar interactions stabilizes a specific magnetic configuration and the modification of magnetic properties of nanoclusters due to change in structural properties, leading to an enhancement of their orbital momentum, especially in 3D transition metals. Since nanoclusters inevitable exhibit superparamagnetism, the determination of the orbital momentum of nanoclusters suffers from the need of high magnetic fields and extremely low temperatures. Therefore, even the search for enhanced magnetic materials is jeopardized by this limitation. In the present work, we have grown cobalt nanoclusters on Au(110) by electron beam deposition under ultra-high vacuum conditions. Scanning tunneling microscopy and low energy electron diffraction confirmed the preparation of a clean Au surface as well as the formation of pure Co nanoclusters in the range of the equivalent of 1-4 monolayers. The magnetization of Cobalt clusters was confirmed by X-ray Magnetic Circular Dichroism (XMCD) measured at the new PGM beamline at the Brazilian Synchrotron Radiation Laboratory (LNLS). A reasonably low magnetic field (1.1 Tesla) was used and the measurements were done at room temperature. By fixing the spin momentum and determining the average angle between the incident X-ray photon and the total magnetic moment, we clearly observe the enhancement of Co orbital momentum as coverage decreases down to approximately 1.5 monolayers. The procedure of determination of the orbital momentum a low magnetic fields will be discussed in detail. (author)

  11. Entanglement in Anderson Nanoclusters

    CERN Document Server

    Samuelsson, Peter

    2007-01-01

    We investigate the two-particle spin entanglement in magnetic nanoclusters described by the periodic Anderson model. An entanglement phase diagram is obtained, providing a novel perspective on a central property of magnetic nanoclusters, namely the temperature dependent competition between local Kondo screening and nonlocal Ruderman-Kittel-Kasuya-Yoshida spin ordering. We find that multiparticle entangled states are present for finite magnetic field as well as in the mixed valence regime and away from half filling. Our results emphasize the role of charge fluctuations.

  12. Hyaluronan-modified superparamagnetic iron oxide nanoparticles for bimodal breast cancer imaging and photothermal therapy

    Directory of Open Access Journals (Sweden)

    Yang R

    2016-12-01

    Full Text Available Rui-Meng Yang,1,* Chao-Ping Fu,2,* Jin-Zhi Fang,1 Xiang-Dong Xu,1 Xin-Hua Wei,1 Wen-Jie Tang,1 Xin-Qing Jiang,1 Li-Ming Zhang2 1Department of Radiology, Guangzhou First People’s Hospital, Guangzhou Medical University, 2School of Materials Science and Engineering, School of Chemistry, Sun Yat-sen University, Guangzhou, China *These authors contributed equally to this work Abstract: Theranostic nanoparticles with both imaging and therapeutic abilities are highly promising in successful diagnosis and treatment of the most devastating cancers. In this study, the dual-modal imaging and photothermal effect of hyaluronan (HA-modified superparamagnetic iron oxide nanoparticles (HA-SPIONs, which was developed in a previous study, were investigated for CD44 HA receptor-overexpressing breast cancer in both in vitro and in vivo experiments. Heat is found to be rapidly generated by near-infrared laser range irradiation of HA-SPIONs. When incubated with CD44 HA receptor-overexpressing MDA-MB-231 cells in vitro, HA-SPIONs exhibited significant specific cellular uptake and specific accumulation confirmed by Prussian blue staining. The in vitro and in vivo results of magnetic resonance imaging and photothermal ablation demonstrated that HA-SPIONs exhibited significant negative contrast enhancement on T2-weighted magnetic resonance imaging and photothermal effect targeted CD44 HA receptor-overexpressing breast cancer. All these results indicated that HA-SPIONs have great potential for effective diagnosis and treatment of cancer. Keywords: iron oxide nanoparticles, surface functionalization, bioactive glycosaminoglycan, magnetic resonance imaging, cellular uptake, breast carcinoma

  13. Magnetic-responsive hybrids of Fe3O4 nanoparticles with β-lactoglobulin amyloid fibrils and nanoclusters.

    Science.gov (United States)

    Bolisetty, Sreenath; Vallooran, Jijo J; Adamcik, Jozef; Mezzenga, Raffaele

    2013-07-23

    We report on the synthesis and magnetic-responsive behavior of hybrids formed by dispersing negatively charged iron oxide (Fe3O4) magnetic nanoparticles in positively charged β-lactoglobulin protein solutions at acidic pH, followed by heating at high temperatures. Depending on the pH used, different hybrid aggregates can be obtained, such as nanoparticle-modified amyloid fibrils (pH 3) and spherical nanoclusters (pH 4.5). We investigate the effect of magnetic fields of varying strengths (0-5 T) on the alignment of these Fe3O4-modified amyloid fibrils and spherical nanoclusters using a combination of scattering, birefringence and microscopic techniques and we find a strong alignment of the hybrids upon increasing the intensity of the magnetic field, which we quantify via 2D and 3D order parameters. We also demonstrate the possibility of controlling magnetically the sol-gel behavior of these hybrids: addition of salt (NaCl, 150 mM) to a solution containing nanoparticles modified with β-lactoglobulin amyloid fibrils (2 wt % fibrils modified with 0.6 wt % Fe3O4 nanoparticles) induces first the formation of a reversible gel, which can then be converted back to solution upon application of a moderate magnetic field of 1.1 T. These hybrids offer a new appealing functional colloidal system in which the aggregation, orientational order and rheological behavior can be efficiently controlled in a purely noninvasive way by external magnetic fields of weak intensity.

  14. Hyaluronan-modified superparamagnetic iron oxide nanoparticles for bimodal breast cancer imaging and photothermal therapy

    Science.gov (United States)

    Yang, Rui-Meng; Fu, Chao-Ping; Fang, Jin-Zhi; Xu, Xiang-Dong; Wei, Xin-Hua; Tang, Wen-Jie; Jiang, Xin-Qing; Zhang, Li-Ming

    2017-01-01

    Theranostic nanoparticles with both imaging and therapeutic abilities are highly promising in successful diagnosis and treatment of the most devastating cancers. In this study, the dual-modal imaging and photothermal effect of hyaluronan (HA)-modified superparamagnetic iron oxide nanoparticles (HA-SPIONs), which was developed in a previous study, were investigated for CD44 HA receptor-overexpressing breast cancer in both in vitro and in vivo experiments. Heat is found to be rapidly generated by near-infrared laser range irradiation of HA-SPIONs. When incubated with CD44 HA receptor-overexpressing MDA-MB-231 cells in vitro, HA-SPIONs exhibited significant specific cellular uptake and specific accumulation confirmed by Prussian blue staining. The in vitro and in vivo results of magnetic resonance imaging and photothermal ablation demonstrated that HA-SPIONs exhibited significant negative contrast enhancement on T2-weighted magnetic resonance imaging and photothermal effect targeted CD44 HA receptor-overexpressing breast cancer. All these results indicated that HA-SPIONs have great potential for effective diagnosis and treatment of cancer. PMID:28096667

  15. Ion irradiation of Fe-Fe oxide core-shell nanocluster films. Effect of interface on stability of magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    McCloy, John S. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Jiang, Weilin [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Droubay, Timothy C. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Varga, Tamas [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Kovarik, Libor [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Sundararajan, Jennifer A. [Univ. of Idaho, Moscow, ID (United States); Kaur, Maninder [Univ. of Idaho, Moscow, ID (United States); Qiang, You [Univ. of Idaho, Moscow, ID (United States); Burks, Edward [Univ. of California, Davis, CA (United States); Liu, Kai [Univ. of California, Davis, CA (United States)

    2013-08-23

    A cluster deposition method was used to produce films of loosely aggregated nanoclusters (NC) of Fe core-Fe3O4 shell or fully oxidized Fe3O4. Films of these NC on Si(100) or MgO(100)/Fe3O4(100) were irradiated to 1016 Si2+/cm2 near room temperature using an ion accelerator. Ion irradiation creates structural change in the NC film with corresponding chemical and magnetic changes which depend on the initial oxidation state of the cluster. Films were characterized using magnetometry (hysteresis, first order reversal curves), microscopy (transmission electron, helium ion), and x-ray diffraction. In all cases, the particle sizes increased due to ion irradiation, and when a core of Fe is present, irradiation reduces the oxide shells to lower valent Fe species. These results show that ion irradiated behavior of the nanocluster films depends strongly on the initial nanostructure and chemistry, but in general saturation magnetization decreases slightly.

  16. Recyclable magnetic nanocluster crosslinked with poly(ethylene oxide)-block-poly(2-vinyl-4,4-dimethylazlactone) copolymer for adsorption with antibody.

    Science.gov (United States)

    Prai-In, Yingrak; Boonthip, Chatchai; Rutnakornpituk, Boonjira; Wichai, Uthai; Montembault, Véronique; Pascual, Sagrario; Fontaine, Laurent; Rutnakornpituk, Metha

    2016-10-01

    Surface modification of magnetic nanoparticle (MNP) with poly(ethylene oxide)-block-poly(2-vinyl-4,4-dimethylazlactone) (PEO-b-PVDM) diblock copolymers and its application as recyclable magnetic nano-support for adsorption with antibody were reported herein. PEO-b-PVDM copolymers were first synthesized via a reversible addition-fragmentation chain-transfer (RAFT) polymerization using poly(ethylene oxide) chain-transfer agent as a macromolecular chain transfer agent to mediate the RAFT polymerization of VDM. They were then grafted on amino-functionalized MNP by coupling with some azlactone rings of the PVDM block to form magnetic nanoclusters with tunable cluster size. The nanocluster size could be tuned by adjusting the chain length of the PVDM block. The nanoclusters were successfully used as efficient and recyclable nano-supports for adsorption with anti-rabbit IgG antibody. They retained higher than 95% adsorption of the antibody during eight adsorption-separation-desorption cycles, indicating the potential feasibility in using this novel hybrid nanocluster as recyclable support in cell separation applications.

  17. Effect of irregularities of nanosatellites position and size on collective electric and magnetic plasmonic resonances in spherical nanoclusters.

    Science.gov (United States)

    Vallecchi, Andrea; Albani, Matteo; Capolino, Filippo

    2013-03-25

    Spherical nanoclusters (NCs) with a central dielectric core surrounded by several satellite plasmonic nanospheres have been recently investigated as aggregates supporting electric and magnetic collective resonances. Notably, the collective magnetic resonance has been exploited to provide magnetic properties in optics, i.e., materials with macroscopic relative permeability different from unity. The NCs discussed in this paper can be realized using state-of-the-art nanochemistry self-assembly techniques. Accordingly, perfectly regular disposition of the nanoplasmonic satellites is not possible and this paper constitutes the first comprehensive analysis of the effect of such irregularities onto the electric and magnetic collective resonances. In particular we will show that the peak of the scattering cross section associated to the magnetic resonance is very sensitive to certain irregularities and significantly less to others. It is shown here that "artificial magnetic" properties of NCs are preserved for certain degrees of irregularities of the nanosatellites positions, however they are strongly affected by irregularities in the plasmonic nanosatellites sizes and by the presence of "defects" caused by the absence of satellites in the process of self-assembly around the dielectric core. The "artificial electric" resonance is instead less affected by irregularities mainly because of its wider frequency bandwidth.

  18. One-step microwave-assisted synthesis of water-dispersible Fe3O4 magnetic nanoclusters for hyperthermia applications

    Science.gov (United States)

    Sathya, Ayyappan; Kalyani, S.; Ranoo, Surojit; Philip, John

    2017-10-01

    To realize magnetic hyperthermia as an alternate stand-alone therapeutic procedure for cancer treatment, magnetic nanoparticles with optimal performance, within the biologically safe limits, are to be produced using simple, reproducible and scalable techniques. Herein, we present a simple, one-step approach for synthesis of water-dispersible magnetic nanoclusters (MNCs) of superparamagnetic iron oxide by reducing of Fe2(SO4)3 in sodium acetate (alkali), poly ethylene glycol (capping ligand), and ethylene glycol (solvent and reductant) in a microwave reactor. The average size and saturation magnetization of the MNC's are tuned from 27 to 52 nm and 32 to 58 emu/g by increasing the reaction time from 10 to 600 s. Transmission electron microscopy images reveal that each MNC composed of large number of primary Fe3O4 nanoparticles. The synthesised MNCs show excellent colloidal stability in aqueous phase due to the adsorbed PEG layer. The highest SAR value of 215 ± 10 W/gFe observed in 52 nm size MNC at a frequency of 126 kHz and field of 63 kA/m suggest the potential use of these MNC in hyperthermia applications. This study further opens up the possibilities to develop metal ion-doped MNCs with tunable sizes suitable for various biomedical applications using microwave assisted synthesis.

  19. Tuning the magnetic interactions in GaAs:Mn/MnAs hybrid structures by controlling shape and position of MnAs nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Elm, Matthias Thomas

    2010-07-01

    In this work the magnetic properties of hexagonal MnAs nanoclusters and their influence on the transport properties of GaAs:Mn /MnAs hybrid structures were studied. Various arrangements of isolated nanoclusters and cluster chains were grown on (111)B-GaAs substrates by SA-MOVPE. The first part of this work deals with the manufacturing process of the different cluster arrangements investigated. By a suitable pre-structuring of the substrate it was possible to influence the cluster size, cluster shape and cluster position systematically. Preparing various arrangements it could be shown that the hexagonal nanoclusters prefer to grow along their a-axes. In the second part, the magnetic properties of the nanoclusters were studied. Ferromagnetic resonance (FMR) measurements show a hard magnetic axis perpendicular to the sample plane, i.e. parallel to the c-axis. By measurements, where the magnetic field was rotated in the sample plane, it could be demonstrated that the orientation of the magnetization can be forced into a certain direction by controlling the cluster shape. These results are confirmed by measurements using magnetic force microscopy. The third part deals with the influence of the nanoclusters and their arrangement on the transport properties of the GaAs:Mn matrix. For temperatures above 30 K the structures investigated show positive as well as negative magnetoresistance effects, which are typical for granular GaAs:Mn/MnAs hybrid structures. This behaviour can be explained in the context of transport in extended band states. The size of the magnetoresistance effects correlates strongly with the respective cluster arrangement of the sample. This behaviour has been predicted theoretically and could be confirmed experimentally in the context of this work. Below 30 K large positive magnetoresistance effects show up for the regular cluster arrangements, which cannot be observed for hybrid structures with random cluster distributions. These large positive

  20. Ion irradiation of Fe-Fe oxide core-shell nanocluster films: Effect of interface on stability of magnetic properties

    Energy Technology Data Exchange (ETDEWEB)

    McCloy, John S.; Jiang, Weilin; Droubay, Timothy C.; Varga, Tamas; Kovarik, Libor [Pacific Northwest National Laboratory, 902 Battelle Blvd., PO Box 999, Richland, Washington 99352 (United States); Sundararajan, Jennifer A.; Kaur, Maninder; Qiang, You [Department of Physics, University of Idaho, Moscow, Idaho 83844 (United States); Burks, Edward C.; Liu, Kai [Department of Physics, University of California, Davis, California 95616 (United States)

    2013-08-28

    A cluster deposition method was used to produce films of loosely aggregated nanoclusters (NCs) of Fe core-Fe{sub 3}O{sub 4} shell or fully oxidized Fe{sub 3}O{sub 4}. Films of these NC on Si(100) or MgO(100)/Fe{sub 3}O{sub 4}(100) were irradiated to 10{sup 16} Si{sup 2+}/cm{sup 2} near room temperature using an ion accelerator. Ion irradiation creates structural change in the NC film with corresponding chemical and magnetic changes which depend on the initial oxidation state of the cluster. Films were characterized using magnetometry (hysteresis, first order reversal curves), microscopy (transmission electron, helium ion), and x-ray diffraction. In all cases, the particle sizes increased due to ion irradiation, and when a core of Fe is present, irradiation reduces the oxide shells to lower valent Fe species. These results show that ion irradiated behavior of the NC films depends strongly on the initial nanostructure and chemistry, but in general saturation magnetization decreases slightly.

  1. Magnetic-field-dependent assembly of silica-coated magnetite nanoclusters probed by Ultra-Small-Angle X-ray Scattering (USAXS)

    Energy Technology Data Exchange (ETDEWEB)

    Malik, Vikash [Physics Department, University of Wisconsin Milwaukee, 1900 E. Kenwood Blvd., Milwaukee, WI 53211 (United States); Suthar, Kamleshkumar J. [Advanced Photon Source, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL 60439 (United States); Mancini, Derrick C. [Physical Sciences and Engineering, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL 60439 (United States); Ilavsky, Jan, E-mail: ilavsky@aps.anl.gov [Advanced Photon Source, Argonne National Laboratory, 9700 S. Cass Ave., Argonne, IL 60439 (United States)

    2014-03-15

    Colloidal suspension of the silica coated magnetic nanoclusters (MNCs) was used to study the magnetic field mediated assembly of magnetic nanoparticles. The spatial arrangement of these MNCs in colloidal suspension was studied using the ultra-small-angle X-ray scattering (USAXS) technique with magnetic field applied in directions orthogonal and parallel to the scattering vector. In situ magnetic field analysis of the USAXS scattering measurement showed anisotropic behavior that can be attributed to the formation of colloidal crystals. During magnetization, the clustered magnetic core induces a large dipole moment, and the thickness of the silica shell helps keep distance between the neighboring particles. The assembly of these hybrid nanostructured particles was found to be dependent on the strength and orientation of this external magnetic field. The dipolar chains formed of MNCs arranged themselves into colloidal crystals formed by two-dimensional magnetic sheets. The structure factor calculations suggested that the lattice parameters of these colloidal crystals can be tuned by changing the strength of the external magnetic field. These experiments shed light on the stimuli-responsive assembly of magnetic colloidal nanoparticles that leads to the creation of tunable photonic crystals. - Highlights: • In situ analysis of Magnetically tunable colloidal nanocluster using Ultra Small Angle X-ray Scattering (USAXS) under uniform magnetic field. • The colloidal super-lattice structure was analyzed in magnetic field along the direction parallel and perpendicular to scattering vector. • Structure factors were extracted by subtracting form factor from the USAXS data using Irena software tool. • The observed super-lattice structural spacing can be tuned by extent of the strength of external magnetic field. • The structure factor calculations showed that the colloidal crystal has the hexagonal packing.

  2. Magnetite nanocluster@poly(dopamine)-PEG@ indocyanine green nanobead with magnetic field-targeting enhanced MR imaging and photothermal therapy in vivo.

    Science.gov (United States)

    Wu, Ming; Wang, Qingtang; Zhang, Da; Liao, Naishun; Wu, Lingjie; Huang, Aimin; Liu, Xiaolong

    2016-05-01

    Multifunctional nanomaterials with the magnetic resonance imaging (MRI) guided tumor photothermal ablation ability have been extensively applied in biomedical research as one of the most exciting and challenging strategies for cancer treatment. Nevertheless, most of these nanomaterials still suffer from low accumulation in tumor tissues and insufficient photothermal ablation of tumors so far. Here, we report a novel approach to overcome these limitations using a core-shell magnetite nanocluster@poly(dopamine)-PEG@ICG nanobead compositing of magnetite nanocluster core with coating of poly(dopamine), then further conjugating with polyethylene glycol (PEG) and adsorbing indocyanine green (ICG) on the surface. The adsorbed ICG in the nanobead displays a higher photostability and photothermal conversion ability than free ICG, as well as additional photothermal effect rather than magnetite nanocluster and poly(dopamine), which endow the nanobead with enhanced photothermal killing efficiency against cancer cells under near-infrared (NIR) laser irritation. Furthermore, it is proved that these nanobeads have excellent biocompatibility, T2-weighted MR imaging and magnetic field targeting ability. By applying an external magnetic field (MF) focused on the targeted tumor, a magnetic targeting mediated enhanced accumulation is observed at tumor site as proved by a darker T2-weighted MR image. Utilizing the magnetic targeting strategy, enhanced photothermal tumor ablation was achieved under laser irradiation in vivo, which is reflected by the degree of tumor tissue damage and tumor growth delay. Therefore, this nanobead integrates the abilities of magnetic field-targeting, MR imaging and photothermal cancer therapy, and might be a promising theranostic platform for tumor treatment.

  3. Biocompatible Low-Retention Superparamagnetic Iron Oxide Nanoclusters as Contrast Agents for Magnetic Resonance Imaging of Liver Tumor.

    Science.gov (United States)

    Wei, Yushuang; Liao, Rufang; Liu, Haijuan; Li, Huan; Xu, Haibo; Zhou, Qibing

    2015-05-01

    Although superparamagnetic iron oxide (SPIO) nanoparticles have been developed as a contrast agent for magnetic resonance imaging (MRI), acute iron overload due to the persistently high retention of SPIOs in the liver and spleen that are slowly converted to ferroproteins is a serious safety concern. Here, we report that the addition of poly-L-lysine polymers to an SPIO hydroxyethyl starch solution produced tightly controlled, monodispersed nanoparticles in a size-dependent manner as effective contrast agents for the MRI of liver tumors. High MRI contrast was demonstrated with an orthotopic liver tumor model at a low injection dose. Simultaneously, rapid bioclearance of excess iron in the lung and spleen and in blood serum was observed within 24 h post-injection. The full excretion of excess iron was confirmed in urine post-intravenous injection, suggesting that the effective clearance of SPIOs could be achieved with our SPIO nanoclusters as a liver imaging contrast agent to resolve acute iron overload in the clinical usage of SPIOs as a contrast agent.

  4. Magnetic-field-dependent assembly of silica-coated magnetite nanoclusters probed by Ultra-Small-Angle X-ray Scattering (USAXS)

    Science.gov (United States)

    Malik, Vikash; Suthar, Kamleshkumar J.; Mancini, Derrick C.; Ilavsky, Jan

    2014-03-01

    Colloidal suspension of the silica coated magnetic nanoclusters (MNCs) was used to study the magnetic field mediated assembly of magnetic nanoparticles. The spatial arrangement of these MNCs in colloidal suspension was studied using the ultra-small-angle X-ray scattering (USAXS) technique with magnetic field applied in directions orthogonal and parallel to the scattering vector. In situ magnetic field analysis of the USAXS scattering measurement showed anisotropic behavior that can be attributed to the formation of colloidal crystals. During magnetization, the clustered magnetic core induces a large dipole moment, and the thickness of the silica shell helps keep distance between the neighboring particles. The assembly of these hybrid nanostructured particles was found to be dependent on the strength and orientation of this external magnetic field. The dipolar chains formed of MNCs arranged themselves into colloidal crystals formed by two-dimensional magnetic sheets. The structure factor calculations suggested that the lattice parameters of these colloidal crystals can be tuned by changing the strength of the external magnetic field. These experiments shed light on the stimuli-responsive assembly of magnetic colloidal nanoparticles that leads to the creation of tunable photonic crystals.

  5. Voltage-dependent magnetic phase transition in magneto-electric epitaxial Cr2O3 nanoclusters

    Science.gov (United States)

    Halley, David; Najjari, Nabil; Godel, Florian; Hamieh, Mohamad; Doudin, Bernard; Henry, Yves

    2016-06-01

    We observe, as a function of temperature, a second order magnetic phase transition in nanometric Cr2O3 clusters that are epitaxially embedded in an insulating MgO matrix. They are investigated through their tunnel magneto-resistance signature, the MgO layer being used as a tunnel barrier. We infer the small magnetic dipoles carried by the Cr2O3 clusters and provide evidence of a magnetic phase transition at low temperature in those clusters: they evolve from an anti ferromagnetic state, with zero net moment close to 0 K, to a weak ferromagnetic state that saturates above about 10 K. The influence of magneto-electric effects on the weak ferromagnetic phase is also striking: the second order transition temperature turns out to be linearly dependent on the applied electric field.

  6. Catechol-derivatized poly(vinyl alcohol) as a coating molecule for magnetic nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Burnand, David [Adolphe Merkle Institute, University of Fribourg, Route de l' Ancienne Papéterie CP209, 1723 Marly 1 (Switzerland); Chemistry Department, University of Fribourg, Chemin du Musée 9, 1700 Fribourg (Switzerland); Monnier, Christophe A.; Redjem, Anthony [Adolphe Merkle Institute, University of Fribourg, Route de l' Ancienne Papéterie CP209, 1723 Marly 1 (Switzerland); Schaefer, Mark [Chemistry Department, University of Fribourg, Chemin du Musée 9, 1700 Fribourg (Switzerland); Rothen-Rutishauser, Barbara [Adolphe Merkle Institute, University of Fribourg, Route de l' Ancienne Papéterie CP209, 1723 Marly 1 (Switzerland); Kilbinger, Andreas, E-mail: andreas.kilbinger@unifr.ch [Chemistry Department, University of Fribourg, Chemin du Musée 9, 1700 Fribourg (Switzerland); Petri-Fink, Alke, E-mail: alke.fink@unifr.ch [Adolphe Merkle Institute, University of Fribourg, Route de l' Ancienne Papéterie CP209, 1723 Marly 1 (Switzerland); Chemistry Department, University of Fribourg, Chemin du Musée 9, 1700 Fribourg (Switzerland)

    2015-04-15

    Surface functionalization of superparamagnetic iron oxide nanoparticles (SPIONs) remains indispensable in promoting colloidal stability and biocompatibility. We propose a well-defined and characterized synthesis of a new catechol-functionalized RAFT (reversible addition–fragmentation chain transfer) poly(vinyl alcohol) polymer, which can be anchored onto hydrophobic SPIONs via a one-pot emulsion ligand exchange process. Both single and clustered nanoparticles are obtained and can be separated from each other. As clustered SPIONs are receiving increasing attention, this new macroligand might be of considerable interest for both basic and applied sciences. - Highlights: • We prepared well-defined polymer coated magnetic nanoparticles. • We used polyvinyl alcohol (PVA) as an alternative to commonly used plyethylene glycol (PEG). • We strongly anchored the polymer on the magnetic nanoparticles' surfaces. • We developed a one-pot emulsion ligand exchange process. • We obtained single coated particles and well defined magnetic clusters, which we successfully separated.

  7. Structure analyses of Cu nanoclusters in the soft magnetic Fe85.2Si1B9P4Cu0.8 alloy by XAFS and fcc cluster model

    Science.gov (United States)

    Matsuura, M.; Nishijima, M.; Konno, K.; Ofuchi, H.; Takenaka, K.; Makino, A.

    2016-05-01

    Size of the clusters and structure details of fcc Cu clusters in nanocrystalline soft magnetic alloy of Fe85-86Si1-2B8P4Cu1 (NANOMET) are investigated. A linear combination fitting of XAFS data indicates that about 30% of Cu atoms are partitioned in the fcc clusters and the rest in the amorphous matrix. EXAFS of the fcc Cu nanocluster embedded in amorphous matrix is calculated on the basis of a simple fcc structure model using FEFF9. Surface effect of the nanoclusters is considered by counting a fraction of the nearest neighbour atoms in amorphous matrix. Good agreement with the experimental result is obtained for the fcc nanocluster with 9 coordination shells which consists of total 177 atoms within 1.5 nm in a diameter.

  8. Selective-area growth and magnetic characterization of MnAs/AlGaAs nanoclusters on insulating Al{sub 2}O{sub 3} layers crystallized on Si(111) substrates

    Energy Technology Data Exchange (ETDEWEB)

    Sakita, Shinya; Hara, Shinjiro, E-mail: hara@rciqe.hokudai.ac.jp [Research Center for Integrated Quantum Electronics, Hokkaido University, North 13 West 8, Sapporo 060-8628 (Japan); Elm, Matthias T. [Institute of Experimental Physics I, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, 35392 Giessen (Germany); Institute of Physical Chemistry, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 17, 35392 Giessen (Germany); Klar, Peter J. [Institute of Experimental Physics I, Justus-Liebig-University Giessen, Heinrich-Buff-Ring 16, 35392 Giessen (Germany)

    2016-01-25

    We report on selective-area metal-organic vapor phase epitaxy and magnetic characterization of coupled MnAs/AlGaAs nanoclusters formed on thin Al{sub 2}O{sub 3} insulating layers crystallized on Si(111) substrates. Cross-sectional transmission electron microscopy reveals that poly-crystalline γ-Al{sub 2}O{sub 3} grains are formed after an annealing treatment of the amorphous Al{sub 2}O{sub 3} layers deposited by atomic layer deposition on Si(111) substrates. The 〈111〉 direction of the γ-Al{sub 2}O{sub 3} grains tends to be oriented approximately parallel to the 〈111〉 direction of the Si substrate. We observe that hexagonal MnAs nanoclusters on AlGaAs buffer layers grown by selective-area metal-organic vapor phase epitaxy on partially SiO{sub 2}-masked Al{sub 2}O{sub 3} insulator crystallized on Si(111) substrates are oriented with the c-axis along the 〈111〉 direction of the substrates, but exhibit a random in-plane orientation. A likely reason is the random orientation of the poly-crystalline γ-Al{sub 2}O{sub 3} grains in the Al{sub 2}O{sub 3} layer plane. Magnetic force microscopy studies at room temperature reveal that arrangements of coupled MnAs nanoclusters exhibit a complex magnetic domain structure. Such arrangements of coupled MnAs nanoclusters may also show magnetic random telegraph noise, i.e., jumps between two discrete resistance levels, in a certain temperature range, which can be explained by thermally activated changes of the complex magnetic structure of the nanocluster arrangements.

  9. Passivation of cobalt nanocluster assembled thin films with hydrogen

    DEFF Research Database (Denmark)

    Romero, C.P.; Volodin, A.; Di Vece, M.

    2012-01-01

    The effect of hydrogen passivation on bare and Pd capped cobalt nanocluster assembled thin films was studied with Rutherford backscattering spectrometry (RBS) and magnetic force microscopy (MFM) after exposure to ambient conditions. The nanoclusters are produced in a laser vaporization cluster...

  10. The Nanocluster Trap endstation at BESSY II

    Directory of Open Access Journals (Sweden)

    Tobias Lau

    2017-05-01

    Full Text Available The Nanocluster Trap endstation at BESSY II combines a cryogenic linear radio-frequency ion trap with an applied magnetic field for x-ray magnetic circular dichroism studies of cold and size-selected trapped ions. Applications include atomic, molecular, and cluster ions as well as ionic complexes.

  11. Transcatheter intra-arterial infusion of doxorubicin loaded porous magnetic nano-clusters with iodinated oil for the treatment of liver cancer.

    Science.gov (United States)

    Jeon, Min Jeong; Gordon, Andrew C; Larson, Andrew C; Chung, Jin Wook; Kim, Young Il; Kim, Dong-Hyun

    2016-05-01

    A promising strategy for liver cancer treatment is to deliver chemotherapeutic agents with multifunctional carriers into the tumor tissue via intra-arterial (IA) transcatheter infusion. These carriers should release drugs within the target tissue for prolonged periods and permit intra-procedural multi-modal imaging of selective tumor delivery. This targeted transcatheter delivery approach is enabled via the arterial blood supply to liver tumors and utilized in current clinical practice which is called chemoembolization or radioembolization. During our study, we developed Doxorubicin (Dox) loaded porous magnetic nano-clusters (Dox-pMNCs). The porous structure and carboxylic groups on the MNCs achieved high-drug loading efficiency and sustained drug release, along with magnetic properties resulting in high MRI T2-weighted image contrast. Dox-pMNC within iodinated oil, Dox-pMNCs, and Dox within iodinated oil were infused via hepatic arteries to target liver tumors in a rabbit model. MRI and histological evaluations revealed that the long-term drug release and retention of Dox-pMNCs within iodinated oil induced significantly enhanced liver cancer cell death.

  12. Dual Recognition Strategy for Specific and Sensitive Detection of Bacteria Using Aptamer-Coated Magnetic Beads and Antibiotic-Capped Gold Nanoclusters.

    Science.gov (United States)

    Cheng, Dan; Yu, Mengqun; Fu, Fei; Han, Weiye; Li, Gan; Xie, Jianping; Song, Yang; Swihart, Mark T; Song, Erqun

    2016-01-01

    Food poisoning and infectious diseases caused by pathogenic bacteria such as Staphylococcus aureus (SA) are serious public health concerns. A method of specific, sensitive, and rapid detection of such bacteria is essential and important. This study presents a strategy that combines aptamer and antibiotic-based dual recognition units with magnetic enrichment and fluorescent detection to achieve specific and sensitive quantification of SA in authentic specimens and in the presence of much higher concentrations of other bacteria. Aptamer-coated magnetic beads (Apt-MB) were employed for specific capture of SA. Vancomycin-stabilized fluorescent gold nanoclusters (AuNCs@Van) were prepared by a simple one-step process and used for sensitive quantification of SA in the range of 32-10(8) cfu/mL with the detection limit of 16 cfu/mL via a fluorescence intensity measurement. And using this strategy, about 70 cfu/mL of SA in complex samples (containing 3 × 10(8) cfu/mL of other different contaminated bacteria) could be successfully detected. In comparison to prior studies, the developed strategy here not only simplifies the preparation procedure of the fluorescent probes (AuNCs@Van) to a great extent but also could sensitively quantify SA in the presence of much higher concentrations of other bacteria directly with good accuracy. Moreover, the aptamer and antibiotic used in this strategy are much less expensive and widely available compared to common-used antibodies, making it cost-effective. This general aptamer- and antibiotic-based dual recognition strategy, combined with magnetic enrichment and fluorescent detection of trace bacteria, shows great potential application in monitoring bacterial food contamination and infectious diseases.

  13. Transition from Superparamagnetism to Ferromagnetic Single-Domain in a Heisenberg Model for Nano-cluster Magnetic System

    Institute of Scientific and Technical Information of China (English)

    SHAO Yuan-Zhi; HE Zhen-Hui

    2000-01-01

    By considering a magnetic system of an ensemble of nanometer clusters without any external magnetic field, the Monte Carlo simulation of the Heisenberg model is used to investigate the transition from a superparamagnetism to a ferromagnetic single-domain state, which is caused by the growth of the clusters. We studied the variation of the dynamic growth exponent P and the transition critical size of the cluster Nc against the reduced temperature t and the uniaxial anisotropy constant A. We found that the growth exponent maximized at a certain temperature,other than being taken as a universal constant as some researchers suggested previously.

  14. Structures and magnetism of mono-palladium and mono-platinum doped Au25(PET)18 nanoclusters.

    Science.gov (United States)

    Tian, Shubo; Liao, Lingwen; Yuan, Jinyun; Yao, Chuanhao; Chen, Jishi; Yang, Jinlong; Wu, Zhikun

    2016-08-01

    Herein we report three important results of widespread interest, which are (1) the crystal structure of [Au24Pt(PET)18](0), (2) the crystal structure of [Au24Pd(PET)18](0) and (3) the main source of magnetism in [Au25(PET)18](0).

  15. Dynamics and Thermodynamics of Nanoclusters

    Directory of Open Access Journals (Sweden)

    Karo Michaelian

    2015-10-01

    Full Text Available The dynamic and thermodynamic properties of nanoclusters are studied in two different environments: the canonical and microcanonical ensembles. A comparison is made to thermodynamic properties of the bulk. It is shown that consistent and reproducible results on nanoclusters can only be obtained in the canonical ensemble. Nanoclusters in the microcanonical ensemble are trapped systems, and inconsistencies will be found if thermodynamic formalism is applied. An analytical model is given for the energy dependence of the phase space volume of nanoclusters, which allows the prediction of both dynamical and thermodynamical properties.

  16. Synthesis and characterization of colloidal fluorescent silver nanoclusters.

    Science.gov (United States)

    Huang, Sherry; Pfeiffer, Christian; Hollmann, Jana; Friede, Sebastian; Chen, Justin Jin-Ching; Beyer, Andreas; Haas, Benedikt; Volz, Kerstin; Heimbrodt, Wolfram; Montenegro Martos, Jose Maria; Chang, Walter; Parak, Wolfgang J

    2012-06-19

    Ultrasmall water-soluble silver nanoclusters are synthesized, and their properties are investigated. The silver nanoclusters have high colloidal stability and show fluorescence in the red. This demonstrates that like gold nanoclusters also silver nanoclusters can be fluorescent.

  17. Electrochemically induced nanocluster migration

    Energy Technology Data Exchange (ETDEWEB)

    Hartl, Katrin [Lehrstuhl Physikalische Chemie, Technische Universitaet Muenchen, Lichtenbergstr. 4, D-85748 Garching (Germany); Department of Chemistry, CS06, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen O (Denmark); Nesselberger, Markus [Department of Chemistry, CS06, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen O (Denmark); Mayrhofer, Karl J.J. [MPI fuer Eisenforschung, Abt. Grenzflaechenchemie und Oberflaechentechnik, Max-Planck-Strasse 1, D-40237 Duesseldorf (Germany); Kunz, Sebastian; Schweinberger, Florian F.; Kwon, GiHan [Lehrstuhl Physikalische Chemie, Technische Universitaet Muenchen, Lichtenbergstr. 4, D-85748 Garching (Germany); Hanzlik, Marianne [Institut fuer Elektronenmikroskopie, Technische Universitaet Muenchen, Lichtenbergstr. 4, D-85748 Garching (Germany); Heiz, Ueli [Lehrstuhl Physikalische Chemie, Technische Universitaet Muenchen, Lichtenbergstr. 4, D-85748 Garching (Germany); Arenz, Matthias, E-mail: m.arenz@kemi.ku.d [Department of Chemistry, CS06, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen O (Denmark)

    2010-12-30

    In the presented study the influence of electrochemical treatments on size-selected Pt nanoclusters (NCs) supported on amorphous carbon is investigated by means of transmission electron microscopy (TEM). Well-defined Pt NCs are prepared by an ultra-high vacuum (UHV) laser vaporization source and deposited with low kinetic energy ({<=}10 eV/cluster) onto TEM gold grids covered by a thin (2 nm) carbon film. After transfer out of UHV Pt NCs are verified to be uniform in size and randomly distributed on the support. Subsequently, the TEM grids are employed as working electrodes in a standard electrochemical three electrode setup and the Pt nanoclusters are subjected to different electrochemical treatments. It is found that the NC arrangement is not influenced by potential hold conditions (at 0.40 V vs. RHE) or by potential cycling in a limited potential window (V{sub max} = 0.55 V vs. RHE). Upon potential cycling to 1.05 V vs. RHE, however, the NCs migrate on the carbon support. Interestingly, migration in oxygen or argon saturated electrolyte leads to NC coalescence, a mechanism discussed for being responsible for performance degradation of low temperature fuel cells, whereas in carbon monoxide saturated electrolyte the Pt NC agglomerate, but remain separated from each other and thus form distinctive structures.

  18. Self-Assembled Superparamagnetic Iron Oxide Nanoclusters for Universal Cell Labeling and MRI

    Science.gov (United States)

    Chen, Shuzhen; Zhang, Jun; Jiang, Shengwei; Lin, Gan; Luo, Bing; Yao, Huan; Lin, Yuchun; He, Chengyong; Liu, Gang; Lin, Zhongning

    2016-05-01

    Superparamagnetic iron oxide (SPIO) nanoparticles have been widely used in a variety of biomedical applications, especially as contrast agents for magnetic resonance imaging (MRI) and cell labeling. In this study, SPIO nanoparticles were stabilized with amphiphilic low molecular weight polyethylenimine (PEI) in an aqueous phase to form monodispersed nanocomposites with a controlled clustering structure. The iron-based nanoclusters with a size of 115.3 ± 40.23 nm showed excellent performance on cellular uptake and cell labeling in different types of cells, moreover, which could be tracked by MRI with high sensitivity. The SPIO nanoclusters presented negligible cytotoxicity in various types of cells as detected using MTS, LDH, and flow cytometry assays. Significantly, we found that ferritin protein played an essential role in protecting stress from SPIO nanoclusters. Taken together, the self-assembly of SPIO nanoclusters with good magnetic properties provides a safe and efficient method for universal cell labeling with noninvasive MRI monitoring capability.

  19. Synthesis and characterization of Fe{sub 0.6}Zn{sub 0.4}Fe{sub 2}O{sub 4} ferrite magnetic nanoclusters using simple thermal decomposition method

    Energy Technology Data Exchange (ETDEWEB)

    Sharifi, Ibrahim; Zamanian, Ali, E-mail: a-zamanian@merc.ac.ir; Behnamghader, Aliasghar

    2016-08-15

    This paper presents experimental results regarding the effect of the quantity of solvent on formation of the Fe–Zn ferrite nanoparticles during thermal decomposition. A ternary system of Fe{sub 0.6}Zn{sub 0.4}Fe{sub 2}O{sub 4} has been synthesized by a thermal decomposition method using metal acetylacetonate in high temperature boiling point solvent and oleic acid. The X-ray diffraction study was used to determine phase purity, crystal structure, and average crystallite size of iron–zinc ferrite nanoparticles. The average crystallite size of nanoparticles was increased from 13 nm to 37 nm as a result of reducing the solvent from 30 ml to 10 ml in a synthesis batch. The diameter of particles and morphology of the particles were determined by transmission electron microscopy (TEM) and field emission scanning electron microscope (FESEM). Mid and far Fourier transform infrared (FT-IR) measurement confirmed monophasic spinel structure of ferrite. Furthermore, the DC magnetic properties of the samples were studied using the vibrating sample magnetometer (VSM). The largest Fe–Zn ferrite nanoparticles exhibited a relatively high saturation magnetization of 96 emu/g. Moreover, Low-field AC susceptibility measurement indicated blocking temperature of nanoparticles around 170–200 K. - Highlights: • Narrow dispersed nanoclusters Fe–Zn ferrites prepared by a simple thermal decomposition route. • Increase of solvent content in reaction cause reduce the size of nanoparticles. • The XRD parameters are refined by the Rietveld method. • Saturation magnetization increases while coercivity decreases with increasing the particle size of ferrites.

  20. Nanocluster technologies for electronics design

    CERN Document Server

    Parker, A J

    2001-01-01

    based electronic systems. The work presented in this thesis covers an investigation into the use of metal nanoclusters in nanoelectronics design. Initial studies explored the interactions of the dodecanethiol passivated gold nanocluster, held in solution with toluene, and the native oxide covered silicon surface. Deposition of the clusters is achieved by pippetting mu-litre quantities of the solution onto the surface, and allowing the solvent to evaporate leaving the clusters as residue. Patterning of the surface with micron scale photoresist structures prior to cluster exposure, led to the selective aggregation of cluster deposits along the resist boundaries. An extension of this technique, examined the flow of the cluster solution along photoresist structures which extended beyond the solution droplet. Investigation into the electronic properties of nanocluster arrays generated non-linear current-voltage curves, which are explained in terms of two very simple models. These results cast doubt over the suitab...

  1. Phosphorescent Nanocluster Light-Emitting Diodes.

    Science.gov (United States)

    Kuttipillai, Padmanaban S; Zhao, Yimu; Traverse, Christopher J; Staples, Richard J; Levine, Benjamin G; Lunt, Richard R

    2016-01-13

    Devices utilizing an entirely new class of earth abundant, inexpensive phosphorescent emitters based on metal-halide nanoclusters are reported. Light-emitting diodes with tunable performance are demonstrated by varying cation substitution to these nanoclusters. Theoretical calculations provide insight about the nature of the phosphorescent emitting states, which involves a strong pseudo-Jahn-Teller distortion.

  2. {Fe6O2}-Based Assembly of a Tetradecanuclear Iron Nanocluster

    Directory of Open Access Journals (Sweden)

    Svetlana G. Baca

    2011-01-01

    Full Text Available The tetradecanuclear FeIII pivalate nanocluster [Fe14O10(OH4(Piv18], comprising a new type of metal oxide framework, has been solvothermally synthesized from a hexanuclear iron pivalate precursor in dichlormethane/acetonitrile solution. Magnetic measurements indicate the presence of very strong antiferromagnetic interactions in the cluster core.

  3. The variable polarization undulator beamline UE52 PGM nanocluster trap at BESSY II

    Directory of Open Access Journals (Sweden)

    Ruslan Ovsyannikov

    2017-02-01

    Full Text Available UE52 PGM nanocluster trap is a soft x-ray beamline at BESSY II that delivers an unfocussed low-divergence beam of variable polarization. Its characteristics are ideally suited for ion trap studies of magnetic properties.

  4. Beta-cyclodextrins conjugated magnetic Fe{sub 3}O{sub 4} colloidal nanoclusters for the loading and release of hydrophobic molecule

    Energy Technology Data Exchange (ETDEWEB)

    Lv, Shaonan; Song, Yubei; Song, Yaya; Zhao, Zhigang; Cheng, Changjing, E-mail: changjing_cheng@163.com

    2014-06-01

    Herein, we report a facile method to prepare beta-cyclodextrin (β-CD)-conjugated magnetic Fe{sub 3}O{sub 4} colloidal nanocrystal clusters (Fe{sub 3}O{sub 4}@GLY-CD) using (3-glycidyloxypropyl) trimethoxysilane (GLY) as the intermediate linker. The resulting Fe{sub 3}O{sub 4}@GLY-CD was characterized by several methods including Fourier transform infrared (FT-IR) spectroscopy, field-emission scanning electron microscopy (SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and vibrating sample magnetometer (VSM). In addition, the loading and release properties of the synthesized Fe{sub 3}O{sub 4}@GLY-CD for the hydrophobic molecule 8-anilino-1-naphthalenesulfonic acid ammonium salt (ANS) were also investigated. The results show that the Fe{sub 3}O{sub 4}@GLY-CD has a spherical structure with an average diameter of 186 nm and high saturated magnetism of 51.2 emu/g. The grafting of β-CD onto Fe{sub 3}O{sub 4} colloidal nanocrystal clusters can markedly increase the loading capacity of ANS because of β-CD/ANS inclusion complex formation. The in vitro delivery profile shows that the release of ANS from the Fe{sub 3}O{sub 4}@GLY-CD nanosystem exhibits an initial burst followed by a slow and steady release. Moreover, Fe{sub 3}O{sub 4}@GLY-CD also demonstrates a temperature-dependent release behavior for ANS owing to the effect of temperature on the association constants of β-CD/ANS inclusion complexes. The developed magnetic hybrid nanomaterial is expected to find potential applications in several fields including separation science and biomedicine.

  5. Nanoclusters a bridge across disciplines

    CERN Document Server

    Jena, Purusottam

    2010-01-01

    This comprehensive book on Nanoclusters comprises sixteen authoritative chapters written by leading researchers in the field. It provides insight into topics that are currently at the cutting edge of cluster science, with the main focus on metal and metal compound systems that are of particular interest in materials science, and also on aspects related to biology and medicine. While there are numerous books on clusters, the focus on clusters as a bridge across disciplines sets this book apart from others. Delivers cutting edge coverage of cluster science Covers a broad range of topics in

  6. Clustomesogens: Liquid Crystalline Hybrid Nanomaterials Containing Functional Metal Nanoclusters.

    Science.gov (United States)

    Molard, Yann

    2016-08-16

    Inorganic phosphorescent octahedral metal nanoclusters fill the gap between metal complexes and nanoparticles. They are finite groups of metal atoms linked by metal-metal bonds, with an exact composition and structure at the nanometer scale. As their phosphorescence internal quantum efficiency can approach 100%, they represent a very attractive class of molecular building blocks to design hybrid nanomaterials dedicated to light energy conversion, optoelectronic, display, lighting, or theragnostic applications. They are obtained as AnM6X(i)8X(a)6 ternary salt powders (A = alkali cation, M = Mo, Re, W, X(i): halogen inner ligand, X(a) = halogen apical ligand) by high temperature solid state synthesis (750-1200 °C). However, their ceramic-like behavior has largely restricted their use as functional components in the past. Since these last two decades, several groups, including ours, started to tackle the challenge of integrating them in easy-to-process materials. Within this context, we have extensively explored the nanocluster ternary salt specificities to develop a new class of self-organized hybrid organic-inorganic nanomaterials known as clustomesogens. These materials, combine the specific properties of nanoclusters (magnetic, electronic, luminescence) with the anisotropy-related properties of liquid crystals (LCs). This Account covers the research and development of clustomesogens starting from the design concepts and synthesis to their introduction in functional devices. We developed three strategies to build such hybrid super- or supramolecules. In the covalent approach, we capitalized on the apical ligand-metal bond iono-covalent character to graft tailor-made organic LC promoters on the {M6X(i)8}(n+) nanocluster cores. The supramolecular approach relies on the host-guest complexation of the ternary cluster salt alkali cations with functional crown ether macrocycles. We showed that the hybrid LC behavior depends on the macrocycles structural features

  7. Electron correlations and silicon nanocluster energetics

    OpenAIRE

    2016-01-01

    The first-principle prediction of nanocluster stable structure is often hampered by the existence of many isomer configurations with energies close to the ground state. This fact attaches additional importance to many-electron effects going beyond density functional theory (DFT), because their contributions may change a subtle energy order of competitive structures. To analyze this problem, we consider, as an example, the energetics of silicon nanoclusters passivated by hydrogen Si$_{10}$H$_{...

  8. An ultrafast look at Au nanoclusters.

    Science.gov (United States)

    Yau, Sung Hei; Varnavski, Oleg; Goodson, Theodore

    2013-07-16

    In the past 20 years, researchers studying nanomaterials have uncovered many new and interesting properties not found in bulk materials. Extensive research has focused on metal nanoparticles (>3 nm) because of their potential applications, such as in molecular electronics, image markers, and catalysts. In particular, the discovery of metal nanoclusters (properties for nanomaterials are intriguing, because for metal nanosystems in this size regime both size and shape determine electronic properties. Remarkably, changes in the optical properties of nanomaterials have provided tremendous insight into the electronic structure of nanoclusters. The success of synthesizing monolayer protected clusters (MPCs) in the condensed phase has allowed scientists to probe the metal core directly. Au MPCs have become the "gold" standard in nanocluster science, thanks to the rigorous structural characterization already accomplished. The use of ultrafast laser spectroscopy on MPCs in solution provides the benefit of directly studying the chemical dynamics of metal nanoclusters (core), and their nonlinear optical properties. In this Account, we investigate the optical properties of MPCs in the visible region using ultrafast spectroscopy. Based on fluorescence up-conversion spectroscopy, we propose an emission mechanism for these nanoclusters. These clusters behave differently from nanoparticles in terms of emission lifetimes as well as two-photon cross sections. Through further investigation of the transient (excited state) absorption, we have found many unique phenomena of nanoclusters, such as quantum confinement effects and vibrational breathing modes. In summary, based on the differences in the optical properties, the distinction between nanoclusters and nanoparticles appears at a size near 2.2 nm. This is consistent with simulations from a free-electron model proposed for MPCs. The use of ultrafast techniques on these nanoclusters can answer many of the fundamental questions about

  9. A nanocluster beacon based on the template transformation of DNA-templated silver nanoclusters.

    Science.gov (United States)

    Teng, Ye; Jia, Xiaofang; Zhang, Shan; Zhu, Jinbo; Wang, Erkang

    2016-01-28

    In this work, we developed a novel light-up nanocluster beacon (NCB) based on shuttling dark silver nanoclusters (NCs) to a bright scaffold through hybridization. The fluorescence enhancement was as high as 70-fold when the two templates were on the opposite sides of the duplexes, enabling sensitive and selective detection of DNA.

  10. Atomically Precise Metal Nanoclusters for Catalytic Application

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Rongchao [Carnegie Mellon Univ., Pittsburgh, PA (United States)

    2016-11-18

    The central goal of this project is to explore the catalytic application of atomically precise gold nanoclusters. By solving the total structures of ligand-protected nanoclusters, we aim to correlate the catalytic properties of metal nanoclusters with their atomic/electronic structures. Such correlation unravel some fundamental aspects of nanocatalysis, such as the nature of particle size effect, origin of catalytic selectivity, particle-support interactions, the identification of catalytically active centers, etc. The well-defined nanocluster catalysts mediate the knowledge gap between single crystal model catalysts and real-world conventional nanocatalysts. These nanoclusters also hold great promise in catalyzing certain types of reactions with extraordinarily high selectivity. These aims are in line with the overall goals of the catalytic science and technology of DOE and advance the BES mission “to support fundamental research to understand, predict, and ultimately control matter and energy at the level of electrons, atoms, and molecules”. Our group has successfully prepared different sized, robust gold nanoclusters protected by thiolates, such as Au25(SR)18, Au28(SR)20, Au38(SR)24, Au99(SR)42, Au144(SR)60, etc. Some of these nanoclusters have been crystallographically characterized through X-ray crystallography. These ultrasmall nanoclusters (< 2 nm diameter) exhibit discrete electronic structures due to quantum size effect, as opposed to quasicontinuous band structure of conventional metal nanoparticles or bulk metals. The available atomic structures (metal core plus surface ligands) of nanoclusters serve as the basis for structure-property correlations. We have investigated the unique catalytic properties of nanoclusters (i.e. not observed in conventional nanogold catalysts) and revealed the structure-selectivity relationships. Highlights of our

  11. Surface-Induced Melting of Metal Nanoclusters

    Institute of Scientific and Technical Information of China (English)

    YANG Quan-Wen; ZHU Ru-Zeng; WEI Jiu-An; WEN Yu-Hua

    2004-01-01

    @@ We investigate the size effect on melting of metal nanoclusters by molecular dynamics simulation and thermodynamic theory based on Kofman's melt model. By the minimization of the free energy of metal nanoclusters with respect to the thickness of the surface liquid layer, it has been found that the nanoclusters of the same metal have the same premelting temperature Tpre = T0 - T0(γsv -γlv -γst)/(ρLξ) (T0 is the melting point of bulk metal, γsv the solid-vapour interfacial free energy, γlv the liquid-vapour interfacial free energy, γsl the solid-liquid interfacial free energy, ρ the density of metal, L the latent heat of bulk metal, and ξ the characteristic length of surface-interface interaction) to be independent of the size of nanoclusters, so that the characteristic length ξ ofa metal can be obtained easily by Tpre, which can be obtained by experiments or molecular dynamics (MD) simulations. The premelting temperature Tpre of Cu is obtained by MD simulations, then ξ is obtained.The melting point Tcm is further predicted by free energy analysis and is in good agreement with the result of our MD simulations. We also predict the maximum premelting-liquid width of Cu nanoclusters with various sizes and the critical size, below which there is no premelting.

  12. Plasmon tsunamis on metallic nanoclusters.

    Science.gov (United States)

    Lucas, A A; Sunjic, M

    2012-03-14

    A model is constructed to describe inelastic scattering events accompanying electron capture by a highly charged ion flying by a metallic nanosphere. The electronic energy liberated by an electron leaving the Fermi level of the metal and dropping into a deep Rydberg state of the ion is used to increase the ion kinetic energy and, simultaneously, to excite multiple surface plasmons around the positively charged hole left behind on the metal sphere. This tsunami-like phenomenon manifests itself as periodic oscillations in the kinetic energy gain spectrum of the ion. The theory developed here extends our previous treatment (Lucas et al 2011 New J. Phys. 13 013034) of the Ar(q+)/C(60) charge exchange system. We provide an analysis of how the individual multipolar surface plasmons of the metallic sphere contribute to the formation of the oscillatory gain spectrum. Gain spectra showing characteristic, tsunami-like oscillations are simulated for Ar(15+) ions capturing one electron in distant collisions with Al and Na nanoclusters.

  13. Fluorescent DNA Stabilized Silver Nanoclusters as Biosensors

    Directory of Open Access Journals (Sweden)

    Alfonso Latorre

    2013-01-01

    Full Text Available DNA stabilized fluorescent silver nanoclusters are promising materials, of which fluorescent properties can be exploited to develop sensors. Particularly, the presence of a DNA strand in the structure has promoted the development of gene sensors where one part of the sensor is able to recognize the target gene sequence. Moreover, since oligonucleotides can be designed to have binding properties (aptamers a variety of sensors for proteins and cells have been developed using silver nanoclusters. In this review the applications of this material as sensors of different biomolecules are summarized.

  14. Chirality in Bare and Passivated Gold Nanoclusters

    CERN Document Server

    Garzon, I L; Rodrigues-Hernandez, J I; Sigal, I; Beltran, M R; Michaelian, K

    2002-01-01

    Chiral structures have been found as the lowest-energy isomers of bare (Au$_{28}$ and Au$_{55}) and thiol-passivated (Au$_{28}(SCH$_{3})$_{16}$ and Au$_{38}$(SCH$_{3}$)$_{24}) gold nanoclusters. The degree of chirality existing in the chiral clusters was calculated using the Hausdorff chirality measure. We found that the index of chirality is higher in the passivated clusters and decreases with the cluster size. These results are consistent with the observed chiroptical activity recently reported for glutahione-passivated gold nanoclusters, and provide theoretical support for the existence of chirality in these novel compounds.

  15. Surface mediated assembly of small, metastable gold nanoclusters

    Science.gov (United States)

    Pettibone, John M.; Osborn, William A.; Rykaczewski, Konrad; Talin, A. Alec; Bonevich, John E.; Hudgens, Jeffrey W.; Allendorf, Mark D.

    2013-06-01

    The unique properties of metallic nanoclusters are attractive for numerous commercial and industrial applications but are generally less stable than nanocrystals. Thus, developing methodologies for stabilizing nanoclusters and retaining their enhanced functionality is of great interest. We report the assembly of PPh3-protected Au9 clusters from a heterogeneous mixture into films consisting of sub 3 nm nanocluster assemblies. The depositing nanoclusters are metastable in solution, but the resulting nanocluster assemblies are stabilized indefinitely in air or fresh solvent. The films exhibit distinct structure from Au nanoparticles observed by X-ray diffraction, and film dissolution data support the preservation of small nanoclusters. UV-Vis spectroscopy, electrospray ionization mass spectrometry, X-ray photoelectron spectroscopy and electron microscopy are used to elucidate information regarding the nanocluster formation and assembly mechanism. Preferential deposition of nanocluster assemblies can be achieved on multiple substrates, including polymer, Cr, Si, SiO2, SiNx, and metal-organic frameworks (MOFs). Unlike other vapor phase coating processes, nanocluster assembly on the MIL-68(In) MOF crystal is capable of preferentially coating the external surface and stabilizing the crystal structure in hydrothermal conditions, which should enhance their storage, separation and delivery capabilities.The unique properties of metallic nanoclusters are attractive for numerous commercial and industrial applications but are generally less stable than nanocrystals. Thus, developing methodologies for stabilizing nanoclusters and retaining their enhanced functionality is of great interest. We report the assembly of PPh3-protected Au9 clusters from a heterogeneous mixture into films consisting of sub 3 nm nanocluster assemblies. The depositing nanoclusters are metastable in solution, but the resulting nanocluster assemblies are stabilized indefinitely in air or fresh solvent. The

  16. Silver nanoclusters emitting weak NIR fluorescence biomineralized by BSA

    Science.gov (United States)

    Li, Baoshun; Li, Jianjun; Zhao, Junwu

    2015-01-01

    Noble metal (e.g., gold and silver) nanomaterials possess unique physical and chemical properties. In present work, silver nanoclusters (also known as silver quantum clusters or silver quantum dots) were synthesized by bovine serum albumin (BSA) biomineralization. The synthesized silver nanoclusters were characterized by UV-VIS absorption spectroscopy, fluorescence spectroscopy, upconversion emission spectroscopy, TEM, HRTEM and FTIR spectroscopy. TEM results showed that the average size of the silver nanoclusters was 2.23 nm. Fluorescence results showed that these silver nanoclusters could emit weak near-infrared (NIR) fluorescence (the central emission wavelength being about 765 nm). And the central excitation wavelength was about 395 nm, in the UV spectral region. These silver nanoclusters showed an extraordinarily large gap (about 370 nm) between the central excitation wavelength and central emission wavelength. In addition, it was found that these silver nanoclusters possess upconversion emission property. Upconversion emission results showed that the upconversion emission spectrum of the silver nanoclusters agreed well with their normal fluorescence emission spectrum. The synthesized silver nanoclusters showed high stability in aqueous solution and it was considered that they might be confined in BSA molecules. It was found that silver nanoclusters might enhance and broaden the absorption of proteins, and the protein absorption peak showed an obvious red shift (being 7 nm) after the formation of silver nanoclusters.

  17. Thermodynamic stability of ligand-protected metal nanoclusters

    Science.gov (United States)

    Taylor, Michael G.; Mpourmpakis, Giannis

    2017-01-01

    Despite the great advances in synthesis and structural determination of atomically precise, thiolate-protected metal nanoclusters, our understanding of the driving forces for their colloidal stabilization is very limited. Currently there is a lack of models able to describe the thermodynamic stability of these ‘magic-number’ colloidal nanoclusters as a function of their atomic-level structural characteristics. Herein, we introduce the thermodynamic stability theory, derived from first principles, which is able to address stability of thiolate-protected metal nanoclusters as a function of the number of metal core atoms and thiolates on the nanocluster shell. Surprisingly, we reveal a fine energy balance between the core cohesive energy and the shell-to-core binding energy that appears to drive nanocluster stabilization. Our theory applies to both charged and neutral systems and captures a large number of experimental observations. Importantly, it opens new avenues for accelerating the discovery of stable, atomically precise, colloidal metal nanoclusters. PMID:28685777

  18. Metal/Metal-Oxide Nanoclusters for Gas Sensor Applications

    Directory of Open Access Journals (Sweden)

    Ahmad I. Ayesh

    2016-01-01

    Full Text Available The development of gas sensors that are based on metal/metal-oxide nanoclusters has attracted intensive research interest in the last years. Nanoclusters are suitable candidates for gas sensor applications because of their large surface-to-volume ratio that can be utilized for selective and rapid detection of various gaseous species with low-power consuming electronics. Herein, nanoclusters are used as building blocks for the construction of gas sensor where the electrical conductivity of the nanoclusters changes dramatically upon exposure to the target gas. In this review, recent progress in the fabrication of size-selected metallic nanoclusters and their utilization for gas sensor applications is presented. Special focus will be given to the enhancement of the sensing performance through the rational functionalization and utilization of different nanocluster materials.

  19. Thermodynamic stability of ligand-protected metal nanoclusters

    Science.gov (United States)

    Taylor, Michael G.; Mpourmpakis, Giannis

    2017-07-01

    Despite the great advances in synthesis and structural determination of atomically precise, thiolate-protected metal nanoclusters, our understanding of the driving forces for their colloidal stabilization is very limited. Currently there is a lack of models able to describe the thermodynamic stability of these `magic-number' colloidal nanoclusters as a function of their atomic-level structural characteristics. Herein, we introduce the thermodynamic stability theory, derived from first principles, which is able to address stability of thiolate-protected metal nanoclusters as a function of the number of metal core atoms and thiolates on the nanocluster shell. Surprisingly, we reveal a fine energy balance between the core cohesive energy and the shell-to-core binding energy that appears to drive nanocluster stabilization. Our theory applies to both charged and neutral systems and captures a large number of experimental observations. Importantly, it opens new avenues for accelerating the discovery of stable, atomically precise, colloidal metal nanoclusters.

  20. Plasmon transmutation: inducing new modes in nanoclusters by adding dielectric nanoparticles.

    Science.gov (United States)

    Wen, Fangfang; Ye, Jian; Liu, Na; Van Dorpe, Pol; Nordlander, Peter; Halas, Naomi J

    2012-09-12

    Planar clusters of coupled plasmonic nanoparticles support nanoscale electromagnetic "hot spots" and coherent effects, such as Fano resonances, with unique near and far field signatures, currently of prime interest for sensing applications. Here we show that plasmonic cluster properties can be substantially modified by the addition of individual, discrete dielectric nanoparticles at specific locations on the cluster, introducing new plasmon modes, or transmuting existing plasmon modes to new ones, in the resulting metallodielectric nanocomplex. Depositing a single carbon nanoparticle in the junction between a pair of adjacent nanodisks induces a metal-dielectric-metal quadrupolar plasmon mode. In a ten-membered cluster, placement of several carbon nanoparticles in junctions between multiple adjacent nanoparticles introduces a collective magnetic plasmon mode into the Fano dip, giving rise to an additional subradiant mode in the metallodielectric nanocluster response. These examples illustrate that adding dielectric nanoparticles to metallic nanoclusters expands the number and types of plasmon modes supported by these new mixed-media nanoscale assemblies.

  1. Fabrication and in vitro characterization of gadolinium-based nanoclusters for simultaneous drug delivery and radiation enhancement

    Science.gov (United States)

    Yoo, Shannon S.; Guo, Linghong; Sun, Xuejun; Shaw, Andrew R.; Yuan, Zhipeng; Löbenberg, Raimar; Roa, Wilson H.

    2016-09-01

    We report the synthesis of a gadolinium hydroxide (Gd(OH)3) nanorod based doxorubicin (Dox) delivery system that can enhance both magnetic resonance imaging contrast and radiation sensitivity. A simple and cost effective wet-chemical method was utilized in the presence of manganese (Mn) ions and Dox to produce the Gd(OH)3:Mn·Dox nanocluster structure. The Gd(OH)3:Mn·Dox nanocluster was composed of Mn-doped Gd(OH)3 nanorods arranged in parallel with Dox as a linker molecule between the adjacent nanorods. No other studies have utilized Dox as both the linker and therapeutic molecule in a nanostructure to date. The Gd(OH)3 nanorod is reported to have no significant cellular or in vivo toxicity, which makes it an ideal base material for this biomedical application. The Gd(OH)3:Mn·Dox nanocluster exhibited paramagnetic behavior and was stable in a colloidal solution. The nanocluster also enabled high Dox loading capacity and specifically released Dox in a sustained and pH-dependent manner. The positively charged Gd(OH)3:Mn·Dox nanoclusters were readily internalized into MDA-MB-231 breast cancer cells via endocytosis, which resulted in intracellular release of Dox. The released Dox in cells was effective in conferring cytotoxicity and inhibiting proliferation of cancer cells. Furthermore, a synergistic anticancer effect could be observed with radiation treatment. Overall, the Gd(OH)3:Mn·Dox nanocluster drug delivery system described herein may have potential utility in clinics as a multifunctional theranostic nanoparticle with combined benefits in both diagnosis and therapy in the management of cancer.

  2. Metal/Metal-Oxide Nanoclusters for Gas Sensor Applications

    OpenAIRE

    Ayesh, Ahmad I.

    2016-01-01

    The development of gas sensors that are based on metal/metal-oxide nanoclusters has attracted intensive research interest in the last years. Nanoclusters are suitable candidates for gas sensor applications because of their large surface-to-volume ratio that can be utilized for selective and rapid detection of various gaseous species with low-power consuming electronics. Herein, nanoclusters are used as building blocks for the construction of gas sensor where the electrical conductivity of the...

  3. Nanocluster formation in Co/Fe implanted ZnO

    Energy Technology Data Exchange (ETDEWEB)

    Bharuth-Ram, K., E-mail: kbr@tlabs.ac.za [Durban University of Technology, Physics Department (South Africa); Masenda, H. [University of the Witwatersrand, School of Physics (South Africa); Doyle, T. B. [iThemba LABS (South Africa); Geburt, S.; Ronning, C. [University of Jena, Institute of Solid State Physics (Germany)

    2015-04-15

    Conversion electron Mössbauer Spectroscopy (CEMS) measurements were made on a ZnO single crystal sample implanted at room temperature (RT) with of 145 and 345 keV {sup 59}Co ions with respective fluences of 1.15×10{sup 16} ions/cm {sup 2} and 4.17×10{sup 16} ions/cm {sup 2}, followed by implantation of 60 keV {sup 57}Fe to a fluence of 0.50×10{sup 16}/cm {sup 2} to yield a ‘box-shaped’ implantation profile with a Co + Fe concentration of about 3.2 at. %. CEM spectra were collected after annealing the sample up to 973 K. The spectra after annealing up to 973 K are similar to spectra observed in other CEMS studies on Fe implanted ZnO, but show a dramatic change after the 973 K annealing step; it is dominated by a doublet component with fit parameters typical of Fe {sup 3+}. Magnetization curves of the sample after the 973 K anneal show hysteresis, with a small residual magnetization at RT that increases at 4 K. The saturation magnetization at 4 K was approximately 0.33 μ{sub B}/CoFe ion, in good agreement with observations for 5–8 nm sized Co nanoclusters in ZnO.

  4. Improving the Stability of Fluorescent Silver Nanoclusters

    Science.gov (United States)

    Swanson, Nicholas; Stanko, Danielle; Campbell, Ian; Wittmershaus, Bruce

    The quantum mechanical nature of noble metal nanoparticles results in them having optical properties much different from the bulk metal. Silver nanoclusters (AgNC), groups of 4 to 20 atoms, are characterized by strong optical transitions in the visible part of the spectrum giving them an appearance like fluorescent organic dyes. These nanoclusters can also have fluorescence quantum yields over 90%. Following the analysis of published results of DNA templated nanoclusters, we created a procedure for synthesizing AgNC. The AgNC have a high fluorescence quantum yield but degrade with a lifetime of only a few days when in solution at room temperature. Our goal in this study was to increase the stability of the AgNC towards improving their value as a fluorescent material in various applications, such as luminescent solar concentrators. To increase their stability, we've chosen to modify our procedure by removing oxygen from the solution after the sample has reacted. Oxygen removal caused a significant increase in the stability of the clusters over a given period of time. This material is based upon work supported by the National Science Foundation under Grant Number NSF-ECCS-1306157.

  5. Formation of solid Kr nanoclusters in MgO

    NARCIS (Netherlands)

    van Huis, MA; van Veen, A; Schut, H; Kooi, BJ; De Hosson, JTM

    2003-01-01

    The phenomenon of positron confinement enables us to investigate the electronic structure of nanoclusters embedded in host matrices. Solid Kr nanoclusters are a very interesting subject of investigation because of the very low predicted value of the positron affinity of bulk Kr. In this work,

  6. Synthesis and characterization of mixed ligand chiral nanoclusters

    KAUST Repository

    Guven, Zekiye P.

    2016-06-22

    Chiral mixed ligand silver nanoclusters were synthesized in the presence of a chiral and an achiral ligand. While the chiral ligand led mostly to the formation of nanoparticles, the presence of the achiral ligand drastically increased the yield of nanoclusters with enhanced chiral properties. © 2016 The Royal Society of Chemistry.

  7. Molecular interactions in particular Van der Waals nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Jungclas, Hartmut; Schmidt, Lothar [Marburg Univ. (Germany). Chemistry Dept.; Komarov, Viacheslav V.; Popova, Anna M. [Marburg Univ. (Germany). Chemistry Dept.; Lomonosov Moscow State Univ. (Russian Federation). Skobeltzin Inst. of Nuclear Physics

    2017-04-01

    A method is presented to analyse the interaction energies in a nanocluster, which is consisting of three neutral molecules bound by non-covalent long range Van der Waals forces. One of the molecules (M{sub 0}) in the nanocluster has a permanent dipole moment, whereas the two other molecules (M{sub 1} and M{sub 2}) are non-polar. Analytical expressions are obtained for the numerical calculation of the dispersion and induction energies of the molecules in the considered nanocluster. The repulsive forces at short intermolecular distances are taken into account by introduction of damping functions. Dispersion and induction energies are calculated for a nanocluster with a definite geometry, in which the polar molecule M{sub 0} is a linear hydrocarbon molecule C{sub 5}H{sub 10} and M{sub 1} and M{sub 2} are pyrene molecules. The calculations are done for fixed distances between the two pyrene molecules. The results show that the induction energies in the considered three-molecular nanocluster are comparable with the dispersion energies. Furthermore, the sum of induction energies in the substructure (M{sub 0}, M{sub 1}) of the considered nanocluster is much higher than the sum of induction energies in a two-molecular nanocluster with similar molecules (M{sub 0}, M{sub 1}) because of the absence of an electrostatic field in the latter case. This effect can be explained by the essential intermolecular induction in the three-molecular nanocluster.

  8. In Vivo Renal Clearance, Biodistribution, Toxicity of Gold nanoclusters

    CERN Document Server

    Zhang, Xiao-Dong; Shen, Xiu; Liu, Pei-Xun; Fan, Fei-Yue; Fan, Sai-Jun; 10.1016/j.biomaterials.2012.03.020

    2012-01-01

    Gold nanoparticles have shown great prospective in cancer diagnosis and therapy, but they can not be metabolized and prefer to accumulate in liver and spleen due to their large size. The gold nanoclusters with small size can penetrate kidney tissue and have promise to decrease in vivo toxicity by renal clearance. In this work, we explore the in vivo renal clearance, biodistribution, and toxicity responses of the BSA- and GSH-protected gold nanoclusters for 24 hours and 28 days. The BSA-protected gold nanoclusters have low-efficient renal clearance and only 1% of gold can be cleared, but the GSH-protected gold nanoclusters have high-efficient renal clearance and 36 % of gold can be cleared after 24 hours. The biodistribution further reveals that 94% of gold can be metabolized for the GSH-protected nanoclusters, but only less than 5% of gold can be metabolized for the BSA-protected nanoclusters after 28 days. Both of the GSH- and BSA-protected gold nanoclusters cause acute infection, inflammation, and kidney fu...

  9. Nanoclusters and Microparticles in Gases and Vapors

    CERN Document Server

    Smirnov, Boris M

    2012-01-01

    Research of processes involving Nanoclusters and Microparticleshas been developing fastin many fields of rescent research, in particular in materials science. To stay at the cutting edge of this development, a sound understanding of the processes is needed. In this work, several processes involving small particles are described, such as transport processes in gases, charging of small particles in gases, chemical processes, atom attachment and quenching of excited atomic particles on surfaces, nucleation, coagulation, coalescence and growth processes for particles and aggregates. This work pres

  10. Peptide-stabilized, fluorescent silver nanoclusters

    DEFF Research Database (Denmark)

    Gregersen, Simon; Vosch, Tom André Jos; Jensen, Knud Jørgen

    2016-01-01

    . Herein, we demonstrate how solid-phase methods can increase throughput dramatically in peptide ligand screening and in initial evaluation of fluorescence intensity and chemical stability of peptide-stabilized AgNCs (P-AgNCs). 9-Fluorenylmethyloxycarbonyl (Fmoc) solid-phase peptide synthesis......Few-atom silver nanoclusters (AgNCs) can exhibit strong fluorescence; however, they require ligands to prevent aggregation into larger nanoparticles. Fluorescent AgNCs in biopolymer scaffolds have so far mainly been synthesized in solution, and peptides have only found limited use compared to DNA...

  11. On the fluctuation mechanism of melting of supported gold nanoclusters.

    Science.gov (United States)

    Pushkin, M A; Troyan, V I; Borisyuk, P V; Borman, V D; Tronin, V N

    2012-11-01

    The size dependence of the melting temperature of Au nanoclusters deposited on SiO2 and HOPG substrates, measured by the elastic-peak electron spectroscopy (EPES) is discussed. The observed behavior of the melting temperature with decrease in clusters' size is qualitatively explained in the framework of the fluctuation mechanism for surface melting. The interaction of nanoclusters with substrate is taken into account by means of the effective surface tension for spherical-segment shaped particles, corresponding to the contact angle of supported nanocluster.

  12. Nonlinear analysis of nano-cluster doped fiber

    Institute of Scientific and Technical Information of China (English)

    LIU Gang; ZHANG Ru

    2007-01-01

    There are prominent nonlinear characteristics that we hope for the semiconductor nano-clusters doped fiber. Refractive index of fiber core can be effectively changed by adulteration. This technology can provide a new method for developing photons components. Because the semiconductor nano-cluster has quantum characteristics,Based on first-order perturbation theory and classical theory of fiber,we deduced refractive index expressions of fiber core,which was semiconductor nano-cluster doped fiber. Finally,third-order nonlinear coefficient equation was gained. Using this equation,we calculated SMF-28 fiber nonlinear coefficient. The equation shows that new third-order coefficient was greater.

  13. A thermochromic silver nanocluster exhibiting dual emission character

    Science.gov (United States)

    Xu, Qing-Qing; Dong, Xi-Yan; Huang, Ren-Wu; Li, Bo; Zang, Shuang-Quan; Mak, Thomas C. W.

    2015-01-01

    A Ag12(SCH2C10H7)6(CF3CO2)6(CH3CN)6 (1) nanocluster modified using naphthalen-2-yl-methanethiol was synthesized and structurally characterized by single crystal X-ray analysis. The targeted luminescent nanocluster displays dual emission with the property of reversible thermochromism spanning from red to bright yellow.A Ag12(SCH2C10H7)6(CF3CO2)6(CH3CN)6 (1) nanocluster modified using naphthalen-2-yl-methanethiol was synthesized and structurally characterized by single crystal X-ray analysis. The targeted luminescent nanocluster displays dual emission with the property of reversible thermochromism spanning from red to bright yellow. Electronic supplementary information (ESI) available: Experimental section and supporting Fig. S1-S6. CCDC 1004246. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4nr05122j

  14. Controllable 5-sulfosalicylic acid assisted solvothermal synthesis of monodispersed superparamagnetic Fe3O4 nanoclusters with tunable size

    Science.gov (United States)

    Wang, Wentao; Tang, Bingtao; Wu, Suli; Gao, Zhanming; Ju, Benzhi; Teng, Xiaoxu; Zhang, Shufen

    2017-02-01

    Monodispersed Fe3O4 nanoclusters were synthesized in a one-pot solvothermal route with 5-sulfosalicylic acid (SSA) as the functional ligand in a mixed-solvent system of diethylene glycol/ethylene glycol (DEG/EG). Nucleation and aggregation growth model was responsible for the formation of secondary structure of the clusters. In the process, the size of the clusters can be effectively controlled by varying the amounts of SSA and the volume ratio of DEG/EG. The nanoclusters exhibited superparamagnetic properties with high saturation magnetization value of about 68.7 emu g-1 at room temperature. The water-soluble small-molecule SSA grafted on the surface of Fe3O4 nanocrystals rendered the superparamagnetic clusters dispersible in water, which is crucial for potential applications in biomedical fields.

  15. Surface modification of adamantane-terminated gold nanoclusters using cyclodextrins.

    Science.gov (United States)

    Yan, Chunyang; Liu, Chao; Abroshan, Hadi; Li, Zhimin; Qiu, Renhua; Li, Gao

    2016-08-17

    The surface functionality of Au38S2(SAdm)20 nanoclusters (-SAdm = adamantanethiolate) in the presence of α-, β-, and γ-cyclodextrins (CDs) is studied. The supramolecular chemistry and host-guest interactions of CDs and the protecting ligands of nanoclusters are investigated using UV-vis and NMR spectroscopies, MALDI mass spectrometry, and molecular dynamics simulations. In contrast to α- and γ-CDs, the results show that β-CDs are capable of efficiently chemisorbing onto the Au38S2(SAdm)20 nanoclusters to yield Au38S2(SAdm)20-(β-CD)2 conjugates. MD simulations revealed that two -SAdm ligands of the nanoparticle with the least steric hindrance are capable to selectively be accommodated into hydrophobic cavity of β-CDs, as furthermore confirmed by NMR spectroscopy. The conjugates largely improve the stability of the nanoclusters in the presence of strong oxidants (e.g., TBHP). Further, the electrochemical properties of Au38S2(SAdm)20 nanoclusters and Au38S2(SAdm)20-(β-CD)2 conjugates are compared. The charge transfer to the redox probe molecules (e.g., K3Fe(CN)6) in solution was monitored by cyclic voltammetry. It is found that β-CDs act as an umbrella to cover the fragile metal cores of the nanoclusters, thereby blocking direct interaction with destabilizing agents and hence quenching the charge transfer process.

  16. Quantification of NS1 dengue biomarker in serum via optomagnetic nanocluster detection

    Science.gov (United States)

    Antunes, Paula; Watterson, Daniel; Parmvi, Mattias; Burger, Robert; Boisen, Anja; Young, Paul; Cooper, Matthew A.; Hansen, Mikkel F.; Ranzoni, Andrea; Donolato, Marco

    2015-11-01

    Dengue is a tropical vector-borne disease without cure or vaccine that progressively spreads into regions with temperate climates. Diagnostic tools amenable to resource-limited settings would be highly valuable for epidemiologic control and containment during outbreaks. Here, we present a novel low-cost automated biosensing platform for detection of dengue fever biomarker NS1 and demonstrate it on NS1 spiked in human serum. Magnetic nanoparticles (MNPs) are coated with high-affinity monoclonal antibodies against NS1 via bio-orthogonal Cu-free ‘click’ chemistry on an anti-fouling surface molecular architecture. The presence of the target antigen NS1 triggers MNP agglutination and the formation of nanoclusters with rapid kinetics enhanced by external magnetic actuation. The amount and size of the nanoclusters correlate with the target concentration and can be quantified using an optomagnetic readout method. The resulting automated dengue fever assay takes just 8 minutes, requires 6 μL of serum sample and shows a limit of detection of 25 ng/mL with an upper detection range of 20000 ng/mL. The technology holds a great potential to be applied to NS1 detection in patient samples. As the assay is implemented on a low-cost microfluidic disc the platform is suited for further expansion to multiplexed detection of a wide panel of biomarkers.

  17. Study on tunable resonator using a cantilevered carbon nanotube encapsulating a copper nanocluster

    Science.gov (United States)

    Kang, Jeong Won; Kim, Ki-Sub; Park, Jungchul; Hwang, Ho Jung

    2011-02-01

    We investigated an ultrahigh frequency carbon nanotube resonator encapsulating a nanocluster, as another tunable resonator, via classical molecular dynamics simulations and continuum models. The fundamental frequency of cantilevered carbon nanotube resonator encapsulating a copper nanocluster could be adjusted by controlling the position of the encapsulated copper nanocluster. Data obtained from the molecular dynamics simulations were analyzed with continuum theory, and we found that statistically the change in the effective mass factor was greatly correlated with the position change of the encapsulated nanocluster.

  18. Size dependence of thermoelectric power of Au, Pd, Pt nanoclusters deposited onto HOPG surface

    OpenAIRE

    Borisyuk, P. V.; V. I. Troyan; Lebedinskii, Yu Yu; Vasilyev, O S

    2016-01-01

    The paper presents the study of tunnel current-voltage characteristics of Au, Pd and Pt nanoclusters deposited onto the highly oriented pyrolytic graphite (HOPG) surface by pulsed laser deposition. The analysis of tunnel current-voltage characteristics obtained by scanning tunneling spectroscopy (STS) allowed to recover the thermoelectric power value of nanoclusters. It was found that the value of thermoelectric power of pulsed laser deposited nanoclusters depends on nanocluster material and ...

  19. Modelling nano-clusters and nucleation.

    Science.gov (United States)

    Catlow, C Richard A; Bromley, Stefan T; Hamad, Said; Mora-Fonz, Miguel; Sokol, Alexey A; Woodley, Scott M

    2010-01-28

    We review the growing role of computational techniques in modelling the structures and properties of nano-particulate oxides and sulphides. We describe the main methods employed, including those based on both electronic structure and interatomic potential approaches. Particular attention is paid to the techniques used in searching for global minima in the energy landscape defined by the nano-particle cluster. We summarise applications to the widely studied ZnO and ZnS systems, to silica nanochemistry and to group IV oxides including TiO(2). We also consider the special case of silica cluster chemistry in solution and its importance in understanding the hydrothermal synthesis of microporous materials. The work summarised, together with related experimental studies, demonstrates a rich and varied nano-cluster chemistry for these materials.

  20. Silver Nanocluster Reparative Effect in Hernioplasty

    Directory of Open Access Journals (Sweden)

    Nikolay M. Anichkov

    2014-06-01

    Full Text Available Background: The acceleration of re-epithelialization and fibroblast differentiation were noted during the experiments with silver nanoclusters (SNs by interrupting the negative development of inflammation at the level of cytokines and promoting a positive course of reparative processes. The aim of this work was to elaborate the experimental model of prosthesis hernioplasty in subcutaneous and intraperitoneal locations of hernioprostheses with SNs, which allowed us to study the course of reparative reactions in all layers of the anterior abdominal wall. Material and Methods: We used a modified hernioprosthesis made from polyester fibers coated with a metal-polymer composition, including the stabilized SN in a concentration of 6.8 and 11.3 mg per 1 g of the hernioprosthesis mesh. During this research we used guinea pigs to study the in vivo tissue reactions. The clinical part of the study included the group of 212 patients who underwent removal of an inguinal hernia. We have identified various factors associated with infectious and toxic effects on the body by determining the level of the serum glutamate-pyruvate-transaminase (SGPT. Results: In implantation of the hernioprostheses, including the high concentration of SN in the laparotomy wound, the exudative component of the inflammation was weakly expressed. It was mostly the proliferative changes that took place. We did not find either CD8-positive type T lymphocytes or PAX5-positive type B activated cells in the exudate. Conclusion: Our research has shown that the use of hernioprostheses that include silver nanoclusters leads to the reduction of inflammation in the exudative phase and to a more favorable course of reparative processes.

  1. Synthesis of crystalline Ge nanoclusters in PE-CVD-deposited SiO2 films

    DEFF Research Database (Denmark)

    Leervad Pedersen, T.P.; Skov Jensen, J.; Chevallier, J.

    2005-01-01

    The synthesis of evenly distributed Ge nanoclusters in plasma-enhanced chemical-vapour-deposited (PE-CVD) SiO2 thin films containing 8 at. % Ge is reported. This is of importance for the application of nanoclusters in semiconductor technology. The average diameter of the Ge nanoclusters can...

  2. Plasmonic enhancement of the magneto-optical response of MnP nanoclusters embedded in GaP epilayers

    Science.gov (United States)

    Monette, Gabriel; Nateghi, Nima; Masut, Remo A.; Francoeur, Sébastien; Ménard, David

    2012-12-01

    We report on the magneto-optical activity of MnP nanoclusters embedded in GaP epilayers and MnP thin film as a function of temperature, magnetic field, and wavelength in the near infrared and visible. The measured Faraday rotation originates from the ferromagnetic magnetization of the metallic MnP phase and exhibits a hysteretic behavior as a function of an externally applied magnetic field closely matching that of the magnetization. The Faraday rotation spectrum of MnP shows a magnetoplasmonic resonance whose energy depends on the MnP filling factor and surrounding matrix permittivity. At resonance, the measured rotary power for the epilayer systems increases by a factor of 2 compared to that of the MnP film in terms of degrees of rotation per MnP thickness for an applied magnetic field of 410 mT. We propose an effective medium model, which qualitatively reproduces the Faraday rotation and the magnetocircular dichroism spectra, quantitatively determines the spectral shift induced by variations in the MnP volume fraction, and demonstrates the influence of the shape and orientation distributions of ellipsoidal MnP nanoclusters on the magneto-optical activity and absorption spectra.

  3. NanoClusters Enhance Drug Delivery in Mechanical Ventilation

    Science.gov (United States)

    Pornputtapitak, Warangkana

    The overall goal of this thesis was to develop a dry powder delivery system for patients on mechanical ventilation. The studies were divided into two parts: the formulation development and the device design. The pulmonary system is an attractive route for drug delivery since the lungs have a large accessible surface area for treatment or drug absorption. For ventilated patients, inhaled drugs have to successfully navigate ventilator tubing and an endotracheal tube. Agglomerates of drug nanoparticles (also known as 'NanoClusters') are fine dry powder aerosols that were hypothesized to enable drug delivery through ventilator circuits. This Thesis systematically investigated formulations of NanoClusters and their aerosol performance in a conventional inhaler and a device designed for use during mechanical ventilation. These engineered powders of budesonide (NC-Bud) were delivered via a MonodoseRTM inhaler or a novel device through commercial endotracheal tubes, and analyzed by cascade impaction. NC-Bud had a higher efficiency of aerosol delivery compared to micronized stock budesonide. The delivery efficiency was independent of ventilator parameters such as inspiration patterns, inspiration volumes, and inspiration flow rates. A novel device designed to fit directly to the ventilator and endotracheal tubing connections and the MonodoseRTM inhaler showed the same efficiency of drug delivery. The new device combined with NanoCluster formulation technology, therefore, allowed convenient and efficient drug delivery through endotracheal tubes. Furthermore, itraconazole (ITZ), a triazole antifungal agent, was formulated as a NanoCluster powder via milling (top-down process) or precipitation (bottom-up process) without using any excipients. ITZ NanoClusters prepared by wet milling showed better aerosol performance compared to micronized stock ITZ and ITZ NanoClusters prepared by precipitation. ITZ NanoClusters prepared by precipitation methods also showed an amorphous state

  4. Relaxation path of metastable nanoclusters in oxide dispersion strengthened materials

    Science.gov (United States)

    Ribis, J.; Thual, M. A.; Guilbert, T.; de Carlan, Y.; Legris, A.

    2017-02-01

    ODS steels are a promising class of structural materials for sodium cooled fast reactor application. The ultra-high density of the strengthening nanoclusters dispersed within the ferritic matrix is responsible of the excellent creep properties of the alloy. Fine characterization of the nanoclusters has been conducted on a Fe-14Cr-0.3Ti-0.3Y2O3 ODS material using High Resolution and Energy Filtered Transmission Electron Microscopy. The nanoclusters exhibit a cubic symmetry possibly identified as f.c.c and display a non-equilibrium YTiCrO chemical composition thought to be stabilized by a vacancy supersaturation. These nanoclusters undergo relaxation towards the Y2Ti2O7-like state as they grow. A Cr shell is observed around the relaxed nano-oxides, this size-dependent shell may form after the release of Cr by the particles. The relaxation energy barrier appears to be higher for the smaller particles probably owing to a volume/surface ratio effect in reason to the full coherency of the nanoclusters.

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

    Directory of Open Access Journals (Sweden)

    Silvia Varela-Aramburu

    2016-09-01

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

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

    Science.gov (United States)

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

    2016-01-01

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

  7. Ligand-Induced Stability of Gold Nanoclusters: Thiolate versus Selenolate.

    Science.gov (United States)

    Kurashige, Wataru; Yamaguchi, Masaki; Nobusada, Katsuyuki; Negishi, Yuichi

    2012-09-20

    Thiolate-protected gold nanoclusters have attracted considerable attention as building blocks for new functional materials and have been extensively researched. Some studies have reported that changing the ligand of these gold nanoclusters from thiolate to selenolate increases cluster stability. To confirm this, in this study, we compare the stabilities of precisely synthesized [Au25(SC8H17)18](-) and [Au25(SeC8H17)18](-) against degradation in solution, thermal dissolution, and laser fragmentation. The results demonstrate that changing the ligand from thiolate to selenolate increases cluster stability in reactions involving dissociation of the gold-ligand bond but reduces cluster stability in reactions involving intramolecular dissociation of the ligand. These results reveal that using selenolate ligands makes it possible to produce gold clusters that are more stable against degradation in solution than thiolate-protected gold nanoclusters.

  8. Superconducting state of metallic nanoclusters and Josephson tunneling networks

    Energy Technology Data Exchange (ETDEWEB)

    Kresin, Vladimir, E-mail: vzkresin@lbl.gov [Lawrence Berkeley Laboratory, University of California at Berkeley, CA 94720 (United States); Ovchinnikov, Yurii [L. Landau Institute for Theoretical Physics, RAN, Moscow 117334 (Russian Federation)

    2014-11-15

    Highlights: • Specific nanoclusters form a new family of high T{sub c} superconductors. • For an isolated cluster the pairing affects its energy spectrum. • Nano-based Josephson tunneling network can transfer a macroscopic superconducting current at high temperatures. • A.c. tunneling network can be synchronized and radiates as a single junction. - Abstract: Metallic nanoclusters form a new family of high temperature superconductors. In principle, the value of T{sub c} can be raised up to room temperature. In addition, one can observe the Josephson tunneling between two clusters. One can build the nanocluster-based tunneling network capable to transfer a macroscopic supercurrent at high temperatures. Such a network can be synchronized and radiate as single junction.

  9. Quantum confinement in GaP nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Laurich, B.K.; Smith, D.C.; Healy, M.D.

    1994-06-01

    We have prepared GaP and GaAs nanoclusters from organometallic condensation reactions of E[Si(ChH{sub 3})3]3 (E = P, As) and GaCl{sub 3}. The size of the as synthesized clusters is 10 {Angstrom} to 15 {Angstrom}. Larger clusters of 20 {Angstrom} to 30 {Angstrom} size were obtained by thermal annealing of the as grown material. X-ray diffraction and transmission electron microscopy confirm the high crystalline quality. A lattice contraction of 6.7% could be seen for 10 {Angstrom} sized GaAs clusters. The clusters are nearly spherical in shape. Optical absorption spectra show a distinct line which can be assigned to the fundamental transition of the quantum confined electronic state. The measured blue shift, with respect to the GaP bulk absorption edge is 0.53 eV. As the cluster is smaller than the exciton radius, we can calculate the cluster size from this blue shift and obtain 20.2 {Angstrom}, consistent with the results from X-ray diffraction of 19.5 {Angstrom} for the same sample.

  10. Fractal Electronic Circuits Assembled From Nanoclusters

    Science.gov (United States)

    Fairbanks, M. S.; McCarthy, D.; Taylor, R. P.; Brown, S. A.

    2009-07-01

    Many patterns in nature can be described using fractal geometry. The effect of this fractal character is an array of properties that can include high internal connectivity, high dispersivity, and enhanced surface area to volume ratios. These properties are often desirable in applications and, consequently, fractal geometry is increasingly employed in technologies ranging from antenna to storm barriers. In this paper, we explore the application of fractal geometry to electrical circuits, inspired by the pervasive fractal structure of neurons in the brain. We show that, under appropriate growth conditions, nanoclusters of Sb form into islands on atomically flat substrates via a process close to diffusion-limited aggregation (DLA), establishing fractal islands that will form the basis of our fractal circuits. We perform fractal analysis of the islands to determine the spatial scaling properties (characterized by the fractal dimension, D) of the proposed circuits and demonstrate how varying growth conditions can affect D. We discuss fabrication approaches for establishing electrical contact to the fractal islands. Finally, we present fractal circuit simulations, which show that the fractal character of the circuit translates into novel, non-linear conduction properties determined by the circuit's D value.

  11. Catalytic photooxidation of pentachlorophenol using semiconductor nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    WILCOXON,JESS P.

    2000-04-17

    Pentachlorophenol (PCP) is a toxic chlorinated aromatic molecule widely used as fungicide, a bactericide and a wood preservation, and thus ubiquitous in the environment. The authors report photo-oxidation of PCP using a variety of nanosize semiconductor metal oxides and sulfides in both aqueous and polar organic solvents and compare the photo-oxidation kinetics of these nanoclusters to widely studied bulk powders like Degussa P-25 TiO{sub 2} and CdS. They study both the light intensity dependence of PCP photooxidation for nanosize SnO{sub 2} and the size dependence of PCP photooxidation for both nanosize SnO{sub 2} and MoS{sub 2}. They find an extremely strong size dependence for the latter which they attribute to its size-dependent band gap and the associated change in redox potentials due to quantum confinement of the hole-electron pair. The authors show that nanosize MoS{sub 2} with a diameter of d=3.0 nm and an absorbance edge of {approximately}450 nm is a very effective photooxidation catalyst for complete PCP mineralization, even when using only visible light irradiation.

  12. Correlation effects in Auger spectra of Ni and Cu nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Troyan, V.I.; Borisyuk, P.V.; Kashurnikov, V.A. [National Research Nuclear University (MEPhI), 31 Kashirskoye shosse, 115409, Moscow (Russian Federation); Krasavin, A.V., E-mail: avkrasavin@gmail.com [National Research Nuclear University (MEPhI), 31 Kashirskoye shosse, 115409, Moscow (Russian Federation); Borman, V.D.; Tronin, V.I. [National Research Nuclear University (MEPhI), 31 Kashirskoye shosse, 115409, Moscow (Russian Federation)

    2013-01-17

    Results of experimental research of exciton-like two-hole states in nanoclusters of narrow-band metals (Ni, Cu) on surface of high-oriented pyrolitic graphite by X-ray photoelectron and Auger electron spectroscopy are presented. It was found that the evolution of the electronic structure in Ni nanoclusters with the decreasing of their sizes can lead to appearance of long-living two-hole states in the valence band. One-particle and two-particle density of states are analyzed, and the Auger-electron spectra confirming the presence of the bound and localized states are obtained.

  13. On the formation of copper nanoparticles in nanocluster aggregation source

    NARCIS (Netherlands)

    Dutka, Mikhail V.; Turkin, Anatoliy A.; Vainchtein, David I.; De Hosson, Jeff Th. M.

    2015-01-01

    The influence of pressure and type of inert gas (Ar and Kr) on the morphology and size distribution of nanoparticles produced in a nanocluster source is studied experimentally. The experimental data are used to validate the model of cluster formation from a supersaturated atomic vapor in an inert bu

  14. On the formation of copper nanoparticles in nanocluster aggregation source

    NARCIS (Netherlands)

    Dutka, Mikhail V.; Turkin, Anatoliy A.; Vainchtein, David I.; De Hosson, Jeff Th. M.

    The influence of pressure and type of inert gas (Ar and Kr) on the morphology and size distribution of nanoparticles produced in a nanocluster source is studied experimentally. The experimental data are used to validate the model of cluster formation from a supersaturated atomic vapor in an inert

  15. Surface Segregation in Supported Pd-Pt Nanoclusters and Alloys

    NARCIS (Netherlands)

    van den Oetelaar, L.C.A.; Nooij, O.W.; Oerlemans, S.; Denier van der Gon, A.W.; Brongersma, H.H.; Lefferts, Leonardus; Roosenbrand, A.G.; van Veen, J.A.R.

    1998-01-01

    Surface segregation processes in Pd-Pt alloys and bimetallic Pd-Pt nanoclusters on alumina and carbon supports (technical catalysts) have been investigated by determining the metal surface composition of these systems by low-energy ion scattering (LEIS). Both Pd-rich (Pd80Pt20) and Pt-rich

  16. Enhanced fluorescence of silver nanoclusters stabilized with branched oligonucleotides.

    Science.gov (United States)

    Latorre, Alfonso; Lorca, Romina; Zamora, Félix; Somoza, Álvaro

    2013-05-28

    DNA stabilized silver nanoclusters (AgNCs) are promising optical materials, whose fluorescence properties can be tuned by the selection of the DNA sequence employed. In this work we have used modified oligonucleotides in the preparation of AgNCs. The fluorescent intensity obtained was 60 times higher than that achieved with standard oligonucleotides.

  17. Nanoclustering as a dominant feature of plasma membrane organization

    NARCIS (Netherlands)

    Garcia-Parajo, M.F.; Cambi, A.; Torreno-Pina, J.A.; Thompson, N.; Jacobson, K.

    2014-01-01

    Early studies have revealed that some mammalian plasma membrane proteins exist in small nanoclusters. The advent of super-resolution microscopy has corroborated and extended this picture, and led to the suggestion that many, if not most, membrane proteins are clustered at the plasma membrane at

  18. Ultrafast coherence transfer in DNA-templated silver nanoclusters

    DEFF Research Database (Denmark)

    Thyrhaug, Erling; Bogh, Sidsel Ammitzbøll; Carro, Miguel

    2017-01-01

    DNA-templated silver nanoclusters of a few tens of atoms or less have come into prominence over the last several years due to very strong absorption and efficient emission. Applications in microscopy and sensing have already been realized, however little is known about the excited-state structure...

  19. On the formation of copper nanoparticles in nanocluster aggregation source

    NARCIS (Netherlands)

    Dutka, Mikhail V.; Turkin, Anatoliy A.; Vainchtein, David I.; De Hosson, Jeff Th. M.

    2015-01-01

    The influence of pressure and type of inert gas (Ar and Kr) on the morphology and size distribution of nanoparticles produced in a nanocluster source is studied experimentally. The experimental data are used to validate the model of cluster formation from a supersaturated atomic vapor in an inert bu

  20. PHOTOOXIDATION OF ORGANIC WASTES USING SEMICONDUCTOR NANOCLUSTERS

    Energy Technology Data Exchange (ETDEWEB)

    Wilcoxon, Jess P.

    2000-12-31

    It would be a major boon to have a visible light absorbing semiconductor catalytic material available, which is also photostable and non-toxic. Such a photocatalyst would make it possible to exploit sunlight as the sole energy source required for detoxification. To this end we have employed our expertise in nanocluster synthesis and processing to make and purify nanoparticles of MoS2. The band-gap and absorbance edges of these nanoparticles can be adjusted by particle size based upon the quantum confinement of the electron-hole pair. In a recent paper we demonstrated the use of these new photocatalysts to destroy phenol, and demonstrated a strong effect of size or band-gap on the rate of photo-oxidation.5 In this research we investigate the photooxidation kinetics and products formed for a standard material, Degussa P-25 TiO2, as compared to nanosize TiO2, SnO2, and MoS2. We examined the light intensity dependence for nanosize SnO2 compared to TiO2 (Degussa), and the effect o f size on photooxidation kinetics for both SnO2 and MoS2. We studied photooxidation in aqueous systems and, for the first time, a system consisting almost entirely of a polar organic, acetonitrile. Our primary objective was to develop an entirely new class of material: nanosize semiconductors with visible bandgaps and to engineer these material's properties to allow us to photooxidize toxic organic compounds in water on a reasonable time scale ({approx}8 hrs). A second objective was to study how certain material properties such as size, surface treatment, and material type affect the efficiency of the photocatalytic process as well as optimizing these features.

  1. Polarization properties of fluorescent BSA protected Au25 nanoclusters

    Science.gov (United States)

    Raut, Sangram; Chib, Rahul; Rich, Ryan; Shumilov, Dmytro; Gryczynski, Zygmunt; Gryczynski, Ignacy

    2013-03-01

    BSA protected gold nanoclusters (Au25) are attracting a great deal of attention due to their unique spectroscopic properties and possible use in biophysical applications. Although there are reports on synthetic strategies, spectroscopy and applications, little is known about their polarization behavior. In this study, we synthesized the BSA protected Au25 nanoclusters and studied their steady state and time resolved fluorescence properties including polarization behavior in different solvents: glycerol, propylene glycol and water. We demonstrated that the nanocluster absorption spectrum can be separated from the extinction spectrum by subtraction of Rayleigh scattering. The nanocluster absorption spectrum is well approximated by three Gaussian components. By a comparison of the emissions from BSA Au25 clusters and rhodamine B in water, we estimated the quantum yield of nanoclusters to be higher than 0.06. The fluorescence lifetime of BSA Au25 clusters is long and heterogeneous with an average value of 1.84 μs. In glycerol at -20 °C the anisotropy is high, reaching a value of 0.35. However, the excitation anisotropy strongly depends on the excitation wavelengths indicating a significant overlap of the different transition moments. The anisotropy decay in water reveals a correlation time below 0.2 μs. In propylene glycol the measured correlation time is longer and the initial anisotropy depends on the excitation wavelength. BSA Au25 clusters, due to long lifetime and high polarization, can potentially be used in studying large macromolecules such as protein complexes with large molecular weight.BSA protected gold nanoclusters (Au25) are attracting a great deal of attention due to their unique spectroscopic properties and possible use in biophysical applications. Although there are reports on synthetic strategies, spectroscopy and applications, little is known about their polarization behavior. In this study, we synthesized the BSA protected Au25 nanoclusters and

  2. Ion-tuned DNA/Ag fluorescent nanoclusters as versatile logic device.

    Science.gov (United States)

    Li, Tao; Zhang, Libing; Ai, Jun; Dong, Shaojun; Wang, Erkang

    2011-08-23

    A novel kind of versatile logic device has been constructed utilizing ion-tuned DNA/Ag fluorescent nanoclusters, with K(+) and H(+) as two inputs. A well-chosen hairpin DNA with a poly-C loop serves as the template for synthesizing two species of Ag nanoclusters. Several G-tracts and C-tracts on its two terminals enable the hairpin DNA to convert into the G-quadruplex and/or i-motif structures upon input of K(+) and H(+). Such a structural change remarkably influences the spectral behaviors of Ag nanoclusters. In particular, different species of Ag nanoclusters have distinct fluorescence responses to the input of K(+) and H(+). These unique features of DNA/Ag nanoclusters enable multiple logic operations via multichannel fluorescence output, indicating the versatility as a molecular logic device. By altering the specific sequence of the hairpin DNA, more logic gates can be constructed utilizing Ag nanoclusters. © 2011 American Chemical Society

  3. Iron-oxide colloidal nanoclusters: from fundamental physical properties to diagnosis and therapy

    Science.gov (United States)

    Kostopoulou, Athanasia; Brintakis, Konstantinos; Lascialfari, Alessandro; Angelakeris, Mavroeidis; Vasilakaki, Marianna; Trohidou, Kalliopi; Douvalis, Alexios P.; Psycharakis, Stylianos; Ranella, Anthi; Manna, Liberato; Lappas, Alexandros

    2014-03-01

    Research on magnetic nanocrystals attracts wide-spread interest because of their challenging fundamental properties, but it is also driven by problems of practical importance to the society, ranging from electronics (e.g. magnetic recording) to biomedicine. In that respect, iron oxides are model functional materials as they adopt a variety of oxidation states and coordinations that facilitate their use. We show that a promising way to engineer further their technological potential in diagnosis and therapy is the assembly of primary nanocrystals into larger colloidal entities, possibly with increased structural complexity. In this context, elevated-temperature nanochemistry (c.f. based on a polyol approach) permitted us to develop size-tunable, low-cytotoxicity iron-oxide nanoclusters, entailing iso-oriented nanocrystals, with enhanced magnetization. Experimental (magnetometry, electron microscopy, Mössbauer and NMR spectroscopies) results supported by Monte Carlo simulations are reviewed to show that such assemblies of surface-functionalized iron oxide nanocrystals have a strong potential for innovation. The clusters' optimized magnetic anisotropy (including microscopic surface spin disorder) and weak ferrimagnetism at room temperature, while they do not undermine colloidal stability, endow them a profound advantage as efficient MRI contrast agents and hyperthermic mediators with important biomedical potential.

  4. Nanocluster building blocks of artificial square spin ice: Stray-field studies of thermal dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Pohlit, Merlin, E-mail: pohlit@physik.uni-frankfurt.de; Porrati, Fabrizio; Huth, Michael; Müller, Jens [Institute of Physics, Goethe-University Frankfurt, Frankfurt/Main (Germany); Ohno, Yuzo; Ohno, Hideo [Laboratory for Nanoelectronics and Spintronics, Research Institute of Electrical Communication, Tohoku University, Sendai (Japan)

    2015-05-07

    We present measurements of the thermal dynamics of a Co-based single building block of an artificial square spin ice fabricated by focused electron-beam-induced deposition. We employ micro-Hall magnetometry, an ultra-sensitive tool to study the stray field emanating from magnetic nanostructures, as a new technique to access the dynamical properties during the magnetization reversal of the spin-ice nanocluster. The obtained hysteresis loop exhibits distinct steps, displaying a reduction of their “coercive field” with increasing temperature. Therefore, thermally unstable states could be repetitively prepared by relatively simple temperature and field protocols allowing one to investigate the statistics of their switching behavior within experimentally accessible timescales. For a selected switching event, we find a strong reduction of the so-prepared states' “survival time” with increasing temperature and magnetic field. Besides the possibility to control the lifetime of selected switching events at will, we find evidence for a more complex behavior caused by the special spin ice arrangement of the macrospins, i.e., that the magnetic reversal statistically follows distinct “paths” most likely driven by thermal perturbation.

  5. Signal integration by lipid-mediated spatial cross talk between Ras nanoclusters.

    Science.gov (United States)

    Zhou, Yong; Liang, Hong; Rodkey, Travis; Ariotti, Nicholas; Parton, Robert G; Hancock, John F

    2014-03-01

    Lipid-anchored Ras GTPases form transient, spatially segregated nanoclusters on the plasma membrane that are essential for high-fidelity signal transmission. The lipid composition of Ras nanoclusters, however, has not previously been investigated. High-resolution spatial mapping shows that different Ras nanoclusters have distinct lipid compositions, indicating that Ras proteins engage in isoform-selective lipid sorting and accounting for different signal outputs from different Ras isoforms. Phosphatidylserine is a common constituent of all Ras nanoclusters but is only an obligate structural component of K-Ras nanoclusters. Segregation of K-Ras and H-Ras into spatially and compositionally distinct lipid assemblies is exquisitely sensitive to plasma membrane phosphatidylserine levels. Phosphatidylserine spatial organization is also modified by Ras nanocluster formation. In consequence, Ras nanoclusters engage in remote lipid-mediated communication, whereby activated H-Ras disrupts the assembly and operation of spatially segregated K-Ras nanoclusters. Computational modeling and experimentation reveal that complex effects of caveolin and cortical actin on Ras nanoclustering are similarly mediated through regulation of phosphatidylserine spatiotemporal dynamics. We conclude that phosphatidylserine maintains the lateral segregation of diverse lipid-based assemblies on the plasma membrane and that lateral connectivity between spatially remote lipid assemblies offers important previously unexplored opportunities for signal integration and signal processing.

  6. Ge nanoclusters in PECVD-deposited glass after heat treating and electron irradiation

    DEFF Research Database (Denmark)

    Ou, Haiyan; Rørdam, Troels Peter; Rottwitt, Karsten

    2007-01-01

    This paper reports the formation of Ge nanoclusters in silica glass thin films deposited by plasma-enhanced chemical vapor deposition (PECVD). We studied the samples by transmission electron microscopy (TEM) and Raman spectroscopy after annealing. TEM investigation shows that the Ge nanoclusters...... at two areaswere formed by different mechanisms. The Ge nanoclusters formed in a single row along the interface of a silicon substrate and the silica glass film by annealing during high-temperature heat treatment. Ge nanoclusters did not initially form in the bulk of the film but could be subsequently...

  7. Nano-clustered Pd catalysts formed on GaN surface for green chemistry

    Science.gov (United States)

    Hirayama, Motoi; Ueta, Yukiko; Konishi, Tomoya; Tsukamoto, Shiro

    2011-05-01

    We have succeeded in observing Pd nano-clusters, catalytic prime elements, on a GaN(0 0 0 1) surface by a scanning tunneling microscope for the first time. After the sample was reused, we found that nano-clusters (width: 11 nm, height: 2.2 nm) existed on the surface which still kept the catalytic activity, resulting that the neutral Pd atoms formed the nano-cluster. Moreover, the S-termination contributed to the formation of the dense and flat structure consisting of the Pd nano-clusters.

  8. On the possibility of controlling the hydrophilic/hydrophobic characteristics of toroid Mo138 nanocluster polyoxometalates

    Science.gov (United States)

    Grzhegorzhevskii, K. V.; Adamova, L. V.; Eremina, E. V.; Ostroushko, A. A.

    2017-03-01

    The possibility of changing the hydrophilic (polar) surfaces of toroid nanocluster polyoxomolibdates to hydrophobic (nonpolar) surfaces via the modification of Mo138 nanoclusters by surfactant molecules (dodecylpyridinium chloride) as a result of the interaction between these compounds in solutions is demonstrated. Benzene and methanol are used as molecular probes (indicators of the condition of nanocluster surfaces). Comparative characteristics of the equilibrium sorption of benzene and methanol vapors on the initial and modified surfaces of the solid polyoxometalate, and data on the sorption of organic molecules on the surfaces of Rhodamine B-modified nanoclusters of the toroid (Mo138) and keplerate (Mo132) types are obtained.

  9. Oxygen reduction catalyzed by gold nanoclusters supported on carbon nanosheets

    Science.gov (United States)

    Wang, Qiannan; Wang, Likai; Tang, Zhenghua; Wang, Fucai; Yan, Wei; Yang, Hongyu; Zhou, Weijia; Li, Ligui; Kang, Xiongwu; Chen, Shaowei

    2016-03-01

    Nanocomposites based on p-mercaptobenzoic acid-functionalized gold nanoclusters, Au102(p-MBA)44, and porous carbon nanosheets have been fabricated and employed as highly efficient electrocatalysts for oxygen reduction reaction (ORR). Au102(p-MBA)44 clusters were synthesized via a wet chemical approach, and loaded onto carbon nanosheets. Pyrolysis at elevated temperatures led to effective removal of the thiolate ligands and the formation of uniform nanoparticles supported on the carbon scaffolds. The nanocomposite structures were characterized by using a wide range of experimental techniques such as transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, UV-visible absorption spectroscopy, thermogravimetric analysis and BET nitrogen adsorption/desorption. Electrochemical studies showed that the composites demonstrated apparent ORR activity in alkaline media, and the sample with a 30% Au mass loading was identified as the best catalyst among the series, with a performance comparable to that of commercial Pt/C, but superior to those of Au102 nanoclusters and carbon nanosheets alone, within the context of onset potential, kinetic current density, and durability. The results suggest an effective approach to the preparation of high-performance ORR catalysts based on gold nanoclusters supported on carbon nanosheets.Nanocomposites based on p-mercaptobenzoic acid-functionalized gold nanoclusters, Au102(p-MBA)44, and porous carbon nanosheets have been fabricated and employed as highly efficient electrocatalysts for oxygen reduction reaction (ORR). Au102(p-MBA)44 clusters were synthesized via a wet chemical approach, and loaded onto carbon nanosheets. Pyrolysis at elevated temperatures led to effective removal of the thiolate ligands and the formation of uniform nanoparticles supported on the carbon scaffolds. The nanocomposite structures were characterized by using a wide range of experimental techniques such as

  10. Circular single domains in hemispherical Permalloy nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Araujo, Clodoaldo I. L de, E-mail: dearaujo@ufv.br; Fonseca, Jakson M. [Departamento de Física, Universidade Federal de Viçosa, 36570-900 Viçosa-MG (Brazil); Sinnecker, João P. [Centro Brasileiro de Pesquisas Físicas, 22290-180 Rio de Janeiro-RJ (Brazil); Delatorre, Rafael G.; Garcia, Nicolas; Pasa, André A. [Departamento de Física, Universidade Federal de Santa Catarina, 88040-900 Florianópolis-SC (Brazil)

    2014-11-14

    We have studied ferromagnetic Permalloy clusters obtained by electrodeposition on n-type silicon. Magnetization measurements reveal hysteresis loops almost independent on temperature and very similar in shape to those obtained in nanodisks with diameter bigger than 150 nm. The spin configuration for the ground state, obtained by micromagnetic simulation, shows topological vortices with random chirality and polarization. This behavior in the small diameter clusters (∼80 nm) is attributed to the Dzyaloshinskii-Moriya interaction that arises in its hemispherical geometries. This magnetization behavior can be utilized to explain the magnetoresistance measured with magnetic field in plane and out of sample plane.

  11. A study of many-body phenomena in metal nanoclusters (Au, Cu) close to their transition to the nonmetallic state

    NARCIS (Netherlands)

    Borman, VD; Borisyuk, PV; Lebid'ko, VV; Pushkin, AA; Tronin, VN; Troyan, [No Value; Antonov, DA; Filatov, DO

    2006-01-01

    The results of a study of many-body phenomena in gold and copper nanoclusters are presented. The measured conductivity as a function of nanocluster height h was found to have a minimum at h approximate to 0.6 nm. Conductivity was local in character at nanocluster sizes l infinity) to nonmetallic (ep

  12. Size Dependence of Atomically Precise Gold Nanoclusters in Chemoselective Hydrogenation and Active Site Structure

    Energy Technology Data Exchange (ETDEWEB)

    Li, Gao [Carnegie Mellon University (CMU); Jiang, Deen [ORNL; Kumar, Santosh [Carnegie Mellon University (CMU); Chen, Yuxiang [Carnegie Mellon University (CMU); Jin, Rongchao [Carnegie Mellon University (CMU)

    2014-01-01

    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 effect 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.

  13. Template free synthesis of natural carbohydrates functionalised fluorescent silver nanoclusters.

    Science.gov (United States)

    Ebrahiminezhad, Alireza; Berenjian, Aydin; Ghasemi, Younes

    2016-06-01

    Template-assisted synthesis is one of the most recognised techniques for fabrication of silver nanoclusters (AgNCs). However, this process is time consuming, toxic and expensive. In this study, the authors report a completely novel approach for the green and facile synthesis of AgNCs using Matricaria chamomilla, without any additional template. Fluorescent and colloidally stable AgNCs with average particle size of 2.4 nm were successfully produced. They found that carbohydrates from Matricaria chamomilla act as an ideal template to generate fluorescent AgNCs. Moreover, oxygen-bearing functional groups were validated to be the active groups for anchoring and reducing of Ag(+) ions. The novel carbohydrate coating method makes the prepared nanoclusters completely hydrophilic and stable in aqueous matrices.

  14. The expanding universe of thiolated gold nanoclusters and beyond.

    Science.gov (United States)

    Jiang, De-en

    2013-08-21

    Thiolated gold nanoclusters form a universe of their own. Researchers in this field are constantly pushing the boundary of this universe by identifying new compositions and in a few "lucky" cases, solving their structures. Such solved structures, even if there are only few, provide important hints for predicting the many identified compositions that are yet to be crystallized or structure determined. Structure prediction is the most pressing issue for a computational chemist in this field. The success of the density functional theory method in gauging the energetic ordering of isomers for thiolated gold clusters has been truly remarkable, but to predict the most stable structure for a given composition remains a great challenge. In this feature article from a computational chemist's point of view, the author shows how one understands and predicts structures for thiolated gold nanoclusters based on his old and new results. To further entertain the reader, the author also offers several "imaginative" structures, claims, and challenges for this field.

  15. Shape and scale dependent diffusivity of colloidal nanoclusters and aggregates

    Science.gov (United States)

    Alcanzare, M. M. T.; Ollila, S. T. T.; Thakore, V.; Laganapan, A. M.; Videcoq, A.; Cerbelaud, M.; Ferrando, R.; Ala-Nissila, T.

    2016-07-01

    The diffusion of colloidal nanoparticles and nanomolecular aggregates, which plays an important role in various biophysical and physicochemical phenomena, is currently under intense study. Here, we examine the shape and size dependent diffusion of colloidal nano- particles, fused nanoclusters and nanoaggregates using a hybrid fluctuating lattice Boltzmann-Molecular Dynamics method. We use physically realistic parameters characteristic of an aqueous solution, with explicitly implemented microscopic no-slip and full-slip boundary conditions. Results from nanocolloids below 10 nm in radii demonstrate how the volume fraction of the hydrodynamic boundary layer influences diffusivities. Full-slip colloids are found to diffuse faster than no-slip particles. We also characterize the shape dependent anisotropy of the diffusion coefficients of nanoclusters through the Green-Kubo relation. Finally, we study the size dependence of the diffusion of nanoaggregates comprising N ≤ 108 monomers and demonstrate that the diffusion coefficient approaches the continuum scaling limit of N-1/3.

  16. Optical properties of Si nanoclusters with passivated surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Dinh, L.N. [Univ. of California, Davis, CA (United States). Dept. of Applied Science]|[Lawrence Livermore National Lab., CA (United States). Chemistry and Materials Science Dept.; Chase, L.L.; Balooch, M.; Siekhaus, W.J. [Lawrence Livermore National Lab., CA (United States). Chemistry and Material Science Dept.; Wooten, F. [Univ. of California, Davis, CA (United States). Dept. of Applied Science

    1996-12-31

    Si nanoclusters with average size of a few nanometers have been synthesized by thermal vaporization of Si in an Ar buffer gas, and passivated with oxygen or atomic hydrogen. High resolution transmission electron microscopy (HRTEM) and X-ray diffraction (XRD) revealed that these nanoclusters were crystalline. All samples showed strong infrared and/or visible photoluminescence (PL) with varying decay times form nanoseconds to microseconds depending on synthesis conditions. Absorption mainly in the Si cores was observed by photoluminescence excitation (PLE) spectroscopy. The visible components of PL spectra were noted to blue shift and broaden as the size of the Si nanocrystals (nc-Si) was reduced, and there were differences in PL spectra for hydrogen and oxygen passivated nc-Si. This data can be explained best by a model involving absorption between quantum confined states in the Si cores and emission by surface/interface states.

  17. Catalytically highly active top gold atom on palladium nanocluster.

    Science.gov (United States)

    Zhang, Haijun; Watanabe, Tatsuya; Okumura, Mitsutaka; Haruta, Masatake; Toshima, Naoki

    2011-10-23

    Catalysis using gold is emerging as an important field of research in connection with 'green' chemistry. Several hypotheses have been presented to explain the markedly high activities of Au catalysts. So far, the origin of the catalytic activities of supported Au catalysts can be assigned to the perimeter interfaces between Au nanoclusters and the support. However, the genesis of the catalytic activities of colloidal Au-based bimetallic nanoclusters is unclear. Moreover, it is still a challenge to synthesize Au-based colloidal catalysts with high activity. Here we now present the 'crown-jewel' concept (Supplementary Fig. S1) for preparation of catalytically highly Au-based colloidal catalysts. Au-Pd colloidal catalysts containing an abundance of top (vertex or corner) Au atoms were synthesized according to the strategy on a large scale. Our results indicate that the genesis of the high activity of the catalysts could be ascribed to the presence of negatively charged top Au atoms.

  18. Optimal control of electromagnetic field using metallic nanoclusters

    Science.gov (United States)

    Grigorenko, Ilya; Haas, Stephan; Balatsky, Alexander; Levi, A. F. J.

    2008-04-01

    The dielectric properties of metallic nanoclusters in the presence of an applied electromagnetic field are investigated using the non-local linear response theory. In the quantum limit we find a nontrivial dependence of the induced field and charge distributions on the spatial separation between the clusters and on the frequency of the driving field. Using a genetic algorithm, these quantum functionalities are exploited to custom-design sub-wavelength lenses with a frequency-controlled switching capability.

  19. Mossbauer Characterization of Iron Oxide Nanoclusters Grown within Aluminosilicate Matrices

    Science.gov (United States)

    2003-01-01

    2Facultad de Ciencias Fisicas , Universidad Mayor de San Marcos, Lima, Peru. 3Centro Brasileiro de Pesquisas Fisicas , Rio de Janeiro, Brasil. ABSTRACT...nanoclusters. Zeolitic and sol-gel derived molecular sieves and a variety of cross-linked and block co-polymers have been used to this purpose [1-41. The...Brasileiro de Pesquisas Fisicas and the NSF: DMR 0074537 for support. Figures 1 and 2 ame reprinted with permission from reference [I]. Copyright 2001

  20. Preparation of nanocomposites containing nanoclusters of transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Milne, S.B.; Lukehart, C.M., Wittig, J.E. [Vanderbilt Univ., Nashville, TN (United States)] [and others

    1996-10-01

    New nanocomposites containing nanoclusters of transition metals have been prepared and characterized by TEM, XRD, and energy dispersive spectroscopy. Organometallic or other coordination compounds functionalized with trialkoxysilyl groups have been synthesized and covalently incorporated into silica xerogels using standard sol-gel techniques. Thermal oxidative treatment of these xerogels in air followed by reduction in hydrogen yielded the desired nanocomposite phases. Using these methods, Mo, Re, Fe, Ru, Os, Pd, Pt, Cu. and Ag nanocomposites have been prepared.

  1. DNase 1 Retains Endodeoxyribonuclease Activity Following Gold Nanocluster Synthesis

    Science.gov (United States)

    2014-07-04

    Gatan). Microscopy samples were prepared for analysis through the following steps: (i) bulk material was ground up using a mortar and pestle , (ii...employed as efficient and fast sensors to augment the current time-consuming DNA contamination analysis techniques. Noble metal nanoclusters (NCs...to metal nanoparticles (NPs), which do not exhibit fluorescence but show plasmonic transitions involving surface electrons. By definition , NCs are

  2. Theory of Nanocluster Size Distributions from Ion Beam Synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, C.W.; Yi, D.O.; Sharp, I.D.; Shin, S.J.; Liao, C.Y.; Guzman, J.; Ager III, J.W.; Haller, E.E.; Chrzan, D.C.

    2008-06-13

    Ion beam synthesis of nanoclusters is studied via both kinetic Monte Carlo simulations and the self-consistent mean-field solution to a set of coupled rate equations. Both approaches predict the existence of a steady state shape for the cluster size distribution that depends only on a characteristic length determined by the ratio of the effective diffusion coefficient to the ion flux. The average cluster size in the steady state regime is determined by the implanted species/matrix interface energy.

  3. Live Cell Surface Labeling with Fluorescent Ag Nanocluster Conjugates†

    OpenAIRE

    Yu, Junhua; Choi, Sungmoon; Richards, Chris I.; Antoku, Yasuko; Dickson, Robert M

    2008-01-01

    DNA-encapsulated silver clusters are readily conjugated to proteins and serve as alternatives to organic dyes and semiconductor quantum dots. Stable and bright on the bulk and single molecule levels, Ag nanocluster fluorescence is readily observed when staining live cell surfaces. Being significantly brighter and more photostable than organics and much smaller than quantum dots with a single point of attachment, these nanomaterials offer promising new approaches for bulk and single molecule b...

  4. Hyperspherical and related views of the dynamics of nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Lombardi, A; Palazzetti, F; Grossi, G; Aquilanti, V [Dipartimento di Chimica, Universita di Perugia, Via Elce di Sotto 8, 06123 Perugia (Italy); Castro Palacio, J C [Departamento de FI sica, Universidad de Pinar del Rio, MartI 270, Esq. 27 de Noviembre, Pinar del Rio (Cuba); Rubayo Soneira, J [Departamento de Fisica General y Matema ticas, Instituto Superior de Ciencias y Tecnologia Nucleares, Quinta de los Molinos, Avenne Carlos III y Luaces, Plaza C. Habana (Cuba)], E-mail: abulafia@dyn.unipg.it

    2009-10-15

    In this paper, we give an account of recent progress in understanding properties of nanoaggregates, following their dynamical behavior by classical mechanics simulations and utilizing tools based on extensions of hyperspherical and related techniques, originally developed for the quantum mechanical treatment of few-body atomic and molecular systems. After an outline of the underlying theory, recent applications exemplifying statistical and thermodynamic aspects of nanoclusters are discussed.

  5. In-vitro Synthesis of Gold Nanoclusters in Neurons

    Science.gov (United States)

    2016-04-01

    Pradeep T. Protein-protected luminescent noble metal quantum clusters : an emerging trend in atomic cluster nanoscience. Nano Rev. 2012;3:14767−14783. 2...5 Approved for public release; distribution is unlimited. 1 1. Introduction Noble metal nanoclusters (NCs) composed of...toxic to the cells based on the results from the 100-mM solutions discussed previously. Potentially, other cell lines might yield brighter clusters

  6. Observation of Body-Centered Cubic Gold Nanocluster.

    Science.gov (United States)

    Liu, Chao; Li, Tao; Li, Gao; Nobusada, Katsuyuki; Zeng, Chenjie; Pang, Guangsheng; Rosi, Nathaniel L; Jin, Rongchao

    2015-08-17

    The structure of nanoparticles plays a critical role in dictating their material properties. Gold is well known to adopt face-centered cubic (fcc) structure. Herein we report the first observation of a body-centered cubic (bcc) gold nanocluster composed of 38 gold atoms protected by 20 adamantanethiolate ligands and two sulfido atoms ([Au38S2(SR)20], where R=C10H15) as revealed by single-crystal X-ray crystallography. This bcc structure is in striking contrast with the fcc structure of bulk gold and conventional Au nanoparticles, as well as the bi-icosahedral structure of [Au38(SCH2CH2Ph)24]. The bcc nanocluster has a distinct HOMO-LUMO gap of ca. 1.5 eV, much larger than the gap (0.9 eV) of the bi-icosahedral [Au38(SCH2CH2Ph)24]. The unique structure of the bcc gold nanocluster may be promising in catalytic applications.

  7. UV luminescence of dendrimer-encapsulated gold nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Shim, Hyeong Seop; Kim, Jun Myung; Sohn, So Hyeong; Han, Noh Soo; Park, Seung Min [Dept. of Chemistry, Kyung Hee University, Seoul (Korea, Republic of)

    2016-10-15

    Size-dependent luminescence color is one of the interesting properties of metal nanocrystals, whose sizes are in the dimension of the Fermi wavelength of an electron. Despite the short Fermi wavelength of electrons in gold (-0.7 nm), luminescence of gold nanoclusters has been reported to range from the near-infrared to near-ultraviolet, depending on the number of atoms in the nanoclusters. The photoluminescence of G4-OH (Au) obtained by the excitation of 266 nm showed UV emission in addition to the well-known blue emission. The higher intensity and red-shifted emission of the gold nanoclusters was distinguished from the emission of dendrimers. The UV emission at 352 nm matched the emission energy of Au{sub 4} in the spherical jellium model, rather than the planar Au{sub 8}, which supported the emission of Au{sub 4} formed in G4-OH. Despite the change of [HAuCl{sub 4} ]/[G4-OH], the relative population between Au{sub 4} and Au{sub 8} was similar in G4-OH(Au), which indicated that the closed electronic and geometric structures stabilized the magic number of Au{sub 4}.

  8. Ab Initio Calculations for the Surface Energy of Silver Nanoclusters

    Science.gov (United States)

    Medasani, Bharat; Vasiliev, Igor; Park, Young Ho

    2007-03-01

    We apply first principles computational methods to study the surface energy and the surface stress of silver nanoparticles. The structures, energies and lattice contractions of spherical Ag nanoclusters are calculated in the framework of density functional theory combined with the generalized gradient approximation. Our calculations predict the surface energies of Ag nanoclusters to be in the range of 1-2 J/m^2. These values are close to the bulk surface energy of silver, but are significantly lower than the recently reported value of 7.2 J/m^2 derived from the Kelvin equation for free Ag nanoparticles. From the lattice contraction and the nearest neighbor interatomic distance, we estimate the surface stress of the silver nanoclusters to be in the the range of 1-1.45 N/m. This result suggests that a liquid droplet model can be employed to evaluate the surface energy and the surface stress of Ag nanoparticles. K. K. Nanda et al., Phys. Rev. Lett. 91, 106102 (2003).

  9. Polyethyleneimine Capped Silver Nanoclusters as Efficient Antibacterial Agents.

    Science.gov (United States)

    Xu, Dong; Wang, Qingyun; Yang, Tao; Cao, Jianzhong; Lin, Qinlu; Yuan, Zhiqin; Li, Le

    2016-03-18

    Development of efficient antibacterial agents is critical for human health. In the present study, we investigated the antibacterial activity of polyethyleneimine (PEI)-capped silver nanoclusters (PEI-AgNCs), based on the fact that nanoclusters normally have higher surface-to-volume ratios than traditional nanomaterials and PEI itself has a strong antimicrobial capacity. We synthesized stable silver nanoclusters by altering PEI molecular weight from 0.6 kDa to 25 kDa and characterized them by UV-Vis absorption and fluorescence spectroscopy and high resolution transmission electron microscopy. The sizes of AgNCs were around 2 nm in diameter and were little influenced by the molecular weight of PEIs. The antibacterial abilities of the four PEI-AgNCs were explored on agar plate and in liquid systems. Our results revealed that the antibacterial activity of PEI-AgNCs is excellent and the reduction of PEI molecular weight could result in the increased antibacterial capacity of PEI-AgNCs. Such proposed new materials might be useful as efficient antibacterial agents in practical clinical applications.

  10. Synthesis of bimetallic gold-silver alloy nanoclusters by simple mortar grinding.

    Science.gov (United States)

    Murugadoss, Arumugam; Kai, Noriko; Sakurai, Hidehiro

    2012-02-21

    A macroscale quantity of bimetallic Au-Ag alloy nanoclusters was achieved through sequential reduction by simple mortar grinding. The chitosan biopolymer was used as both a stabilizing and reducing agent. These nanoclusters exhibit excellent catalytic activity toward the reduction of 4-nitrophenol.

  11. Organic Inorganic Hybrid Solar Cell Efficiency Improvement By Employing Au Nanocluster

    Science.gov (United States)

    2015-06-14

    Specialists Conference Conference Date: June 14, 2015 Organic - Inorganic Hybrid Solar Cell Efficiency Improvement by Employing Au Nanocluster Manisha...tunable conductivity, organic polymer, heterojunction, nanocluster I. INTRODUCTION Recently, organic / inorganic hybrid heterojunction solar cells have...conventional Si p−n junction. These heterojunction devices are intended to exploit the advantageous properties of both organic and inorganic materials

  12. Controlling embedment and surface chemistry of nanoclusters in metal-organic frameworks.

    Science.gov (United States)

    Coupry, D E; Butson, J; Petkov, P S; Saunders, M; O'Donnell, K; Kim, H; Buckley, C; Addicoat, M; Heine, T; Szilágyi, P Á

    2016-04-14

    A combined theoretical and experimental approach demonstrates that nanocluster embedment into the pores of metal-organic frameworks (MOF) may be influenced by the chemical functionalisation of the MOF. Furthermore, this results in the surface functionalisation of the embedded nanoclusters, highlighting the potential of MOF scaffolds for the design and synthesis of novel functional materials.

  13. Synthesis and Doping of Ligand-Protected Atomically-Precise Metal Nanoclusters

    KAUST Repository

    Aljuhani, Maha A.

    2016-05-01

    Rapidly expanding research in nanotechnology has led to exciting progress in a versatile array of applications from medical diagnostics to catalysis. This success resulted from the manipulation of the desired properties of nanomaterials by controlling their size, shape, and composition. Among the most thriving areas of research about nanoparticle is the synthesis and doping of the ligand-protected atomically-precise metal nanoclusters. In this thesis, we developed three different novel metal nanoclusters, such as doped Ag29 with five gold (Au) atoms leading to enhance its quantum yield with remarkable stability. We also developed half-doped (alloyed) cluster of Ni6 nanocluster with molybdenum (Mo). This enabled enhanced stability and better catalytic activity. The third metal nanocluster that we synthesized was Au28 nanocluster by using di-thiolate as the ligand stabilizer instead of mono-thiolate. The new metal clusters obtained have been characterized by spectroscopic, electrochemical and crystallographic methods.

  14. Quantum-sized gold nanoclusters: bridging the gap between organometallics and nanocrystals.

    Science.gov (United States)

    Jin, Rongchao; Zhu, Yan; Qian, Huifeng

    2011-06-06

    This Concept article provides an elementary discussion of a special class of large-sized gold compounds, so-called Au nanoclusters, which lies in between traditional organogold compounds (e.g., few-atom complexes, 2 nm). The discussion is focused on the relationship between them, including the evolution from the Au⋅⋅⋅Au aurophilic interaction in Au(I) complexes to the direct Au-Au bond in clusters, and the structural transformation from the fcc structure in nanocrystals to non-fcc structures in nanoclusters. Thiolate-protected Au(n)(SR)(m) nanoclusters are used as a paradigm system. Research on such nanoclusters has achieved considerable advances in recent years and is expected to flourish in the near future, which will bring about exciting progress in both fundamental scientific research and technological applications of nanoclusters of gold and other metals.

  15. One-step facile synthesis of Pd nanoclusters supported on carbon and their electrochemical property

    Directory of Open Access Journals (Sweden)

    Junjun Shi

    2014-12-01

    Full Text Available Well-crystallized Pd nanoclusters supported on Ketjen Black (KB were successfully fabricated when Pd wires were served as an electrode pair by a solution plasma technique at atmospheric pressure. The synthesis of Pd nanoclusters was almost simultaneous with their dispersion on KB. Pd nanoclusters with the average diameter of about 2 nm were equably distributed on KB, and showed good electrochemical property corresponding to their obvious characteristic peaks. Multi-scan cyclic voltammetry and chronoamperometry clarified that as-prepared Pd nanoclusters have better electrochemical stability in alkaline solution than that of in acidic solution. Thus as-obtained Pd nanoclusters would become a promising electrocatalyst for fuel cells or Li-air batteries.

  16. Development of ultrafine multichannel microfluidic mixer for synthesis of bimetallic nanoclusters: catalytic application of highly monodisperse AuPd nanoclusters stabilized by poly(N-vinylpyrrolidone).

    Science.gov (United States)

    Hayashi, Naoto; Sakai, Yuka; Tsunoyama, Hironori; Nakajima, Atsushi

    2014-09-02

    On account of their novel properties, bimetallic nanoparticles and nanoclusters (NCs) are strong potential candidates for optical, magnetic, and catalytic functional materials. These properties depend on the chemical composition and size (number of constituent atoms) of the NCs. Control of size, structure, and composition is particularly important for fabricating highly functional materials based on bimetallic NCs. Size- and structure-controlled synthesis of two-element alloys can reveal their intrinsic electronic synergistic effects. However, because synergistic enhancement of activity is strongly affected by composition as well as by size and structure, controlled synthesis is a challenging task, particularly in catalytic applications. To investigate catalytic synergistic effects, we have synthesized highly monodisperse, sub-2 nm, solid-solution AuPd NCs stabilized with poly(N-vinylpyrrolidone) (AuPd:PVP) using a newly developed ultrafine microfluidic mixing device with 15 μm wide multiple lamination channels. The synergistic enhancement for catalytic aerobic oxidation of benzyl alcohol exhibited a volcano-shaped trend, with a maximum at 20-65 at. % Pd. From X-ray photoelectron spectroscopic measurements, we confirmed that the enhanced activity originates from the enhanced electron density at the Au sites, donated by Pd sites.

  17. Synthesis of Immunotargeted Magneto-plasmonic Nanoclusters

    Science.gov (United States)

    Wu, Chun-Hsien; Sokolov, Konstantin

    2014-01-01

    Magnetic and plasmonic properties combined in a single nanoparticle provide a synergy that is advantageous in a number of biomedical applications including contrast enhancement in novel magnetomotive imaging modalities, simultaneous capture and detection of circulating tumor cells (CTCs), and multimodal molecular imaging combined with photothermal therapy of cancer cells. These applications have stimulated significant interest in development of protocols for synthesis of magneto-plasmonic nanoparticles with optical absorbance in the near-infrared (NIR) region and a strong magnetic moment. Here, we present a novel protocol for synthesis of such hybrid nanoparticles that is based on an oil-in-water microemulsion method. The unique feature of the protocol described herein is synthesis of magneto-plasmonic nanoparticles of various sizes from primary blocks which also have magneto-plasmonic characteristics. This approach yields nanoparticles with a high density of magnetic and plasmonic functionalities which are uniformly distributed throughout the nanoparticle volume. The hybrid nanoparticles can be easily functionalized by attaching antibodies through the Fc moiety leaving the Fab portion that is responsible for antigen binding available for targeting. PMID:25177973

  18. Importance of configurational contributions to the free energy of nanoclusters

    Directory of Open Access Journals (Sweden)

    M. Posselt

    2013-07-01

    Full Text Available An effective simulation method based on the Wang-Landau Monte Carlo algorithm is used in order to demonstrate the significance of the configurational contributions to the free energy of embedded nanoclusters. Starting from the most stable cluster configuration the simulation provides all geometrically different, but simply connected and sufficiently compact configurations of a nanocluster of a given size and the respective formation energies. The knowledge of these data allows the calculation of the free formation and free binding energy of the cluster at T ≠ 0. The method is applied to coherent Cu clusters in bcc-Fe. It is shown that even at moderate temperatures the configurational contributions to the free formation and binding energy must not be neglected. The dependence of the monomer free binding energy on clusters size is found to change significantly with increasing temperature which has a considerable effect on the pathway of cluster evolution. Therefore, present investigations provide an essential contribution to the improvement of the input parameters for object kinetic Monte Carlo simulations and rate theory used in multi-scale simulations of the nanostructure evolution. The calculation scheme developed in this work is rather general and applicable to many types of embedded nanoclusters. Compared to the method of overlapping distributions hitherto used in some cases to determine the configurational part of the free energy the new method has major advantages. Various tests are performed in order verify the presented approach and to compare with the results of the other calculation procedure. A roadmap is proposed to include the vibrational contributions to the free energy of the clusters within the framework of the method employed in this work.

  19. Organization of copper nanoclusters in Langmuir–Blodgett films

    Indian Academy of Sciences (India)

    G Hemakanthi; Aruna Dhathathreyan; T Ramasami

    2002-02-01

    Stable nanoclusters of Cu were synthesized using Langmuir–Blodgett films of octadecylsuccinic acid (ODSA) as template. The Langmuir–Blodgett films of ODSA formed from subphase containing copper ions were first subjected to sulphidation (S) using sodium sulphide and then hydrogenated (H) using hydrogen gas. Diffuse reflectance UV-visible spectroscopy (DIR-UV-vis), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) used to characterize these films indicated the formation of Cu(0) metallic clusters ranging in size from 3 ∼ 10 nm.

  20. Enantioselective silver nanoclusters: Preparation, characterization and photoluminescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Farrag, Mostafa, E-mail: mostafafarrag@aun.edu.eg

    2016-09-01

    Herein, we report a new wet-synthesis method to separate some water-soluble chiral silver nanoclusters with high yield. The cluster material was obtained by the reduction of silver nitrate with NaBH{sub 4} in the presence of three ligands L-penicillamine (L-pen), D-penicillamine (D-pen) and racemic mixture of penicillamine (rac-pen), functioning as capping ligand. For characterizing all silver cluster samples, the particle size was assessed by transmission electron microscopy (TEM) and powder X-ray diffraction (XRD) and their average chemical formula was determined from thermogravimetric analysis (TGA) and elemental analysis (EA). The particles sizes of all three clusters are 2.1 ± 0.2 nm. The optical properties of the samples were studied by four different methods: UV-vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), photoluminescence spectroscopy (PL) and circular dichroism (CD) spectroscopy. The spectra are dominated by the typical and intense plasmon peak at 486 nm accompanied by a small shoulder at 540 nm. Infrared spectroscopy was measured for the free ligand and protected silver nanoclusters, where the disappearance of the S-H vibrational band (2535–2570 cm{sup −1}) in the silver nanoclusters confirmed anchoring of ligand to the cluster surface through the sulfur atom. PL studies yielded the fluorescent properties of the samples. The main focus of this work, however, lies in the chirality of the particles. For all silver clusters CD spectra were recorded. While for clusters capped with one of the two enantiomers (D- or L-form) typical CD spectra were observed, no significant signals were detected for a racemic ligand mixture. Furthermore, silver clusters show quite large asymmetry factors (up to 3 × 10{sup −4}) in comparison to most other ligand protected clusters. These large factors and bands in the visible range of the spectrum suggest a strong chiral induction from the ligand to the metal core. Textural features of the

  1. Fabrication of metal nanoclusters on graphene grown on Ru(0001)

    Institute of Scientific and Technical Information of China (English)

    ZHANG Hui; FU Qiang; CUI Yi; TAN DaLi; BAO XinHe

    2009-01-01

    Monolayer graphene was epitaxially grown on Ru(0001) through exposure of the Ru(0001) to ethylene at room temperature followed by annealing in ultrahigh vacuum at elevated temperatures. The resulting graphene structures were studied by scanning tunneling microscopy (STM), X-ray photoelectron spec-troscopy (XPS), and ultraviolet photoelectron spectroscopy (UPS). The graphene/Ru(0001) surface was used as a periodic template for growth of metal nanoclusters. Highly dispersed Pt clusters with well controlled size and spatial distribution were fabricated on the surface.

  2. Dynamic study on the transformation process of gold nanoclusters.

    Science.gov (United States)

    Ma, Xiaoqian; Wen, Xiaoming; Toh, Yon-Rui; Huang, Kuo-Yen; Tang, Jau; Yu, Pyng

    2014-11-01

    In this paper, the transformation process from Au8 to Au25 nanoclusters (NCs) is investigated with steady state fluorescence spectroscopy and time-resolved fluorescence spectroscopy at various reaction temperatures and solvent diffusivities. Results demonstrate that Au8 NCs, protected by bovine serum albumin, transform into Au25 NCs under controlled pH values through an endothermic reaction with the activation energy of 74 kJ mol(-1). Meanwhile, the characteristic s-shaped curves describing the formation of Au25 NCs suggest this process involves a diffusion controlled growth mechanism.

  3. Synthesis and characterization of human transferrin-stabilized gold nanoclusters

    Science.gov (United States)

    Le Guével, Xavier; Daum, Nicole; Schneider, Marc

    2011-07-01

    Human transferrin has been biolabelled with gold nanoclusters (Au NCs) using a simple, fast and non-toxic method. These nanocrystals (polyclonal antibody. Additionally, antibody-induced agglomeration demonstrates no alteration in the protein activity and the receptor target ability. MTT and Vialight® Plus tests show no cytotoxicity of these labelled proteins in cells (1 µg ml - 1-1 mg ml - 1). Cell line experiments (A549) indicate also an uptake of the iron loaded fluorescent proteins inside cells. These remarkable data highlight the potential of a new type of non-toxic fluorescent transferrin for imaging and targeting.

  4. Reversible modulation of gold nanoclusters photoluminescence based on electrochromic poly(methylene blue).

    Science.gov (United States)

    Zhang, Hui; Zhai, Yanling; Dong, Shaojun

    2014-11-01

    Reversible photoluminescence (PL) switches based on a complex of gold nanoclusters and electrochromic poly(methylene blue) (PMB) were realized. The gold nanoclusters PL of hybrid device can be modulated reversibly under electrochemical stimulation. Such an electrochromic device presents several advantages, such as large fluorescence contrast under reduction and oxidation potentials, good reversibility and excellent long-time stability. This simple protocol is anticipated to offer important hints for other nanoclusters and electrochromic materials in the field of photoelectric devices. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. Protein mediated synthesis of fluorescent Au-nanoclusters for metal sensory coatings

    Energy Technology Data Exchange (ETDEWEB)

    Vogel, Manja; Raff, Johannes [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Biogeochemistry

    2017-06-01

    Fluorescent Au-nanocluster were successfully synthesized and used for the selective detection of Cu{sup 2} {sup +}. The synthesized Au-BSA-nanoclusters remain functional also after immobilization and show high thermal stability. Additionally, the transfer of the protein mediated Au-nanocluster synthesis route to S-layer proteins was achieved. (The presented work is part of the project BIONEWS dealing with long-term stable cells for the set-up and regeneration of sensor and actor materials for strategic relevant metals, in particular rare earth elements).

  6. Size-dependent mobility of gold nano-clusters during growth on chemically modified graphene

    Energy Technology Data Exchange (ETDEWEB)

    Bell, Gavin R., E-mail: gavin.bell@warwick.ac.uk; Dawson, Peter M.; Pandey, Priyanka A.; Wilson, Neil R. [Department of Physics, University of Warwick, Coventry CV4 7AL (United Kingdom); Mulheran, Paul A. [Department of Chemical and Process Engineering, University of Strathclyde, James Weir Building, 75 Montrose St., Glasgow G1 1XJ (United Kingdom)

    2014-01-01

    Gold nano-clusters were grown on chemically modified graphene by direct sputter deposition. Transmission electron microscopy of the nano-clusters on these electron-transparent substrates reveals an unusual bimodal island size distribution (ISD). A kinetic Monte Carlo model of growth incorporating a size-dependent cluster mobility rule uniquely reproduces the bimodal ISD, providing strong evidence for the mobility of large clusters during surface growth. The cluster mobility exponent of −5/3 is consistent with cluster motion via one-dimensional diffusion of gold atoms around the edges of the nano-clusters.

  7. Size-dependent mobility of gold nano-clusters during growth on chemically modified graphene

    Directory of Open Access Journals (Sweden)

    Gavin R. Bell

    2014-01-01

    Full Text Available Gold nano-clusters were grown on chemically modified graphene by direct sputter deposition. Transmission electron microscopy of the nano-clusters on these electron-transparent substrates reveals an unusual bimodal island size distribution (ISD. A kinetic Monte Carlo model of growth incorporating a size-dependent cluster mobility rule uniquely reproduces the bimodal ISD, providing strong evidence for the mobility of large clusters during surface growth. The cluster mobility exponent of −5/3 is consistent with cluster motion via one-dimensional diffusion of gold atoms around the edges of the nano-clusters.

  8. Kinetically controlled synthesis of Au102(SPh)44 nanoclusters and catalytic application

    Science.gov (United States)

    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

  9. MAGNET

    CERN Multimedia

    by B. Curé

    2011-01-01

    The magnet operation was very satisfactory till the technical stop at the end of the year 2010. The field was ramped down on 5th December 2010, following the successful regeneration test of the turbine filters at full field on 3rd December 2010. This will limit in the future the quantity of magnet cycles, as it is no longer necessary to ramp down the magnet for this type of intervention. This is made possible by the use of the spare liquid Helium volume to cool the magnet while turbines 1 and 2 are stopped, leaving only the third turbine in operation. This obviously requires full availability of the operators to supervise the operation, as it is not automated. The cryogenics was stopped on 6th December 2010 and the magnet was left without cooling until 18th January 2011, when the cryoplant operation resumed. The magnet temperature reached 93 K. The maintenance of the vacuum pumping was done immediately after the magnet stop, when the magnet was still at very low temperature. Only the vacuum pumping of the ma...

  10. Fluorescence enhancement of DNA-silver nanoclusters from guanine proximity

    Energy Technology Data Exchange (ETDEWEB)

    Yeh, Hsin-chih [Los Alamos National Laboratory; Sharma, Jaswinder [Los Alamos National Laboratory; Yoo, Hyojong [Los Alamos National Laboratory; Martinez, Jennifer S [Los Alamos National Laboratory

    2010-01-01

    Oligonucleotide-templated, silver nanoclusters (DNA/Ag NCs) are a versatile set of fluorophores and have already been used for live cell imaging, detection of specific metal ions, and single-nucleotide variation identification. Compared to commonly used organic dyes, these fluorescent nanoclusters have much better photostability and are often a few times brighter. Owing to their small size, simple preparation, and biocompatibility (i.e. made of nontoxic metals), DNA/Ag NCs should find more applications in biological imaging and chemical detection in the years to come. While clearly promising as new fluorophores, DNA/Ag NCs possess a unique and poorly understood dynamic process not shared by organic dyes or photoluminescent nanocrystals - the conversion among different NC species due to silver oxidation/reduction or NC regrouping. While this environmental sensitivity can be viewed as a drawback, in the appropriate context, it can be used as a sensor or reporter. Often reversible, conversions among different NC species have been found to depend upon a number of factors, including time, temperature, oxygen and salt content. In this communication, we report significant fluorescence enhancement of DNA/Ag NCs via interactions with guanine-rich DNA sequences. Moreover, we demonstrated this property can be used for sensitive detection of specific target DNA from a human oncogene (i.e. Braf gene).

  11. PE-CVD fabrication of germanium nanoclusters for memory applications

    Energy Technology Data Exchange (ETDEWEB)

    Duerkop, T. [Institut fuer Materialien und Bauelemente der Elektronik, Leibniz Universitaet Hannover, Appelstrasse 11a, 30167 Hannover (Germany)], E-mail: duerkop@mbe.uni-hannover.de; Bugiel, E. [Institut fuer Materialien und Bauelemente der Elektronik, Leibniz Universitaet Hannover, Appelstrasse 11a, 30167 Hannover (Germany); Costina, I. [IHP GmbH, Im Technologiepark 25, 15236 Frankfurt (Oder) (Germany); Ott, A.; Peibst, R.; Hofmann, K.R. [Institut fuer Materialien und Bauelemente der Elektronik, Leibniz Universitaet Hannover, Appelstrasse 11a, 30167 Hannover (Germany)

    2008-02-15

    We have investigated Ge nanoclusters (Ge-NC) embedded in silicon dioxide, whose fundamental properties promise improved characteristics in NC flash memory devices as compared to Si nanoclusters. We present a simple new method, based on plasma-enhanced CVD (PE-CVD) deposition of amorphous Ge (a-Ge) onto SiO{sub 2}, to create gate stacks with embedded Ge-NC at vertically well-controlled positions suitable for use in flash memory devices. This process minimizes the exposure of Ge to environmental influences by depositing a-Ge as well as a SiO{sub 2} cap layer in situ within the same deposition chamber. Subsequent high-temperature anneals compatible with the temperature budget of CMOS processing are used for the actual cluster formation. Variation of annealing temperature and duration of this step as well as the thickness of the initial Ge layer controls the average cluster radius and density, as determined by transmission electron microscopy (TEM). Measurements of electrical properties show the capability of samples with NC to store charge.

  12. Structural, magnetic and electronic properties of Fe{sub n}Pt{sub 13−n} clusters with n=0–13: A first-principle study

    Energy Technology Data Exchange (ETDEWEB)

    Du, Xiaoli; Liu, Chuan; Zhang, Shengli [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 (China); Wang, Peng [Research Institute of Petroleum Processing, SINOPEC, Beijing 100083 (China); Huang, Shiping, E-mail: huangsp@mail.buct.edu.cn [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 (China); Tian, Huiping [Research Institute of Petroleum Processing, SINOPEC, Beijing 100083 (China)

    2014-11-15

    The structural, magnetic and electronic properties of Fe{sub n}Pt{sub 13−n} (n=0–13) nanoclusters are investigated using a density functional theory. It is found that the original icosahedra structure of Fe{sub n}Pt{sub 13−n} nanoclusters with n=3–8 deforms completely and exhibits the maximum Fe–Pt bonds. Furthermore, all the energetically preferable Fe{sub n}Pt{sub 13−n} (n=0–13) nanoclusters are found to be ferromagnetic coupling, and the magnetic moments of both Fe and Pt are enhanced. The large exchange splitting between the majority and the minority spin states indicates high magnetic moments based on the analysis of electronic density of states. In addition, electrons transfer from Fe to Pt atoms enhances the local atomic magnetic moments of Fe and Pt in Fe{sub n}Pt{sub 13−n} nanoclusters. - Highlights: • Magnetic properties of Fe{sub n}Pt{sub 13−n} are investigated using the density functional theory. • Structure of Fe{sub n}Pt{sub 13−n} nanoclusters with n=3–8 deforms completely. • Electron transfer from Fe to Pt atoms enhances local atomic magnetic moments. • The large exchange splitting in the spin states indicates high magnetic moments.

  13. Tetragonal-Like Phase in Core–Shell Iron Iron-Oxide Nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Kaur, Maninder; McCloy, John S.; Kukkadapu, Ravi; Pearce, Carolyn; Tucek, Jiri; Bowden, Mark; Engelhard, Mark; Arenholz, Elke; Qiang, You

    2017-05-11

    Two sizes of iron/iron-oxide (Fe/Fe-oxide) nanoclusters (NCs) of 10 nm and 35 nm diameters were prepared using a cluster deposition technique. Both these NCs displayed XRD peaks due to body-centered cubic (bcc) Fe0 and magnetite-like phase. Mossbauer spectroscopy (MS) measurements: a) confirmed the core-shell nature of the NCs, b) the Fe-oxide shell to be nanocrystalline and partially oxidized, and c) the Fe-oxide spins are significantly canted. In addition to the bcc Fe and magnetite-like phases, a phase similar to tetragonal σ-Fe-Cr (8% Cr) was CLEARLY evident in the larger NC, based on X-ray diffraction. Origin of the tetragonallike phase in the larger NC was not clear but could be due to significant distortion of the Fe0 core lattice planes; subtle peaks due to this phase were also apparent in the smaller NC. Unambiguous evidence for the presence of such a phase, however, was not clear from MS, X-ray photoelectron spectroscopy, vibrating sample magnetometry, X-ray magnetic circular dichroism, nor transmission electron microscopy. To our knowledge, this is the first report of tetragonallike phase in the Fe/Fe-oxide core-shell systems.

  14. Preparation and surface enhanced Raman scattering behavior of Ag-coated C{sub 60} nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Shi-Zhao; Yin, Die-er; Li, Xiangqing; Mu, Jin, E-mail: mujin@sit.edu.cn

    2013-12-01

    Ag-coated C{sub 60} nanoclusters were prepared and characterized with X-ray diffraction, transmission electron microscopy and nitrogen adsorption–desorption isotherm measurement. The Ag-coated C{sub 60} nanoclusters were assembled on the glass substrate to form a thin film using the layer-by-layer technique. Meanwhile, the surface enhanced Raman scattering (SERS) of musk xylene adsorbed on the film of Ag-coated C{sub 60} nanoclusters was explored. The results indicated that the film of Ag-coated C{sub 60} nanoclusters was a unique SERS-active substrate with a detection limit of 10{sup −9} mol L{sup −1} for musk xylene. Furthermore, the surface enhanced mechanisms were discussed preliminarily.

  15. Melting Properties of Medium-Sized Silicon Nanoclusters: A Molecular Dynamics Study

    Science.gov (United States)

    Li, Haipeng; Xu, Runfeng; Bi, Zetong; Shen, Xiaopeng; Han, Kui

    2017-07-01

    The structures and melting properties of the medium-sized silicon nanoclusters have been comparatively studied using the molecular dynamics method. Structural and thermodynamic parameters are used to characterize the melting properties of the clusters. The size dependence of the melting temperature of silicon nanoclusters is determined using the computation results. Different from the homogeneous melting of bulk silicon, melting of silicon nanoparticles proceeds over a finite temperature range due to surface effects, which shows the heterogeneous melting of nanoclusters. We found that the melting starts at the cluster surface and progressively shifts into the core region. This study provides a fundamental perspective on the melting behaviors of semiconductor silicon nanoclusters at the atomistic level.

  16. The role of oxygen and water on molybdenum nanoclusters for electro catalytic ammonia production

    DEFF Research Database (Denmark)

    Howalt, Jakob Geelmuyden; Vegge, Tejs

    2014-01-01

    . In this study, we present theoretical investigations of the influence of oxygen adsorption and reduction on pure and nitrogen covered molybdenum nanocluster electro catalysts for electrochemical reduction of N2 to NH3 with the purpose of understanding oxygen and water poisoning of the catalyst. Density...... functional theory calculations are used in combination with the computational hydrogen electrode approach to calculate the free energy profile for electrochemical protonation of O and N2 species on cuboctahedral Mo13 nanoclusters. The calculations show that the molybdenum nanocluster will preferentially bind...... are -0.72 V or lower for all oxygen coverages studied, and it is thus possible to (re)activate (partially) oxidized nanoclusters for electrochemical ammonia production, e.g., using a dry proton conductor or an aqueous electrolyte. At lower oxygen coverages, nitrogen molecules can adsorb to the surface...

  17. Nanocluster metal films as thermoelectric material for radioisotope mini battery unit

    Science.gov (United States)

    Borisyuk, P. V.; Krasavin, A. V.; Tkalya, E. V.; Lebedinskii, Yu. Yu.; Vasiliev, O. S.; Yakovlev, V. P.; Kozlova, T. I.; Fetisov, V. V.

    2016-10-01

    The paper is devoted to studying the thermoelectric and structural properties of films based on metal nanoclusters (Au, Pd, Pt). The experimental results of the study of single nanoclusters' tunneling conductance obtained with scanning tunneling spectroscopy are presented. The obtained data allowed us to evaluate the thermoelectric power of thin film consisting of densely packed individual nanoclusters. It is shown that such thin films can operate as highly efficient thermoelectric materials. A scheme of miniature thermoelectric radioisotope power source based on the thorium-228 isotope is proposed. The efficiency of the radioisotope battery using thermoelectric converters based on nanocluster metal films is shown to reach values up to 1.3%. The estimated characteristics of the device are comparable with the parameters of up-to-date radioisotope batteries based on nickel-63.

  18. The Influence of Ultrasound on Formation of Self-organized Uniform Nanoclusters

    Directory of Open Access Journals (Sweden)

    R.M. Peleshchak

    2016-06-01

    Full Text Available The non-linear diffusion-deformation theory of self-organization of nanoclusters of dot defects in semiconductor exposed to ultrasound treatment that considers the interaction of defects among themselves and with atoms of a matrix via the elastic field created by dot defects and an acoustic wave is developed. Within this theory the influence of ultrasound on the conditions of formation of spherical nanoclusters and their radius is investigated. The nanocluster size depending on average concentration of defects and amplitude of an acoustic wave is determined. It is established that ultrasonic treatment of the semiconductor in the process of formation of an ensemble of nanoclusters leads to reduction of dispersion of their sizes.

  19. Automated electrodeposition of bimetallic noble-metal nanoclusters via redox-replacement reactions for electrocatalysis

    CSIR Research Space (South Africa)

    Mkwizu, TS

    2009-01-01

    Full Text Available Nanoclusters of bimetallic composition involving platinum with gold or ruthenium were sequentially deposited via redoxreplacement of electrodeposited sacrificial Cu adlayers for controlling the deposition of the noble metals. These steps were...

  20. Probing the Absorption and Emission Transition Dipole Moment of DNA Stabilized Silver Nanoclusters

    DEFF Research Database (Denmark)

    Hooley, Emma Nicole; Carro Temboury, Miguel R.; Vosch, Tom André Jos

    2017-01-01

    Using single molecule polarization measurements, we investigate the excitation and emission polarization characteristics of DNA stabilized silver nanoclusters (C24-AgNCs). Although small changes in the polarization generally accompany changes to the emission spectrum, the emission and excitation ...

  1. Sub-micron scale patterning of fluorescent silver nanoclusters using low-power laser

    National Research Council Canada - National Science Library

    Kunwar, Puskal; Hassinen, Jukka; Bautista, Godofredo; Ras, Robin H A; Toivonen, Juha

    2016-01-01

    .... A cost-effective fabrication of photostable micron-sized fluorescent silver nanocluster barcode is demonstrated in silver-impregnated polymer films using a low-power continuous-wave laser diode...

  2. Single-Crystal Time-of-Flight Neutron Diffraction and Magic-Angle-Spinning NMR Spectroscopy Resolve the Structure and (1)H and (7)Li Dynamics of the Uranyl Peroxide Nanocluster U60.

    Science.gov (United States)

    Olds, Travis A; Dembowski, Mateusz; Wang, Xiaoping; Hoffman, Christina; Alam, Todd M; Hickam, Sarah; Pellegrini, Kristi L; He, Junhong; Burns, Peter C

    2017-08-21

    Single-crystal time-of-flight neutron diffraction has provided atomic resolution of H atoms of H2O molecules and hydroxyl groups, as well as Li cations in the uranyl peroxide nanocluster U60. Solid-state magic-angle-spinning nuclear magnetic resonance (MAS NMR) spectroscopy was used to confirm the dynamics of these constituents, revealing the transportation of Li atoms and H2O through cluster walls. H atoms of hydroxyl units that are located on the cluster surface are involved in the transfer of H2O and Li cations from inside to outside and vice versa. This exchange occurs as a concerted motion and happens rapidly even in the solid state. As a consequence of its large size and open hexagonal pores, U60 exchanges Li cations more rapidly compared to other uranyl nanoclusters.

  3. Developing a Millifluidic Platform for the Synthesis of Ultrasmall Nanoclusters: Ultrasmall Copper Nanoclusters as a Case Study

    Energy Technology Data Exchange (ETDEWEB)

    Biswas, Sanchita; Miller, Jeffrey T; Li, Yuehao; Nandakumar, Krishnaswamy; Kumar, Challa S.S.R.

    2012-02-02

    The future of lab-on-a-chip devices for the synthesis of nanomaterials hinges on the successful development of high-throughput methods with better control over their size. While significant effort in this direction mainly focuses on developing “difficult to fabricate” complex microfluidic reactors, scant attention has been paid to the “easy to fabricate” and simple millifluidic systems that could provide the required control as well as high throughput. By utilizing numerical simulation of fluids within the millifluidic space at different flow rates, the results presented here show velocity profiles and residence time distributions similar to the case of microfluidics. By significantly reducing the residence time and residence time distribution, a continuous flow synthesis of ultrasmall copper nanoclusters (UCNCs) with exceptional colloidal stability is achieved. In-situ synchrotron-radiation-based X-ray absorption spectroscopy (XAS) reveal that the as-prepared clusters are about 1 nm, which is further supported by transmission electron microscopy and UV–vis spectroscopy studies. The clusters reported here are the smallest ever produced using a lab-on-a-chip platform. When supported on silica, they are found to efficiently catalyze C–H oxidation reactions, hitherto unknown to be catalyzed by Cu. This work suggests that a millifluidic platform can be an inexpensive, versatile, easy-to-use, and powerful tool for nanoparticle synthesis in general, and more specifically for ultrasmall nanoclusters (UNCs).

  4. Enhancement of the Hydrogen Evolution Reaction from Ni-MoS2 Hybrid Nanoclusters

    Science.gov (United States)

    2016-01-01

    This report focuses on a novel strategy for the preparation of transition metal–MoS2 hybrid nanoclusters based on a one-step, dual-target magnetron sputtering, and gas condensation process demonstrated for Ni-MoS2. Aberration-corrected STEM images coupled with EDX analysis confirms the presence of Ni and MoS2 in the hybrid nanoclusters (average diameter = 5.0 nm, Mo:S ratio = 1:1.8 ± 0.1). The Ni-MoS2 nanoclusters display a 100 mV shift in the hydrogen evolution reaction (HER) onset potential and an almost 3-fold increase in exchange current density compared with the undoped MoS2 nanoclusters, the latter effect in agreement with reported DFT calculations. This activity is only reached after air exposure of the Ni-MoS2 hybrid nanoclusters, suggested by XPS measurements to originate from a Ni dopant atoms oxidation state conversion from metallic to 2+ characteristic of the NiO species active to the HER. Anodic stripping voltammetry (ASV) experiments on the Ni-MoS2 hybrid nanoclusters confirm the presence of Ni-doped edge sites and reveal distinctive electrochemical features associated with both doped Mo-edge and doped S-edge sites which correlate with both their thermodynamic stability and relative abundance.

  5. Photoluminescent Gold Nanoclusters in Cancer Cells: Cellular Uptake, Toxicity, and Generation of Reactive Oxygen Species.

    Science.gov (United States)

    Matulionyte, Marija; Dapkute, Dominyka; Budenaite, Laima; Jarockyte, Greta; Rotomskis, Ricardas

    2017-02-10

    In recent years, photoluminescent gold nanoclusters have attracted considerable interest in both fundamental biomedical research and practical applications. Due to their ultrasmall size, unique molecule-like optical properties, and facile synthesis gold nanoclusters have been considered very promising photoluminescent agents for biosensing, bioimaging, and targeted therapy. Yet, interaction of such ultra-small nanoclusters with cells and other biological objects remains poorly understood. Therefore, the assessment of the biocompatibility and potential toxicity of gold nanoclusters is of major importance before their clinical application. In this study, the cellular uptake, cytotoxicity, and intracellular generation of reactive oxygen species (ROS) of bovine serum albumin-encapsulated (BSA-Au NCs) and 2-(N-morpholino) ethanesulfonic acid (MES)capped photoluminescent gold nanoclusters (Au-MES NCs) were investigated. The results showed that BSA-Au NCs accumulate in cells in a similar manner as BSA alone, indicating an endocytotic uptake mechanism while ultrasmall Au-MES NCs were distributed homogeneously throughout the whole cell volume including cell nucleus. The cytotoxicity of BSA-Au NCs was negligible, demonstrating good biocompatibility of such BSA-protected Au NCs. In contrast, possibly due to ultrasmall size and thin coating layer, Au-MES NCs exhibited exposure time-dependent high cytotoxicity and higher reactivity which led to highly increased generation of reactive oxygen species. The results demonstrate the importance of the coating layer to biocompatibility and toxicity of ultrasmall photoluminescent gold nanoclusters.

  6. Ligand-exchange synthesis of selenophenolate-capped Au25 nanoclusters.

    Science.gov (United States)

    Meng, Xiangming; Xu, Qian; Wang, Shuxin; Zhu, Manzhou

    2012-07-21

    We report the synthesis and characterization of selenophenolate-capped 25-gold-atom nanoclusters via a ligand-exchange approach. In this method, phenylethanethiolate (PhCH(2)CH(2)S) capped Au(25) nanoclusters are utilized as the starting material, which is subject to ligand-exchange with selenophenol (PhSeH). The as-obtained cluster product is confirmed to be selenophenolate-protected Au(25) nanoclusters through characterization by electrospray ionization (ESI) and matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS), thermogravimetric analysis (TGA), elemental analysis (EA), UV-Vis and (1)H/(13)C NMR spectroscopies. The ligand-exchange synthesis of [Au(25)(SePh)(18)](-)[(C(8)H(17))(4)N](+) nanoclusters demonstrates that the core size of gold nanoclusters is retained in the thiolate-to-selenolate exchange process and that the 18 surface thiolate ligands can be completely exchanged by selenophenolate, rather than giving rise to a mixed ligand shell on the cluster. The two types of Au(25)L(18) (L = thiolate or selenolate) nanoclusters also show some differences in stability and optical properties.

  7. Synthesis of selenolate-protected Au18(SeC6H5)14 nanoclusters.

    Science.gov (United States)

    Xu, Qian; Wang, Shuxin; Liu, Zhao; Xu, Guoyong; Meng, Xiangming; Zhu, Manzhou

    2013-02-07

    This work reports the first synthesis of selenophenolate-protected Au(18)(SePh)(14) nanoclusters. This cluster exhibits distinct differences from its thiolate analogue in terms of optical absorption properties. The Au(18)(SePh)(14) nanoclusters were obtained via a controlled reaction of Au(25)(SCH(2)CH(2)Ph)(18) with selenophenol. Electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) revealed the crude product to contain predominantly Au(18)(SePh)(14) nanoclusters, and side products include Au(15)(SePh)(13), Au(19)(SePh)(15) and Au(20)(SePh)(16). High-performance liquid chromatography (HPLC) was employed to isolate Au(18)(SePh)(14) nanoclusters. The results of thermogravimetric analysis (TGA), elemental analysis (EA), and (1)H/(13)C NMR spectroscopy confirmed the cluster composition. To the best of our knowledge, this is the first report of selenolate-protected Au(18) nanoclusters. Future theoretical and X-ray crystallographic work will reveal the geometric structure and the nature of selenolate-gold bonding in the nanocluster.

  8. Design of an ultrasmall Au nanocluster-CeO2 mesoporous nanocomposite catalyst for nitrobenzene reduction.

    Science.gov (United States)

    Chong, Hanbao; Li, Peng; Xiang, Ji; Fu, Fangyu; Zhang, Dandan; Ran, Xiaorong; Zhu, Manzhou

    2013-08-21

    In this work we are inspired to explore gold nanoclusters supported on mesoporous CeO2 nanospheres as nanocatalysts for the reduction of nitrobenzene. Ultrasmall Au nanoclusters (NCs) and mesoporous CeO2 nanospheres were readily synthesized and well characterized. Due to their ultrasmall size, the as-prepared Au clusters can be easily absorbed into the mesopores of the mesoporous CeO2 nanospheres. Owing to the unique mesoporous structure of the CeO2 support, Au nanoclusters in the Au@CeO2 may effectively prevent the aggregation which usually results in a rapid decay of the catalytic activity. It is notable that the ultrasmall gold nanoclusters possess uniform size distribution and good dispersibility on the mesoporous CeO2 supports. Compared to other catalyst systems with different oxide supports, the as-prepared Au nanocluster-CeO2 nanocomposite nanocatalysts showed efficient catalytic performance in transforming nitrobenzene into azoxybenzene. In addition, a plausible mechanism was deeply investigated to explain the transforming process. Au@CeO2 exhibited efficient catalytic activity for reduction of nitrobenzene. This strategy may be easily extended to fabricate many other heterogeneous catalysts including ultrasmall metal nanoclusters and mesoporous oxides.

  9. Photoluminescent Gold Nanoclusters in Cancer Cells: Cellular Uptake, Toxicity, and Generation of Reactive Oxygen Species

    Science.gov (United States)

    Matulionyte, Marija; Dapkute, Dominyka; Budenaite, Laima; Jarockyte, Greta; Rotomskis, Ricardas

    2017-01-01

    In recent years, photoluminescent gold nanoclusters have attracted considerable interest in both fundamental biomedical research and practical applications. Due to their ultrasmall size, unique molecule-like optical properties, and facile synthesis gold nanoclusters have been considered very promising photoluminescent agents for biosensing, bioimaging, and targeted therapy. Yet, interaction of such ultra-small nanoclusters with cells and other biological objects remains poorly understood. Therefore, the assessment of the biocompatibility and potential toxicity of gold nanoclusters is of major importance before their clinical application. In this study, the cellular uptake, cytotoxicity, and intracellular generation of reactive oxygen species (ROS) of bovine serum albumin-encapsulated (BSA-Au NCs) and 2-(N-morpholino) ethanesulfonic acid (MES)-capped photoluminescent gold nanoclusters (Au-MES NCs) were investigated. The results showed that BSA-Au NCs accumulate in cells in a similar manner as BSA alone, indicating an endocytotic uptake mechanism while ultrasmall Au-MES NCs were distributed homogeneously throughout the whole cell volume including cell nucleus. The cytotoxicity of BSA-Au NCs was negligible, demonstrating good biocompatibility of such BSA-protected Au NCs. In contrast, possibly due to ultrasmall size and thin coating layer, Au-MES NCs exhibited exposure time-dependent high cytotoxicity and higher reactivity which led to highly increased generation of reactive oxygen species. The results demonstrate the importance of the coating layer to biocompatibility and toxicity of ultrasmall photoluminescent gold nanoclusters. PMID:28208642

  10. MAGNET

    CERN Multimedia

    B. Curé

    2012-01-01

      The magnet was energised at the beginning of March 2012 at a low current to check all the MSS safety chains. Then the magnet was ramped up to 3.8 T on 6 March 2012. Unfortunately two days later an unintentional switch OFF of the power converter caused a slow dump. This was due to a misunderstanding of the CCC (CERN Control Centre) concerning the procedure to apply for the CMS converter control according to the beam-mode status at that time. Following this event, the third one since 2009, a discussion was initiated to define possible improvement, not only on software and procedures in the CCC, but also to evaluate the possibility to upgrade the CMS hardware to prevent such discharge from occurring because of incorrect procedure implementations. The magnet operation itself was smooth, and no power cuts took place. As a result, the number of magnetic cycles was reduced to the minimum, with only two full magnetic cycles from 0 T to 3.8 T. Nevertheless the magnet suffered four stops of the cryogeni...

  11. MAGNET

    CERN Multimedia

    Benoit Curé

    2010-01-01

    Operation of the magnet has gone quite smoothly during the first half of this year. The magnet has been at 4.5K for the full period since January. There was an unplanned short stop due to the CERN-wide power outage on May 28th, which caused a slow dump of the magnet. Since this occurred just before a planned technical stop of the LHC, during which access in the experimental cavern was authorized, it was decided to leave the magnet OFF until 2nd June, when magnet was ramped up again to 3.8T. The magnet system experienced a fault also resulting in a slow dump on April 14th. This was triggered by a thermostat on a filter choke in the 20kA DC power converter. The threshold of this thermostat is 65°C. However, no variation in the water-cooling flow rate or temperature was observed. Vibration may have been the root cause of the fault. All the thermostats have been checked, together with the cables, connectors and the read out card. The tightening of the inductance fixations has also been checked. More tem...

  12. MAGNET

    CERN Multimedia

    B. Curé

    2012-01-01

      Following the unexpected magnet stops last August due to sequences of unfortunate events on the services and cryogenics [see CMS internal report], a few more events and initiatives again disrupted the magnet operation. All the magnet parameters stayed at their nominal values during this period without any fault or alarm on the magnet control and safety systems. The magnet was stopped for the September technical stop to allow interventions in the experimental cavern on the detector services. On 1 October, to prepare the transfer of the liquid nitrogen tank on its new location, several control cables had to be removed. One cable was cut mistakenly, causing a digital input card to switch off, resulting in a cold-box (CB) stop. This tank is used for the pre-cooling of the magnet from room temperature down to 80 K, and for this reason it is controlled through the cryogenics control system. Since the connection of the CB was only allowed for a field below 2 T to avoid the risk of triggering a fast d...

  13. Synthesis and magnetic properties of multiwalled carbon nanotubes decorated with magnetite nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Pistone, A., E-mail: pistone@unime.it [Department of Electronic Engineering, Chemistry and Industrial Engineering, University of Messina, Messina I-98166 (Italy); Iannazzo, D.; Fazio, M. [Department of Electronic Engineering, Chemistry and Industrial Engineering, University of Messina, Messina I-98166 (Italy); Celegato, F.; Barrera, G.; Tiberto, P. [INRIM Electromagnetism Division, Torino (Italy); Giordano, A.; Azzerboni, B.; Galvagno, S. [Department of Electronic Engineering, Chemistry and Industrial Engineering, University of Messina, Messina I-98166 (Italy)

    2014-02-15

    Magnetite particles with nanoscale sizes were deposited along multiwalled carbon nanotubes (MWCNT) through a simple, effective and reproducible chemical route. The structure, morphology and magnetic properties of the hybrid materials were characterized by XRD, SEM, TEM, EDX, VSM. The characterization results show that the surface of nanotubes was loaded with iron oxides nanoclusters and each nanocluster is composed by several nanocrystals with a mean diameter of 10 nm. The experimental magnetic hysteretic behavior has been also studied by means of the Preisach model and a good agreement between experimental data and numerical computations was found.

  14. MAGNET

    CERN Multimedia

    B. Curé

    2012-01-01

      The magnet and its sub-systems were stopped at the beginning of the winter shutdown on 8th December 2011. The magnet was left without cooling during the cryogenics maintenance until 17th January 2012, when the cryoplant operation resumed. The magnet temperature reached 93 K. The vacuum pumping was maintained during this period. During this shutdown, the yearly maintenance was performed on the cryogenics, the vacuum pumps, the magnet control and safety systems, and the power converter and discharge lines. Several preventive actions led to the replacement of the electrovalve command coils, and the 20A DC power supplies of the magnet control system. The filters were cleaned on the demineralised water circuits. The oil of the diffusion pumps was changed. On the cryogenics, warm nitrogen at 343 K was circulated in the cold box to regenerate the filters and the heat exchangers. The coalescing filters have been replaced at the inlet of both the turbines and the lubricant trapping unit. The active cha...

  15. MAGNET

    CERN Multimedia

    Benoit Curé

    2010-01-01

    The magnet was successfully operated at the end of the year 2009 despite some technical problems on the cryogenics. The magnet was ramped up to 3.8 T at the end of November until December 16th when the shutdown started. The magnet operation met a few unexpected stops. The field was reduced to 3.5 T for about 5 hours on December 3rd due to a faulty pressure sensor on the helium compressor. The following day the CERN CCC stopped unintentionally the power converters of the LHC and the experiments, triggering a ramp down that was stopped at 2.7 T. The magnet was back at 3.8 T about 6 hours after CCC sent the CERN-wide command. Three days later, a slow dump was triggered due to a stop of the pump feeding the power converter water-cooling circuit, during an intervention on the water-cooling plant done after several disturbances on the electrical distribution network. The magnet was back at 3.8 T in the evening the same day. On December 10th a break occurred in one turbine of the cold box producing the liquid ...

  16. MAGNET

    CERN Multimedia

    B. Curé

    2013-01-01

      The magnet was operated without any problem until the end of the LHC run in February 2013, apart from a CERN-wide power glitch on 10 January 2013 that affected the CMS refrigerator, causing a ramp down to 2 T in order to reconnect the coldbox. Another CERN-wide power glitch on 15 January 2013 didn’t affect the magnet subsystems, the cryoplant or the power converter. At the end of the magnet run, the reconnection of the coldbox at 2.5 T was tested. The process will be updated, in particular the parameters of some PID valve controllers. The helium flow of the current leads was reduced but only for a few seconds. The exercise will be repeated with the revised parameters to validate the automatic reconnection process of the coldbox. During LS1, the water-cooling services will be reduced and many interventions are planned on the electrical services. Therefore, the magnet cryogenics and subsystems will be stopped for several months, and the magnet cannot be kept cold. In order to avoid unc...

  17. MAGNET

    CERN Multimedia

    B. Curé

    2011-01-01

    The CMS magnet has been running steadily and smoothly since the summer, with no detected flaw. The magnet instrumentation is entirely operational and all the parameters are at their nominal values. Three power cuts on the electrical network affected the magnet run in the past five months, with no impact on the data-taking as the accelerator was also affected at the same time. On 22nd June, a thunderstorm caused a power glitch on the service electrical network. The primary water cooling at Point 5 was stopped. Despite a quick restart of the water cooling, the inlet temperature of the demineralised water on the busbar cooling circuit increased by 5 °C, up to 23.3 °C. It was kept below the threshold of 27 °C by switching off other cooling circuits to avoid the trigger of a slow dump of the magnet. The cold box of the cryogenics also stopped. Part of the spare liquid helium volume was used to maintain the cooling of the magnet at 4.5 K. The operators of the cryogenics quickly restarted ...

  18. Interaction of size-selected gold nanoclusters with dopamine

    Science.gov (United States)

    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.

  19. Simultaneous expression and transportation of insulin by supramolecular polysaccharide nanocluster

    Science.gov (United States)

    Zhang, Yu-Hui; Zhang, Ying-Ming; Zhao, Qi-Hui; Liu, Yu

    2016-01-01

    Drug/gene transportation systems with stimuli-responsive release behaviors are becoming research hotspots in biochemical and biomedical fields. In this work, a glucose-responsive supramolecular nanocluster was successfully constructed by the intermolecular complexation of phenylboronic acid modified β-cyclodextrin with adamantane modified polyethylenimine, which could be used as a biocompatible carrier for insulin and pCMV3-C-GFPSpark-Ins DNA which could express insulin co-delivery. Benefiting from the response capability of phenylboronic acid moiety toward glucose, the encapsulated insulin could be specifically released and the corresponding targeted DNA could efficiently express insulin in HepG2 cell, accompanied by the high-level insulin release in vitro. Our results demonstrate that the simultaneous insulin drug delivery and insulin gene transfection in a controlled mode may have great potential in the clinical diabetes treatments. PMID:26948978

  20. Cytotoxicity of nucleus-targeting fluorescent gold nanoclusters

    Science.gov (United States)

    Zhao, Jing-Ya; Cui, Ran; Zhang, Zhi-Ling; Zhang, Mingxi; Xie, Zhi-Xiong; Pang, Dai-Wen

    2014-10-01

    Gold nanoclusters (AuNCs) with ultra small sizes and unique fluorescence properties have shown promising potential for imaging the nuclei of living cells. However, little is known regarding the potential cytotoxicity of AuNCs after they enter the cell nucleus. The aim of this study is to investigate whether and how nucleus-targeting AuNCs affect the normal functioning of cells. Highly stable, water-soluble and bright fluorescent Au25NCs (the core of each nanocluster is composed of 25 gold atoms) were synthesized. Specific targeting of Au25NCs to the cell nucleus was achieved by conjugating the TAT peptide to the Au25NCs. Cell viability, cell morphology, cell apoptosis/necrosis, reactive oxygen species (ROS) level and mitochondrial membrane potential examinations were performed on different cell lines exposed to the nucleus-targeting Au25NCs. We found that the nucleus-targeting Au25NCs caused cell apoptosis in a dose-dependent manner. A possible mechanism for the cytotoxicity of the nucleus-targeting Au25NCs was proposed as follows: the nucleus-targeting Au25NCs induce the production of ROS, resulting in the oxidative degradation of mitochondrial components, in turn leading to apoptosis via a mitochondrial damage pathway. This work facilitates a better understanding of the toxicity of AuNCs, especially nucleus-targeting AuNCs.Gold nanoclusters (AuNCs) with ultra small sizes and unique fluorescence properties have shown promising potential for imaging the nuclei of living cells. However, little is known regarding the potential cytotoxicity of AuNCs after they enter the cell nucleus. The aim of this study is to investigate whether and how nucleus-targeting AuNCs affect the normal functioning of cells. Highly stable, water-soluble and bright fluorescent Au25NCs (the core of each nanocluster is composed of 25 gold atoms) were synthesized. Specific targeting of Au25NCs to the cell nucleus was achieved by conjugating the TAT peptide to the Au25NCs. Cell viability, cell

  1. Thumb Imprint Based Detection of Hyperbilirubinemia Using Luminescent Gold Nanoclusters

    Science.gov (United States)

    Basu, Srestha; Sahoo, Amaresh Kumar; Paul, Anumita; Chattopadhyay, Arun

    2016-12-01

    Early and easy detection of diseases, using point-of-care and inexpensive devices, not only provides option for early treatment but also reduces the risk of propagation. Herein we report the fabrication of a robust film based luminescence indicator of bilirubin, which can indicate hyperbilirubinemia through the thumb imprint of the patient. The UV-light induced luminescence intensity of the film, made out of chitosan stabilised gold (Au) nanoclusters, which was effectively quenched in the presence of Cu2+ ions, recovered in the presence of bilirubin from skin or blood serum. Moreover, the sensitivity of detection of bilirubin was tuneable with the amount of Cu2+ added, thereby facilitating the detection of the desired concentration range of bilirubin.

  2. Simultaneous expression and transportation of insulin by supramolecular polysaccharide nanocluster

    Science.gov (United States)

    Zhang, Yu-Hui; Zhang, Ying-Ming; Zhao, Qi-Hui; Liu, Yu

    2016-03-01

    Drug/gene transportation systems with stimuli-responsive release behaviors are becoming research hotspots in biochemical and biomedical fields. In this work, a glucose-responsive supramolecular nanocluster was successfully constructed by the intermolecular complexation of phenylboronic acid modified β-cyclodextrin with adamantane modified polyethylenimine, which could be used as a biocompatible carrier for insulin and pCMV3-C-GFPSpark-Ins DNA which could express insulin co-delivery. Benefiting from the response capability of phenylboronic acid moiety toward glucose, the encapsulated insulin could be specifically released and the corresponding targeted DNA could efficiently express insulin in HepG2 cell, accompanied by the high-level insulin release in vitro. Our results demonstrate that the simultaneous insulin drug delivery and insulin gene transfection in a controlled mode may have great potential in the clinical diabetes treatments.

  3. A comparison of interatomic potentials for modeling tungsten nanocluster structures

    Science.gov (United States)

    Hao, Jiannan; Shu, Xiaolin; Jin, Shuo; Zhang, Xuesong; Zhang, Ying; Lu, Guang-Hong

    2017-02-01

    Molecular dynamic simulation is utilized to study the nanocluster and the fuzz structure on the PFM surface of tungsten. The polyhedral and linear cluster structures based on the icosahedron, cuboctahedron and rhombic dodecahedron are built up. Three interatomic potentials are used in calculating the relationship between the cluster energy and the number of atoms. The results are compared with first-principles calculation to show each potential's best application scale. Furthermore, the transition between the icosahedral and the cuboctahedral clusters is observed in molecular dynamic simulation at different temperatures, which follows a critical curve for different numbers of atoms. The linear structures are proved to be stable at experimental temperatures by thermodynamics. The work presents a selection of interatomic potentials in simulating tungsten cluster systems and helps researchers understand the growth and evolution laws of clusters and the fuzz-like structure formation process in fusion devices.

  4. Efficient Radioisotope Energy Transfer by Gold Nanoclusters for Molecular Imaging.

    Science.gov (United States)

    Volotskova, Olga; Sun, Conroy; Stafford, Jason H; Koh, Ai Leen; Ma, Xiaowei; Cheng, Zhen; Cui, Bianxiao; Pratx, Guillem; Xing, Lei

    2015-08-26

    Beta-emitting isotopes Fluorine-18 and Yttrium-90 are tested for their potential to stimulate gold nanoclusters conjugated with blood serum proteins (AuNCs). AuNCs excited by either medical radioisotope are found to be highly effective ionizing radiation energy transfer mediators, suitable for in vivo optical imaging. AuNCs synthesized with protein templates convert beta-decaying radioisotope energy into tissue-penetrating optical signals between 620 and 800 nm. Optical signals are not detected from AuNCs incubated with Technetium-99m, a pure gamma emitter that is used as a control. Optical emission from AuNCs is not proportional to Cerenkov radiation, indicating that the energy transfer between the radionuclide and AuNC is only partially mediated by Cerenkov photons. A direct Coulombic interaction is proposed as a novel and significant mechanism of energy transfer between decaying radionuclides and AuNCs.

  5. Jump electroconductivity in the laser deposited nanoclustered structures

    Science.gov (United States)

    Antipov, A.; Shagurina, A.; Osipov, A.; Istratov, A.; Skryabin, I.; Arakelian, S.

    2017-01-01

    The quantum states verification in cluster semiconductor/metallic structures by jump/tunneling electroconductivity and possible mechanisms for their implementation are considered in experiment and theory. By our laser ablation technique we have nanostructurized the films for which the ability to control the change in their electrical properties does exist by variation of the topology for the system. The granular conductivity specificity has been under study. The current-voltage characteristics behavior has been measured for a nanocluster bimetallic film (Au+Ag), and the experiments for multilayer bimetal thin films of the different composition have been carried out. Two associated mechanisms for electroconductivity occur in the case, i.e. tunnel transition for electrons and electron activation in the frames of the shell model for a cluster system, in dependence on the nanostructure topology.

  6. Information processing schemes based on monolayer protected metallic nanoclusters.

    Science.gov (United States)

    Cervera, Javier; Mafé, Salvador

    2011-09-01

    Nanostructures are potentially useful as building blocks to complement future electronics because of their high versatility and packing densities. The fabrication and characterization of particular nanostructures and the use of new theoretical tools to describe their properties are receiving much attention. However, the integration of these individual systems into general schemes that could perform simple tasks is also necessary because modern electronics operation relies on the concerted action of many basic units. We review here new conceptual schemes that can allow information processing with ligand or monolayer protected metallic nanoclusters (MPCs) on the basis of the experimentally demonstrated and theoretically described electrical characteristics of these nanostructures. In particular, we make use of the tunnelling current through a metallic nanocluster attached to the electrodes by ligands. The nanostructure is described as a single electron transistor (SET) that can be gated by an external potential. This fact permits exploiting information processing schemes in approximately defined arrays of MPCs. These schemes include: (i) binary, multivalued, and reversible logic gates; (ii) an associative memory and a synchronization circuit; and (iii) two signal processing nanodevices based on parallel arrays of MPCs and nanoswitches. In each case, the practical operation of the nanodevice is based on the SET properties of MPCs reported experimentally. We examine also some of the practical problems that should be addressed in future experimental realizations: the stochastic nature of the electron tunnelling, the relatively low operation temperatures, and the limited reliability caused by the weak signals involved and the nanostructure variability. The perspectives to solve these problems are based on the potentially high degree of scalability of the nanostructures.

  7. MAGNETS

    Science.gov (United States)

    Hofacker, H.B.

    1958-09-23

    This patent relates to nmgnets used in a calutron and more particularly to means fur clamping an assembly of magnet coils and coil spacers into tightly assembled relation in a fluid-tight vessel. The magnet comprises windings made up of an assembly of alternate pan-cake type coils and spacers disposed in a fluid-tight vessel. At one end of the tank a plurality of clamping strips are held firmly against the assembly by adjustable bolts extending through the adjacent wall. The foregoing arrangement permits taking up any looseness which may develop in the assembly of coils and spacers.

  8. Nanocluster model of intermetallic compounds with giant unit cells: beta, beta'-Mg(2)Al(3) polymorphs.

    Science.gov (United States)

    Blatov, Vladislav A; Ilyushin, Gregory D; Proserpio, Davide M

    2010-02-15

    A novel method for the computational description of intermetallics as an assembly of nanoclusters was improved and applied to extremely complicated crystal structures of beta, beta'-Mg(2)Al(3) polymorphs. Using the TOPOS program package that implements the method, we separated two types of two-shell primary nanoclusters A, A1, A2, and B consisting of 57-63 atoms that completely compose the structures of the polymorphs. The nanocluster model interprets structural disordering in beta-Mg(2)Al(3): the disordered atoms form the inner shell of the nanocluster A, while the outer shells of all nanoclusters are preserved. The self-assembly of the beta, beta'-Mg(2)Al(3) crystal structures was considered within the hierarchical scheme: 0D primary polyhedral clusters (coordination polyhedra) --> 0D two-shell primary nanoclusters A, A1, A2, or B --> 0D supracluster-precursor AB(2) --> 1D primary chain --> 2D microlayer --> 3D microframework. The self-assembly scheme proves the similarity of beta, beta'-Mg(2)Al(3) to other extremely complicated Samson's phases, NaCd(2) and ZrZn(22); the spatial arrangement of the centers of nanoclusters in these structures as well as the topology of the corresponding network conform to the Laves phase MgCu(2). Using the TOPOS procedure of searching for finite fragments in infinite nets we found that nanocluster B is a typical fragment of intermetallic compounds: it exists in intermetallics belonging to 42 Pearson classes. The nanocluster A was found only in two Pearson classes: cF464 and hP238, while the nanoclusters A1 and A2 occur in beta'-Mg(2)Al(3) only. Thus, the nanoclusters A, A1, and A2 can be considered as "determinants" of the corresponding structures.

  9. MAGNET

    CERN Multimedia

    B. Curé

    2011-01-01

    The magnet ran smoothly in the last few months until a fast dump occurred on 9th May 2011. Fortunately, this occurred in the afternoon of the first day of the technical stop. The fast dump was due to a valve position controller that caused the sudden closure of a valve. This valve is used to regulate the helium flow on one of the two current leads, which electrically connects the coil at 4.5 K to the busbars at room temperature. With no helium flow on the lead, the voltage drop and the temperatures across the leads increase up to the defined thresholds, triggering a fast dump through the Magnet Safety System (MSS). The automatic reaction triggered by the MSS worked properly. The helium release was limited as the pressure rise was just at the limit of the safety valve opening pressure. The average temperature of the magnet reached 72 K. It took four days to recover the temperature and refill the helium volumes. The faulty valve controller was replaced by a spare one before the magnet ramp-up resumed....

  10. A scalable synthesis of highly stable and water dispersible Ag 44(SR)30 nanoclusters

    KAUST Repository

    AbdulHalim, Lina G.

    2013-01-01

    We report the synthesis of atomically monodisperse thiol-protected silver nanoclusters [Ag44(SR)30] m, (SR = 5-mercapto-2-nitrobenzoic acid) in which the product nanocluster is highly stable in contrast to previous preparation methods. The method is one-pot, scalable, and produces nanoclusters that are stable in aqueous solution for at least 9 months at room temperature under ambient conditions, with very little degradation to their unique UV-Vis optical absorption spectrum. The composition, size, and monodispersity were determined by electrospray ionization mass spectrometry and analytical ultracentrifugation. The produced nanoclusters are likely to be in a superatom charge-state of m = 4-, due to the fact that their optical absorption spectrum shares most of the unique features of the intense and broadly absorbing nanoparticles identified as [Ag44(SR) 30]4- by Harkness et al. (Nanoscale, 2012, 4, 4269). A protocol to transfer the nanoclusters to organic solvents is also described. Using the disperse nanoclusters in organic media, we fabricated solid-state films of [Ag44(SR)30]m that retained all the distinct features of the optical absorption spectrum of the nanoclusters in solution. The films were studied by X-ray diffraction and photoelectron spectroscopy in order to investigate their crystallinity, atomic composition and valence band structure. The stability, scalability, and the film fabrication method demonstrated in this work pave the way towards the crystallization of [Ag44(SR)30]m and its full structural determination by single crystal X-ray diffraction. Moreover, due to their unique and attractive optical properties with multiple optical transitions, we anticipate these clusters to find practical applications in light-harvesting, such as photovoltaics and photocatalysis, which have been hindered so far by the instability of previous generations of the cluster. © 2013 The Royal Society of Chemistry.

  11. Electrical transport properties in Fe-Cr nanocluster-assembled granular films

    Science.gov (United States)

    Wang, Xiong-Zhi; Wang, Lai-Sen; Zhang, Qin-Fu; Liu, Xiang; Xie, Jia; Su, A.-Mei; Zheng, Hong-Fei; Peng, Dong-Liang

    2017-09-01

    The Fe100-xCrx nanocluster-assembled granular films with Cr atomic fraction (x) ranging from 0 to 100 were fabricated by using a plasma-gas-condensation cluster deposition system. The TEM characterization revealed that the uniform Fe clusters were coated with a Cr layer to form a Fe-Cr core-shell structure. Then, the as-prepared Fe100-xCrx nanoclusters were randomly assembled into a granular film in vacuum environments with increasing the deposition time. Because of the competition between interfacial resistance and shunting effect of Cr layer, the room temperature resistivity of the Fe100-xCrx nanocluster-assembled granular films first increased and then decreased with increasing the Cr atomic fraction (x), and revealed a maximum of 2 × 104 μΩ cm at x = 26 at.%. The temperature-dependent longitudinal resistivity (ρxx), magnetoresistance (MR) effect and anomalous Hall effect (AHE) of these Fe100-xCrx nanocluster-assembled granular films were also studied systematically. As the x increased from 0 to 100, the ρxx of all samples firstly decreased and then increased with increasing the measuring temperature. The dependence of ρxx on temperature could be well addressed by a mechanism incorporated for the fluctuation-induced-tunneling (FIT) conduction process and temperature-dependent scattering effect. It was found that the anomalous Hall effect (AHE) had no legible scaling relation in Fe100-xCrx nanocluster-assembled granular films. However, after deducting the contribution of tunneling effect, the scaling relation was unambiguous. Additionally, the Fe100-xCrx nanocluster-assembled granular films revealed a small negative magnetoresistance (MR), which decreased with the increase of x. The detailed physical mechanism of the electrical transport properties in these Fe100-xCrx nanocluster-assembled granular films was also studied.

  12. Green synthesis of peptide-templated gold nanoclusters as novel fluorescence probes for detecting protein kinase activity.

    Science.gov (United States)

    Song, Wei; Liang, Ru-Ping; Wang, Ying; Zhang, Li; Qiu, Jian-Ding

    2015-06-21

    A green method was employed for synthesizing peptide-templated nanoclusters without requiring strong reducing agents. Using synthetic peptide-gold nanoclusters as fluorescence probes, a novel assay for detecting protein kinase is developed based on phosphorylation against carboxypeptidase Y digestion.

  13. Synthesis of biocompatible AuAgS/Ag{sub 2}S nanoclusters and their applications in photocatalysis and mercury detection

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Qian; Chen, Shenna; Zhang, Lingyang; Huang, Haowen, E-mail: hhwn09@163.com; Liu, Fengping [Hunan University of Science and Technology, Key Laboratory of Theoretical Organic Chemistry and Function Molecule, Ministry of Education, Hunan Provincial University Key Laboratory of QSAR/QSPR, School of Chemistry and Chemical Engineering (China); Liu, Xuanyong, E-mail: xyliu@mail.sic.ac.cn [Chinese Academy of Sciences, State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics (China)

    2014-12-15

    In this paper, a facile approach for preparation of AuAgS/Ag{sub 2}S nanoclusters was developed. The unique AuAgS/Ag{sub 2}S nanoclusters capped with biomolecules exhibit interesting excellent optical and catalytic properties. The fluorescent AuAgS/Ag{sub 2}S nanoclusters show tunable luminescence depending on the nanocluster size. The apoptosis assay demonstrated that the AuAgS/Ag{sub 2}S nanoclusters showed low cytotoxicity and good biocompatibility. Therefore, the nanoclusters can be used not only as a probe for labeling cells but also for their photocatalytic activity for photodegradation of organic dye. Moreover, a highly selective and sensitive assay for detection of mercury including Hg{sup 2+} and undissociated mercury complexes was developed based on the quenching fluorescent AuAgS/Ag{sub 2}S nanoclusters, which provides a promising approach for determining various forms of Hg in the mercury-based compounds in environment. These unique nanoclusters may have potential applications in biological labeling, sensing mercury, and photodegradation of various organic pollutants in waste water.Graphical Abstract.

  14. Synthesis of biocompatible AuAgS/Ag2S nanoclusters and their applications in photocatalysis and mercury detection

    Science.gov (United States)

    Zhao, Qian; Chen, Shenna; Zhang, Lingyang; Huang, Haowen; Liu, Fengping; Liu, Xuanyong

    2014-12-01

    In this paper, a facile approach for preparation of AuAgS/Ag2S nanoclusters was developed. The unique AuAgS/Ag2S nanoclusters capped with biomolecules exhibit interesting excellent optical and catalytic properties. The fluorescent AuAgS/Ag2S nanoclusters show tunable luminescence depending on the nanocluster size. The apoptosis assay demonstrated that the AuAgS/Ag2S nanoclusters showed low cytotoxicity and good biocompatibility. Therefore, the nanoclusters can be used not only as a probe for labeling cells but also for their photocatalytic activity for photodegradation of organic dye. Moreover, a highly selective and sensitive assay for detection of mercury including Hg2+ and undissociated mercury complexes was developed based on the quenching fluorescent AuAgS/Ag2S nanoclusters, which provides a promising approach for determining various forms of Hg in the mercury-based compounds in environment. These unique nanoclusters may have potential applications in biological labeling, sensing mercury, and photodegradation of various organic pollutants in waste water.

  15. Three-dimensional macroporous carbon/hierarchical Co3O4 nanoclusters for nonenzymatic electrochemical glucose sensor

    Science.gov (United States)

    Wang, Li; Zhang, Yayun; Xie, Yingzhen; Yu, Jie; Yang, Han; Miao, Longfei; Song, Yonghai

    2017-04-01

    A novel supporting material named as three-dimensional kenaf stem-derived carbon (3D-KSCs) was used to load hierarchical Co3O4 nanoclusters for electrochemical sensing glucose. The 3D-KSCs/hierarchical Co3O4 nanoclusters were constructed by two steps. Los of acicular precursor nanoclusters firstly grew on the channels of 3D-KSCs densely by hydrothermal method and then the as-prepared 3D-KSCs/hierarchical Co3O4 nanoclusters was obtained by thermal pyrolysis of the 3D-KSCs/precursors nanocomposites at 400 °C. The 3D macroporous configuration of 3D-KSCs resulted in lots of hierarchical Co3O4 nanoclusters arrayed on the surface of 3D-KSCs owing to its large enough specific surface area, which effectively avoided their aggregations and improved the stability of nanocomposites. The obtained 3D-KSCs/hierarchical Co3O4 nanoclusters showed a large number of needle-shaped and layered Co3O4 nanoclusters uniformly grew on the macropore's walls of 3D-KSC. Due to its unique nanostructures, the 3D-KSCs/hierarchical Co3O4 nanoclusters integrated electrode showed superior performance for nonenzymatic electrochemical glucose sensing, showing wide linear range (0.088-7.0 mM) and low detection limit of 26 μM. It might be a new strategy to prepare nanostructures on 3D-KSC for future applications.

  16. MAGNET

    CERN Multimedia

    B. Curé

    2013-01-01

    The magnet is fully stopped and at room temperature. The maintenance works and consolidation activities on the magnet sub-systems are progressing. To consolidate the cryogenic installation, two redundant helium compressors will be installed as ‘hot spares’, to avoid the risk of a magnet downtime in case of a major failure of a compressor unit during operation. The screw compressors, their motors, the mechanical couplings and the concrete blocks are already available and stored at P5. The metallic structure used to access the existing compressors in SH5 will be modified to allow the installation of the two redundant ones. The plan is to finish the installation and commissioning of the hot spare compressors before the summer 2014. In the meantime, a bypass on the high-pressure helium piping will be installed for the connection of a helium drier unit later during the Long Shutdown 1, keeping this installation out of the schedule critical path. A proposal is now being prepared for the con...

  17. MAGNET

    CERN Multimedia

    B. Curé

    MAGNET During the winter shutdown, the magnet subsystems went through a full maintenance. The magnet was successfully warmed up to room temperature beginning of December 2008. The vacuum was broken later on by injecting nitrogen at a pressure just above one atmosphere inside the vacuum tank. This was necessary both to prevent any accidental humidity ingress, and to allow for a modification of the vacuum gauges on the vacuum tank and maintenance of the diffusion pumps. The vacuum gauges had to be changed, because of erratic variations on the measurements, causing spurious alarms. The new type of vacuum gauges has been used in similar conditions on the other LHC experiments and without problems. They are shielded against the stray field. The lubricants of the primary and diffusion pumps have been changed. Several minor modifications were also carried out on the equipment in the service cavern, with the aim to ease the maintenance and to allow possible intervention during operation. Spare sensors have been bough...

  18. MAGNET

    CERN Multimedia

    Benoit Curé

    2010-01-01

    The magnet worked very well at 3.8 T as expected, despite a technical issue that manifested twice in the cryogenics since June. All the other magnet sub-systems worked without flaw. The issue in the cryogenics was with the cold box: it could be observed that the cold box was getting progressively blocked, due to some residual humidity and air accumulating in the first thermal exchanger and in the adsorber at 65 K. This was later confirmed by the analysis during the regeneration phases. An increase in the temperature difference between the helium inlet and outlet across the heat exchanger and a pressure drop increase on the filter of the adsorber were observed. The consequence was a reduction of the helium flow, first compensated by the automatic opening of the regulation valves. But once they were fully opened, the flow and refrigeration power reduced as a consequence. In such a situation, the liquid helium level in the helium Dewar decreased, eventually causing a ramp down of the magnet current and a field...

  19. MAGNET

    CERN Multimedia

    Benoit Curé.

    The magnet operation restarted end of June this year. Quick routine checks of the magnet sub-systems were performed at low current before starting the ramps up to higher field. It appeared clearly that the end of the field ramp down to zero was too long to be compatible with the detector commissioning and operations plans. It was decided to perform an upgrade to keep the ramp down from 3.8T to zero within 4 hours. On July 10th, when a field of 1.5T was reached, small movements were observed in the forward region support table and it was decided to fix this problem before going to higher field. At the end of July the ramps could be resumed. On July 28th, the field was at 3.8T and the summer CRAFT exercise could start. This run in August went smoothly until a general CERN wide power cut took place on August 3rd, due to an insulation fault on the high voltage network outside point 5. It affected the magnet powering electrical circuit, as it caused the opening of the main circuit breakers, resulting in a fast du...

  20. Au Nanocluster assisted PCE improvement in PEDOT: PSS - Si Hybrid Devices

    Science.gov (United States)

    Sharma, Manisha; Pudasaini, Pushpa Raj; Ayon, Arturo A.

    2015-03-01

    Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), a P-type organic polymer is frequently employed in the fabrication of heterojunction p-n solar cell devices due to its proper HOMO-LUMO band gap as well as its tunable conductivity. In this report we describe the incorporation of gold (Au) nanoclusters in the PEDOT:PSS blend and its influence on the power-conversion-efficiency (PCE) on planar silicon (Si) hybrid heterojunction solar cell devices. Specifically, the reference samples without the aforementioned nanoclusters, were measured to exhibit a 6.10% PCE, value that increased to 7.55% upon the addition of the Au nanoclusters. The observed increase in the PCE is attributed to the enhanced electrical conductivity of the PEDOT:PSS films due to the incorporation of the nanoclusters, which is directly reflected in their improved fill factor. It is further theorized that the presence of Au nanoclusters in the insulating PSS layer in the PEDOT:PSS blend have a positive influence in the charge collection effectiveness of the devices produced. Considering that the Au nanoparticles involved in this research exercise had an average size of only 4 nm, it is considered that plasmonic effects did not play a relevant role in the observed PCE improvement.

  1. Highly fluorescent gold nanoclusters based sensor for the detection of quercetin

    Energy Technology Data Exchange (ETDEWEB)

    Chen Zhanguang, E-mail: kqlu@stu.edu.cn; Qian Sihua [Shantou University, Department of Chemistry (China); Chen Junhui, E-mail: chenjupush@126.com [Peking University Shenzhen Hospital, Interventional Oncology and Minimally Invasive Therapies Department (China); Chen Xi [Guangdong Pharmaceutical University (China)

    2012-12-15

    In this contribution, novel luminescent gold nanoclusters were synthesized by utilizing bovine serum albumin as templates with a simple, rapid, and one-pot procedure. The as-prepared gold nanoclusters were highly dispersed in aqueous solution and emitted an intense red fluorescence under UV light (365 nm). They exhibited strong fluorescence and the maximum excitation and emission wavelengths were 480 and 613.5 nm. In addition, the bovine serum albumin-stabilized gold nanoclusters were successfully utilized as novel fluorescent probes for the detection of quercetin for the first time. It was found that the addition of quercetin induced the strong fluorescence intensity of the gold nanoclusters to decrease. The decrease in fluorescence intensity of the gold nanoclusters caused by quercetin allowed the sensitive detection of quercetin in the range of 8.9 Multiplication-Sign 10{sup -8}-1.8 Multiplication-Sign 10{sup -4} mol L{sup -1}. The detection limit for quercetin is 1.8 Multiplication-Sign 10{sup -8} mol L{sup -1} at a signal-to-noise ratio of 3. The present sensor for quercetin detection possessed a low detection limit and wide linear range. In addition, the real samples were analyzed with satisfactory results.

  2. Highly fluorescent gold nanoclusters based sensor for the detection of quercetin

    Science.gov (United States)

    Chen, Zhanguang; Qian, Sihua; Chen, Junhui; Chen, Xi

    2012-12-01

    In this contribution, novel luminescent gold nanoclusters were synthesized by utilizing bovine serum albumin as templates with a simple, rapid, and one-pot procedure. The as-prepared gold nanoclusters were highly dispersed in aqueous solution and emitted an intense red fluorescence under UV light (365 nm). They exhibited strong fluorescence and the maximum excitation and emission wavelengths were 480 and 613.5 nm. In addition, the bovine serum albumin-stabilized gold nanoclusters were successfully utilized as novel fluorescent probes for the detection of quercetin for the first time. It was found that the addition of quercetin induced the strong fluorescence intensity of the gold nanoclusters to decrease. The decrease in fluorescence intensity of the gold nanoclusters caused by quercetin allowed the sensitive detection of quercetin in the range of 8.9 × 10-8-1.8 × 10-4 mol L-1. The detection limit for quercetin is 1.8 × 10-8 mol L-1 at a signal-to-noise ratio of 3. The present sensor for quercetin detection possessed a low detection limit and wide linear range. In addition, the real samples were analyzed with satisfactory results.

  3. Synthesis and Optical Properties of Au-Ag Alloy Nanoclusters with Controlled Composition

    Directory of Open Access Journals (Sweden)

    J. F. Sánchez-Ramírez

    2008-01-01

    Full Text Available Colloidal solid-solution-like Au-Ag alloy nanoclusters of different compositions were synthesized through citrate reduction of mixed metal ions of low concentrations, without using any other protective or capping agents. Optical absorption of the alloy nanoclusters was studied both theoretically and experimentally. The position of the surface plasmon resonance (SPR absorption band of the nanoclusters could be tuned from 419 nm to 521 nm through the variation of their composition. Considering effective dielectric constant of the alloy, optical absorption spectra for the nanoclusters were calculated using Mie theory, and compared with the experimentally obtained spectra. Theoretically obtained optical spectra well resembled the experimental spectra when the true size distribution of the nanoparticles was considered. High-resolution transmission electron microscopy (HREM, high-angle annular dark field (HAADF imaging, and energy dispersive spectroscopy (EDS revealed the true alloy nature of the nanoparticles with nominal composition being preserved. The synthesis technique can be extended to other bimetallic alloy nanoclusters containing Ag.

  4. Nanocrystals and Nanoclusters as Cocatalysts for Photocatalytic Water Splitting

    KAUST Repository

    Sinatra, Lutfan

    2016-12-04

    studied for the photocatalytic H2 production in order to explore the synergistic effect of the plasmonic resonance from the Au nanoparticles and pn-junction between Cu2O and TiO2. Additionally, the plasmonic effect of the Au films was also studied and utilized in order to improve the PWS. Secondly, the nanoscaling of cocatalysts was studied in order to improve the efficiency thereof and to reduce the cost of the cocatalyst materials. Moreover, it is sought to explore the quantum size effect on the properties of the cocatalyst and their effect on the photocatalytic reaction. Atomically precise Au and Ni nanoclusters were employed in these studies. Au nanoclusters were studied in relation to the cocatalysts in the photocatalytic water splitting, and Ni nanoclusters were studied in relation to the cocatalysts in the electrocatalytic water oxidation. The results of these studies will provide new insights in relation to the strategy used in order to develop efficient cocatalysts for the purpose of photocatalytic water splitting.

  5. Formation of functionalized nanoclusters by solvent evaporation and their effect on the physicochemical properties of dental composite resins.

    Science.gov (United States)

    Rodríguez, Henry A; Giraldo, Luis F; Casanova, Herley

    2015-07-01

    The aim of this work was to study the effect of silica nanoclusters (SiNC), obtained by a solvent evaporation method and functionalized by 3-methacryloxypropyltrimethoxysilane (MPS) and MPS+octyltrimethoxysilane (OTMS) (50/50wt/wt), on the rheological, mechanical and sorption properties of urethane dimethylacrylate (UDMA)/triethylenglycol dimethacrylate (TEGDMA) (80/20wt/wt) resins blend. Silica nanoparticles (SiNP) were silanized with MPS or MPS+OTMS (50/50wt/wt) and incorporated in an UDMA-isopropanol mix to produce functionalized silica nanoclusters after evaporating the isopropanol. The effect of functionalized SiNC on resins rheological properties was determined by large and small deformation tests. Mechanical, thermal, sorption and solubility properties were evaluated for composite materials. The UDMA/TEGDMA (80/20wt/wt) resins blend with added SiNC (ca. 350nm) and functionalized with MPS showed a Newtonian flow behavior associated to their spheroidal shape, whereas the resins blend with nanoclusters silanized with MPS+OTMS (50/50wt/wt) (ca. 400nm) showed a shear-thinning behavior due to nanoclusters irregular shape. Composite materials prepared with bare silica nanoclusters showed lower compressive strength than functionalized silica nanoclusters. MPS functionalized nanoclusters showed better mechanical properties but higher water sorption than functionalized nanoclusters with both silane coupling agents, MPS and OTMS. The solvent evaporation method applied to functionalized nanoparticles showed to be an alternative way to the sinterization method for producing nanoclusters, which improved some dental composite mechanical properties and reduced water sorption. The shape of functionalized silica nanoclusters showed to have influence on the rheological properties of SiNC resin suspensions and the mechanical and sorption properties of light cured composites. Copyright © 2015 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  6. Charge Carrier Dynamics at Silver Nanocluster-Molecular Acceptor Interfaces

    KAUST Repository

    Almansaf, Abdulkhaleq

    2017-07-01

    A fundamental understanding of interfacial charge transfer at donor-acceptor interfaces is very crucial as it is considered among the most important dynamical processes for optimizing performance in many light harvesting systems, including photovoltaics and photo-catalysis. In general, the photo-generated singlet excitons in photoactive materials exhibit very short lifetimes because of their dipole-allowed spin radiative decay and short diffusion lengths. In contrast, the radiative decay of triplet excitons is dipole forbidden; therefore, their lifetimes are considerably longer. The discussion in this thesis primarily focuses on the relevant parameters that are involved in charge separation (CS), charge transfer (CT), intersystem crossing (ISC) rate, triplet state lifetime, and carrier recombination (CR) at silver nanocluster (NCs) molecular-acceptors interfaces. A combination of steady-state and femto- and nanosecond broadband transient absorption spectroscopies were used to investigate the charge carrier dynamics in various donor-acceptor systems. Additionally, this thesis was prolonged to investigate some important factors that influence the charge carrier dynamics in Ag29 silver NCs donor-acceptor systems, such as the metal doping and chemical structure of the nanocluster and molecular acceptors. Interestingly, clear correlations between the steady-state measurements and timeresolved spectroscopy results are found. In the first study, we have investigated the interfacial charge transfer dynamics in positively charged meso units of 5, 10, 15, 20-tetra (1- methyl-4-pyridino)-porphyrin tetra (p-toluene sulfonate) (TMPyP) and neutral charged 5, 10, 15, 20-tetra (4-pyridyl)-porphyrin (TPyP), with negatively charged undoped and gold (Au)- doped silver Ag29 NCs. Moreover, this study showed the impact of Au doping on the charge carrier dynamics of the system. In the second study, we have investigated the interfacial charge transfer dynamics in [Pt2 Ag23 Cl7 (PPh3

  7. MAGNET

    CERN Multimedia

    Benoit Curé

    The magnet subsystems resumed operation early this spring. The vacuum pumping was restarted mid March, and the cryogenic power plant was restarted on March 30th. Three and a half weeks later, the magnet was at 4.5 K. The vacuum pumping system is performing well. One of the newly installed vacuum gauges had to be replaced at the end of the cool-down phase, as the values indicated were not coherent with the other pressure measurements. The correction had to be implemented quickly to be sure no helium leak could be at the origin of this anomaly. The pressure measurements have been stable and coherent since the change. The cryogenics worked well, and the cool-down went quite smoothly, without any particular difficulty. The automated start of the turbines had to be fine-tuned to get a smooth transition, as it was observed that the cooling power delivered by the turbines was slightly higher than needed, causing the cold box to stop automatically. This had no consequence as the cold box safety system acts to keep ...

  8. MAGNET

    CERN Multimedia

    B. Curé

    During the winter shutdown, the magnet subsystems went through a full maintenance. The magnet was successfully warmed up to room temperature beginning of December 2008. The vacuum was broken later on by injecting nitrogen at a pressure just above one atmosphere inside the vacuum tank. This was necessary both to prevent any accidental humidity ingress, and to allow for a modification of the vacuum gauges on the vacuum tank and maintenance of the diffusion pumps. The vacuum gauges had to be changed, because of erratic variations on the measurements, causing spurious alarms. The new type of vacuum gauges has been used in similar conditions on the other LHC experiments and without problems. They are shielded against the stray field. The lubricants of the primary and diffusion pumps have been changed. Several minor modifications were also carried out on the equipment in the service cavern, with the aim to ease the maintenance and to allow possible intervention during operation. Spare sensors have been bought. Th...

  9. Layered Double Hydroxide Nanoclusters: Aqueous, Concentrated, Stable, and Catalytically Active Colloids toward Green Chemistry.

    Science.gov (United States)

    Tokudome, Yasuaki; Morimoto, Tsuyoshi; Tarutani, Naoki; Vaz, Pedro D; Nunes, Carla D; Prevot, Vanessa; Stenning, Gavin B G; Takahashi, Masahide

    2016-05-24

    Increasing attention has been dedicated to the development of nanomaterials rendering green and sustainable processes, which occur in benign aqueous reaction media. Herein, we demonstrate the synthesis of another family of green nanomaterials, layered double hydroxide (LDH) nanoclusters, which are concentrated (98.7 g/L in aqueous solvent), stably dispersed (transparent sol for >2 weeks), and catalytically active colloids of nano LDHs (isotropic shape with the size of 7.8 nm as determined by small-angle X-ray scattering). LDH nanoclusters are available as colloidal building blocks to give access to meso- and macroporous LDH materials. Proof-of-concept applications revealed that the LDH nanocluster works as a solid basic catalyst and is separable from solvents of catalytic reactions, confirming the nature of nanocatalysts. The present work closely investigates the unique physical and chemical features of this colloid, the formation mechanism, and the ability to act as basic nanocatalysts in benign aqueous reaction systems.

  10. XAFS studies of monodisperse Au nanoclusters formation in the etching process

    Science.gov (United States)

    Yang, Lina; Huang, Ting; Liu, Wei; Bao, Jie; Huang, Yuanyuan; Cao, Yuanjie; Yao, Tao; Sun, Zhihu; Wei, Shiqiang

    2016-05-01

    Understanding the formation mechanism of gold nanoclusters is essential to the development of their synthetic chemistry. Here, by using x-ray absorption fine-structure (XAFS) spectroscopy, UV-Vis and MS spectra, the formation process of monodisperse Au13 nanoclusters is investigated. We find that a critical step involving the formation of smaller Au8-Au11 metastable intermediate clusters induced by the HCl + HSR etching of the polydisperse Aun precursor clusters occurs firstly. Then these intermediate species undergo a size-growth to Au13 cores, followed by a slow structure rearrangement to reach the final stable structure. This work enriches the understanding of cluster formation chemistry and may guide the way towards the design and the controllable synthesis of nanoclusters.

  11. Crystal structure of selenolate-protected Au24(SeR)20 nanocluster.

    Science.gov (United States)

    Song, Yongbo; Wang, Shuxin; Zhang, Jun; Kang, Xi; Chen, Shuang; Li, Peng; Sheng, Hongting; Zhu, Manzhou

    2014-02-26

    We report the X-ray structure of a selenolate-capped Au24(SeR)20 nanocluster (R = C6H5). It exhibits a prolate Au8 kernel, which can be viewed as two tetrahedral Au4 units cross-joined together without sharing any Au atoms. The kernel is protected by two trimeric Au3(SeR)4 staple-like motifs as well as two pentameric Au5(SeR)6 staple motifs. Compared to the reported gold-thiolate nanocluster structures, the features of the Au8 kernel and pentameric Au5(SeR)6 staple motif are unprecedented and provide a structural basis for understanding the gold-selenolate nanoclusters.

  12. Coherent Fano resonances in a plasmonic nanocluster enhance optical four-wave mixing

    Science.gov (United States)

    Zhang, Yu; Wen, Fangfang; Zhen, Yu-Rong; Nordlander, Peter; Halas, Naomi J.

    2013-01-01

    Plasmonic nanoclusters, an ordered assembly of coupled metallic nanoparticles, support unique spectral features known as Fano resonances due to the coupling between their subradiant and superradiant plasmon modes. Within the Fano resonance, absorption is significantly enhanced, giving rise to highly localized, intense near fields with the potential to enhance nonlinear optical processes. Here, we report a structure supporting the coherent oscillation of two distinct Fano resonances within an individual plasmonic nanocluster. We show how this coherence enhances the optical four-wave mixing process in comparison with other double-resonant plasmonic clusters that lack this property. A model that explains the observed four-wave mixing features is proposed, which is generally applicable to any third-order process in plasmonic nanostructures. With a larger effective susceptibility χ(3) relative to existing nonlinear optical materials, this coherent double-resonant nanocluster offers a strategy for designing high-performance third-order nonlinear optical media. PMID:23690571

  13. Analysis of the applicability of Ni, Cu, Au, Pt, and Pd nanoclusters for data recording

    Science.gov (United States)

    Redel', L. V.; Gafner, S. L.; Gafner, Yu. Ya.; Zamulin, I. S.; Goloven'ko, Zh. V.

    2017-02-01

    The applicability of individual Ni, Cu, Au, Pt, and Pd nanoclusters as data bits in next generation memory devices constructed on the phase-change carrier principle is studied. To this end, based on the modified tight-binding potential (TB-SMA), structure formation from the melt of nanoparticles of these metals to 10 nm in diameter was simulated by the molecular dynamics method. The effect of various crystallization conditions on the formation of the internal structures of Ni, Cu, Au, Pt, and Pd nanoclusters is studied. The stability boundaries of various crystalline isomers are analyzed. The obtained systematic features are compared for nanoparticles of copper, nickel, gold, platinum, and palladium of identical sizes. It is concluded that platinum nanoclusters of diameter D > 8 nm are the best materials among studied metals for producing memory elements based on phase transitions.

  14. XAFS study on thiol etching of diphosphine-stabilized gold nanoclusters

    Science.gov (United States)

    Bao, Jie; Yang, Lina; Huang, Ting; Sun, Zhihu; Yao, Tao; Jiang, Yong; Wei, Shiqiang

    2017-08-01

    Thiol-etching triphenylphosphine (PPh3)-protected Au nanoclusters has been widely used to synthesize thiolated Au nanoclusters, while few studies have been reported on the thiol-etching reaction starting from diphosphine-protected Au clusters. Here the thiol-etching reaction in chloroform (CHCl3) for 1,5-Bis(diphenylphosphino) pentane (L5) protected Au11 nanoclusters is presented, and synchrotron radiation X-ray absorption fine structure, UV-vis absorption and mass spectra are combined to identify the reaction products. It is revealed that a gold(I)-thiolate complex Au2L5(RS) is produced, contrary to the case of thiol-etching PPh3-protected Au clusters where formation of thermodynamically stable Au25 or Au11 clusters is achieved.

  15. Crystal structure and electronic properties of a thiolate-protected Au24 nanocluster

    Science.gov (United States)

    Das, Anindita; Li, Tao; Li, Gao; Nobusada, Katsuyuki; Zeng, Chenjie; Rosi, Nathaniel L.; Jin, Rongchao

    2014-05-01

    Solving the total structures of gold nanoclusters is of critical importance for understanding their electronic, optical and catalytic properties. Herein, we report the X-ray structure of a charge-neutral Au24(SCH2Ph-tBu)20 nanocluster. This structure features a bi-tetrahedral Au8 kernel protected by four tetrameric staple-like motifs. Electronic structure analysis is further carried out and the optical absorption spectrum is interpreted. The Au24(SCH2Ph-tBu)20, Au23(S-c-C6H11)16 and Au25(SCH2CH2Ph)18 nanoclusters constitute the first crystallographically characterized ``trio''.Solving the total structures of gold nanoclusters is of critical importance for understanding their electronic, optical and catalytic properties. Herein, we report the X-ray structure of a charge-neutral Au24(SCH2Ph-tBu)20 nanocluster. This structure features a bi-tetrahedral Au8 kernel protected by four tetrameric staple-like motifs. Electronic structure analysis is further carried out and the optical absorption spectrum is interpreted. The Au24(SCH2Ph-tBu)20, Au23(S-c-C6H11)16 and Au25(SCH2CH2Ph)18 nanoclusters constitute the first crystallographically characterized ``trio''. Electronic supplementary information (ESI) available: Experimental and supporting Fig. S1-S3. CCDC NUMBER(1000102). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4nr01350f

  16. Phenotypic Screening Identifies Protein Synthesis Inhibitors as H-Ras-Nanocluster-Increasing Tumor Growth Inducers.

    Science.gov (United States)

    Najumudeen, Arafath K; Posada, Itziar M D; Lectez, Benoit; Zhou, Yong; Landor, Sebastian K-J; Fallarero, Adyary; Vuorela, Pia; Hancock, John; Abankwa, Daniel

    2015-12-15

    Ras isoforms H-, N-, and K-ras are each mutated in specific cancer types at varying frequencies and have different activities in cell fate control. On the plasma membrane, Ras proteins are laterally segregated into isoform-specific nanoscale signaling hubs, termed nanoclusters. As Ras nanoclusters are required for Ras signaling, chemical modulators of nanoclusters represent ideal candidates for the specific modulation of Ras activity in cancer drug development. We therefore conducted a chemical screen with commercial and in-house natural product libraries using a cell-based H-ras-nanoclustering FRET assay. Next to established Ras inhibitors, such as a statin and farnesyl-transferase inhibitor, we surprisingly identified five protein synthesis inhibitors as positive regulators. Using commonly employed cycloheximide as a representative compound, we show that protein synthesis inhibition increased nanoclustering and effector recruitment specifically of active H-ras but not of K-ras. Consistent with these data, cycloheximide treatment activated both Erk and Akt kinases and specifically promoted H-rasG12V-induced, but not K-rasG12V-induced, PC12 cell differentiation. Intriguingly, cycloheximide increased the number of mammospheres, which are enriched for cancer stem cells. Depletion of H-ras in combination with cycloheximide significantly reduced mammosphere formation, suggesting an exquisite synthetic lethality. The potential of cycloheximide to promote tumor cell growth was also reflected in its ability to increase breast cancer cell tumors grown in ovo. These results illustrate the possibility of identifying Ras-isoform-specific modulators using nanocluster-directed screening. They also suggest an unexpected feedback from protein synthesis inhibition to Ras signaling, which might present a vulnerability in certain tumor cell types.

  17. Photoluminescent gold nanoclusters as sensing probes for uropathogenic Escherichia coli.

    Directory of Open Access Journals (Sweden)

    Po-Han Chan

    Full Text Available Glycan-bound nanoprobes have been demonstrated as suitable sensing probes for bacteria containing glycan binding sites. In this study, we demonstrated a facile approach for generating glycan-bound gold nanoclusters (AuNCs. The generated AuNCs were used as sensing probes for corresponding target bacteria. Mannose-capped AuNCs (AuNCs@Mann were generated and used as the model sensors for target bacteria. A one-step synthesis approach was employed to generate AuNCs@Mann. In this approach, an aqueous solution of tetrachloroauric acid and mannoside that functionized with a thiol group (Mann-SH was stirred at room temperature for 48 h. The mannoside functions as reducing and capping agent. The size of the generated AuNCs@Mann is 1.95±0.27 nm, whereas the AuNCs with red photoluminescence have a maximum emission wavelength of ~630 nm (λexcitation = 375 nm. The synthesis of the AuNCs@Mann was accelerated by microwave heating, which enabled the synthesis of the AuNCs@Mann to complete within 1 h. The generated AuNCs@Mann are capable of selectively binding to the urinary tract infection isolate Escherichia coli J96 containing the mannose binding protein FimH expressed on the type 1 pili. On the basis of the naked eye observation, the limit of detection of the sensing approach is as low as ~2×10(6 cells/mL.

  18. Photoluminescent gold nanoclusters as sensing probes for uropathogenic Escherichia coli.

    Science.gov (United States)

    Chan, Po-Han; Ghosh, Bhaswati; Lai, Hong-Zheng; Peng, Hwei-Ling; Mong, Kwok Kong Tony; Chen, Yu-Chie

    2013-01-01

    Glycan-bound nanoprobes have been demonstrated as suitable sensing probes for bacteria containing glycan binding sites. In this study, we demonstrated a facile approach for generating glycan-bound gold nanoclusters (AuNCs). The generated AuNCs were used as sensing probes for corresponding target bacteria. Mannose-capped AuNCs (AuNCs@Mann) were generated and used as the model sensors for target bacteria. A one-step synthesis approach was employed to generate AuNCs@Mann. In this approach, an aqueous solution of tetrachloroauric acid and mannoside that functionized with a thiol group (Mann-SH) was stirred at room temperature for 48 h. The mannoside functions as reducing and capping agent. The size of the generated AuNCs@Mann is 1.95±0.27 nm, whereas the AuNCs with red photoluminescence have a maximum emission wavelength of ~630 nm (λexcitation = 375 nm). The synthesis of the AuNCs@Mann was accelerated by microwave heating, which enabled the synthesis of the AuNCs@Mann to complete within 1 h. The generated AuNCs@Mann are capable of selectively binding to the urinary tract infection isolate Escherichia coli J96 containing the mannose binding protein FimH expressed on the type 1 pili. On the basis of the naked eye observation, the limit of detection of the sensing approach is as low as ~2×10(6) cells/mL.

  19. Silver Nanoclusters: From Design Principles to Practical Applications

    KAUST Repository

    Abdulhalim, Lina G.

    2015-12-08

    A strategy based on reticulating metal ions and organic ligands into atomically precise gold and silver nanoclusters (NCs) with high monodispersity has been advanced to a point that allows the design of NCs with strict stoichiometries, functionalities and valence. Of the Ag NCs discovered, Ag44 is the most studied, not only due to its high absorption that transcends the visible spectrum suitable for photovoltaics but also because of its long excited state lifetime, as revealed by nanosecond transient absorption spectroscopy. A major principle discovered in this dissertation is the ability to produce Ag44 in scalable amounts and with high stability in addition to modulation of the functional groups of the organic ligands via a fast and complete ligand exchange process. This new discovery has led to the development of synthetic designs in which new sizes were obtained by varying the reaction parameters (e.g., ligands functionality, reaction temperature and time), namely, Ag29 using dithiols and phosphines. The synthesized NCs possess tetravalent functionalities that facilitate their crystallization and characterization. Furthermore, Ag29 glows red and is therefore a possible candidate for sensing and imaging applications.

  20. Rigid rod spaced fullerene as building block for nanoclusters

    Indian Academy of Sciences (India)

    Pallikara K Sudeep; James P Varkey; K George Thomas; Manappurathu V George; Prashant V Kamat

    2003-10-01

    By using phenylacetylene based rigid-rod linkers (PhA), we have successfully synthesized two fullerene derivatives, C60-PhA and C60-PhA-C60. The absorption spectral features of C60, as well as that of the phenylacetylene moiety are retained in the monomeric forms of these fullerene derivatives, ruling out the possibility of any strong interaction between the two chromophores in the ground state. Both the fullerene derivatives form optically transparent clusters, absorbing in the UV-Vis region; this clustering leads to a significant increase in their molar extinction coefficients. TEM characterization of the C60-PhA showed large spherical clusters, with sizes ranging from 150-350 nm, while an elongated wire-type structure was observed for the bisfullerene derivative (C60-PhA-C60). AFM section analysis studies of isolated nanoclusters of C60-PhA-C60, deposited on mica, indicate that smaller clusters associate to form larger nanostructures.

  1. Growth and characterization of barium oxide nanoclusters on YSZ(111)

    Energy Technology Data Exchange (ETDEWEB)

    Nachimuthu, Ponnusamy; Kim, Yong Joo; Kuchibhatla, Satyanarayana V N T; Yu, Zhongqing; Jiang, Weilin; Engelhard, Mark H.; Shutthanandan, V.; Szanyi, Janos; Thevuthasan, Suntharampillai

    2009-08-13

    Barium oxide (BaO) was grown on YSZ(111) substrate by oxygen-plasma-assisted molecular beam epitaxy (OPA-MBE). In-situ reflection high-energy electron diffraction, ex-situ x-ray diffraction, atomic force microscopy and x-ray photoelectron spectroscopy have confirmed that the BaO grows as clusters on YSZ(111). During and following the growth under UHV conditions, BaO remains in single phase. When exposed to ambient conditions, the clusters transformed to BaCO3 and/or Ba(OH)2 H2O. However, in a few attempts of BaO growth, XRD results show a fairly single phase cubic BaO with a lattice constant of 0.5418(1) nm. XPS results show that exposing BaO clusters to ambient conditions results in the formation BaCO3 on the surface and partly Ba(OH)2 throughout in the bulk. Based on the observations, it is concluded that the BaO nanoclusters grown on YSZ(111) are highly reactive in ambient conditions. The variation in the reactivity of BaO between different attempts of the growth is attributed to the cluster size.

  2. Ag29(BDT)12(TPP)4: A Tetravalent Nanocluster

    KAUST Repository

    AbdulHalim, Lina G.

    2015-06-24

    The bottom-up assembly of nanoparticles into diverse ordered solids is a challenge because it requires nanoparticles, which are often quasi-spherical, to have interaction anisotropy akin to atoms and molecules. Typically, anisotropy has been introduced by changing the shape of the inorganic nanoparticle core. Here, we present the design, self-assembly, optical properties and total structural determination of Ag29(BDT)12(TPP)4, an atomically precise tetravalent nanocluster (NC) (BDT: 1,3-benzenedithiols; TPP: triphenylphosphine). It features four unique tetrahedrally symmetrical binding surface sites facilitated by the supramolecular assembly of 12 BDT—wide footprint bidentate thiols—in the ligand shell. When each of these sites was selectively functionalized by a single phosphine ligand, particle stability, synthetic yield and the propensity to self-assemble into macroscopic crystals increased. The solid crystallized NCs have a substantially narrowed optical bandgap compared to that of the solution state, suggesting strong inter-particle electronic coupling occurs in the solid state.

  3. Formation of fivefold axes in the FCC-metal nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Myasnichenko, Vladimir S., E-mail: virtson@gmail.com [Altai State Technical University, 46 Lenina av., Barnaul 656038 (Russian Federation); Starostenkov, Mikhail D. [Altai State Technical University, 46 Lenina av., Barnaul 656038 (Russian Federation)

    2012-11-01

    Highlights: Black-Right-Pointing-Pointer Formation of fcc-metal nanoclusters having the fivefold symmetry. Black-Right-Pointing-Pointer Formation of the cores of icosahedral symmetry in the gold, silver and copper nanoparticles. Black-Right-Pointing-Pointer Construction of bimetallic clusters with icosahedral symmetry and increased fractal dimensionality. - Abstract: Formation of atomistic structures of metallic Cu, Au, Ag clusters and bimetallic Cu-Au clusters was studied with the help of molecular dynamics using the many-body tight-binding interatomic potential. The simulation of the crystallization process of clusters with the number of atoms ranging from 300 to 1092 was carried out. The most stable configurations of atoms in the system, corresponding to the minimum of potential energy, was found during super-fast cooling from 1000 K. Atoms corresponding to fcc, hcp, and Ih phases were identified by the method of common neighbor analysis. Incomplete icosahedral core can be discovered at the intersection of one of the Ih axes with the surface of monometallic cluster. The decahedron-shaped structure of bimetallic Cu-Au cluster with seven completed icosahedral cores was obtained. The principles of the construction of small bimetallic clusters with icosahedral symmetry and increased fractal dimensionality were offered.

  4. First-Principles Investigation of Ag-Doped Gold Nanoclusters

    Directory of Open Access Journals (Sweden)

    Fei-Yue Fan

    2011-05-01

    Full Text Available Gold nanoclusters have the tunable optical absorption property, and are promising for cancer cell imaging, photothermal therapy and radiotherapy. First-principle is a very powerful tool for design of novel materials. In the present work, structural properties, band gap engineering and tunable optical properties of Ag-doped gold clusters have been calculated using density functional theory. The electronic structure of a stable Au20 cluster can be modulated by incorporating Ag, and the HOMO–LUMO gap of Au20−nAgn clusters is modulated due to the incorporation of Ag electronic states in the HOMO and LUMO. Furthermore, the results of the imaginary part of the dielectric function indicate that the optical transition of gold clusters is concentration-dependent and the optical transition between HOMO and LUMO shifts to the low energy range as the Ag atom increases. These calculated results are helpful for the design of gold cluster-based biomaterials, and will be of interest in the fields of radiation medicine, biophysics and nanoscience.

  5. Absorption spectra of alkali-C₆₀ nanoclusters.

    Science.gov (United States)

    Rabilloud, Franck

    2014-10-28

    We investigate the absorption spectra of alkali-doped C60 nanoclusters, namely C60Nan, C60Kn, and C60Lin, with n = 1, 2, 6, 12, in the framework of the time-dependent density-functional theory (TDDFT). We study the dependence of the absorption spectra on the nature of the alkali. We show that in few cases the absorption spectra depend on the arrangement of the alkali atoms over the fullerene, though sometimes the absorption spectra do not allow us to distinguish between different configurations. When only one or two alkali atoms are adsorbed on the fullerene, the optical response of alkali-doped C60 is similar to that of the anion C60(-) with a strong response in the UV domain. In contrast, for higher concentration of alkali, a strong optical response is predicted in the visible range, particularly when metal-metal bonds are formed. The weak optical response of the I(h)-symmetry C60Li12 is proposed to be used as a signature of its structure.

  6. A strategy to find minimal energy nanocluster structures.

    Science.gov (United States)

    Rogan, José; Varas, Alejandro; Valdivia, Juan Alejandro; Kiwi, Miguel

    2013-11-05

    An unbiased strategy to search for the global and local minimal energy structures of free standing nanoclusters is presented. Our objectives are twofold: to find a diverse set of low lying local minima, as well as the global minimum. To do so, we use massively the fast inertial relaxation engine algorithm as an efficient local minimizer. This procedure turns out to be quite efficient to reach the global minimum, and also most of the local minima. We test the method with the Lennard-Jones (LJ) potential, for which an abundant literature does exist, and obtain novel results, which include a new local minimum for LJ13 , 10 new local minima for LJ14 , and thousands of new local minima for 15≤N≤65. Insights on how to choose the initial configurations, analyzing the effectiveness of the method in reaching low-energy structures, including the global minimum, are developed as a function of the number of atoms of the cluster. Also, a novel characterization of the potential energy surface, analyzing properties of the local minima basins, is provided. The procedure constitutes a promising tool to generate a diverse set of cluster conformations, both two- and three-dimensional, that can be used as an input for refinement by means of ab initio methods. Copyright © 2013 Wiley Periodicals, Inc.

  7. Exotic high activity surface patterns in PtAu nanoclusters

    KAUST Repository

    Mokkath, Junais Habeeb

    2013-05-09

    The structure and chemical ordering of PtAu nanoclusters of 79, 135, and 201 atoms are studied via a combination of a basin hopping atom-exchange technique (to locate the lowest energy homotops at fixed composition), a symmetry orbit technique (to find the high symmetry isomers), and density functional theory local reoptimization (for determining the most stable homotop). The interatomic interactions between Pt and Au are derived from the empirical Gupta potential. The lowest energy structures show a marked tendency toward PtcoreAushell chemical ordering by enrichment of the more cohesive Pt in the core region and of Au in the shell region. We observe a preferential segregation of Pt atoms to (111) facets and Au atoms to (100) facets of the truncated octahedron cluster motif. Exotic surface patterns are obtained particularly for Pt-rich compositions, where Pt atoms are being surrounded by Au atoms. These surface arrangements boost the catalytic activity by creating a large number of active sites. © 2013 American Chemical Society.

  8. "light-on" sensing of antioxidants using gold nanoclusters

    KAUST Repository

    Hu, Lianzhe

    2014-05-20

    Depletion of intracellular antioxidants is linked to major cytotoxic events and cellular disorders, such as oxidative stress and multiple sclerosis. In addition to medical diagnosis, determining the concentration of antioxidants in foodstuffs, food preservatives, and cosmetics has proved to be very vital. Gold nanoclusters (Au-NCs) have a core size below 2 nm and contain several metal atoms. They have interesting photophysical properties, are readily functionalized, and are safe to use in various biomedical applications. Herein, a simple and quantitative spectroscopic method based on Au-NCs is developed to detect and image antioxidants such as ascorbic acid. The sensing mechanism is based on the fact that antioxidants can protect the fluorescence of Au-NCs against quenching by highly reactive oxygen species. Our method shows great accuracy when employed to detect the total antioxidant capacity in commercial fruit juice. Moreover, confocal fluorescence microscopy images of HeLa cells show that this approach can be successfully used to image antioxidant levels in living cells. Finally, the potential application of this "light-on" detection method in multiple logic gate fabrication was discussed using the fluorescence intensity of Au-NCs as output. © 2014 American Chemical Society.

  9. Synthesis and characterization of human transferrin-stabilized gold nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Le Guevel, Xavier; Schneider, Marc [Pharmaceutical Nanotechnology, Saarland University, Saarbruecken (Germany); Daum, Nicole, E-mail: Marc.Schneider@mx.uni-saarland.de [Drug Delivery, Helmholtz Institute for Pharmaceutical Research Saarland (HIPS), Saarbruecken (Germany)

    2011-07-08

    Human transferrin has been biolabelled with gold nanoclusters (Au NCs) using a simple, fast and non-toxic method. These nanocrystals (<2 nm) are stabilized in the protein via sulfur groups and have a high fluorescence emission in the near infrared region (QY = 4.3%; {lambda}{sub em} = 695 nm). Structural investigation and photophysical measurements show a high population of clusters formed of 22-33 gold atoms covalently bound to the transferrin. In solutions with pH ranging from 5 to 10 and in buffer solutions (PBS, HEPES), those biolabelled proteins exhibit a good stability. No significant quenching effect of the fluorescent transferrin has been detected after iron loading of iron-free transferrin (apoTf) and in the presence of a specific polyclonal antibody. Additionally, antibody-induced agglomeration demonstrates no alteration in the protein activity and the receptor target ability. MTT and Vialight Plus tests show no cytotoxicity of these labelled proteins in cells (1 {mu}g ml{sup -1}-1 mg ml{sup -1}). Cell line experiments (A549) indicate also an uptake of the iron loaded fluorescent proteins inside cells. These remarkable data highlight the potential of a new type of non-toxic fluorescent transferrin for imaging and targeting.

  10. Atomic-scale structure of single-layer MoS2 nanoclusters

    DEFF Research Database (Denmark)

    Helveg, S.; Lauritsen, J. V.; Lægsgaard, E.

    2000-01-01

    We have studied using scanning tunneling microscopy (STM) the atomic-scale realm of molybdenum disulfide (MoS2) nanoclusters, which are of interest as a model system in hydrodesulfurization catalysis. The STM gives the first real space images of the shape and edge structure of single-layer MoS2 n...... nanoparticles synthesized on Au(lll), and establishes a new picture of the active edge sires of the nanoclusters. The results demonstrate a way to get detailed atomic-scale information on catalysts in general....

  11. Fabrication, Study of Optical Properties and Structure of Most Stable (CdP2)n Nanoclusters

    OpenAIRE

    Yeshchenko, O. A.; Dmitruk, I. M.; Koryakov, S. V.; Galak, M. P.

    2005-01-01

    CdP2 nanoclusters were fabricated by incorporation into pores of zeolite Na-X and by laser ablation. Absorption and photoluminescence (PL) spectra of CdP2 nanoclusters in zeolite were measured at the temperatures of 4.2, 77 and 293 K. Both absorption and PL spectra consist of two bands blue shifted with respect to bulk crystal. We performed the calculations aimed to find the most stable clusters in the size region up to size of the zeolite Na-X supercage. The most stable clusters are (CdP2)6 ...

  12. Self-organized arrays of Cd nanocluster on Si (111)-7×7 surface

    Science.gov (United States)

    Hao, Shao-Jie; Xiao, Hua-Fang; Ye, Juan; Sun, Kai; Tao, Min-Long; Tu, Yu-Bing; Wang, Ya-Li; Xie, Zheng-Bo; Wang, Jun-Zhong

    2017-02-01

    We studied the self-organization of Cd clusters on Si(111)-7×7 surface with an ultrahigh vacuum scanning tunneling microcopy (STM). Highly-ordered arrays of Cd nanoclusters have been fabricated by elevating the substrate temperature. The Cd clusters occupy equally the faulted and unfaulted half-unit cells of Si(111)-7×7 without obvious preference to either of them, forming Cd cluster pairs or hexamers. Furthermore, high-resolution STM images demonstrate that the charge transfer between Cd and Si atoms is responsible for cluster-cluster attractions, which in turn drive the self-organization of Cd nanoclusters into highly ordered arrays.

  13. Tetrahedral 1B4Sb nanoclusters in GaP:(B, Sb)

    Energy Technology Data Exchange (ETDEWEB)

    Elyukhin, V A, E-mail: elyukhin@cinvestav.m [Departamento de Ingenieria Electrica-SEES, CINVESTAV-IPN, Avenida IPN 2508, Col. San Pedro Zacatenco, C. P. 07360, Mexico, D. F. (Mexico)

    2009-05-01

    Self-assembling conditions of 1B4Sb tetrahedral nanoclusters in GaP doped with boron and Sb isoelectronic impurities are represented in the ultradilute and dilute limits of the boron and Sb contents, respectively. The fulfilled estimates demonstrated the preferential complete or almost complete allocation of boron atoms in 1B4Sb nanoclusters at temperatures of 500 {sup 0}C and 900 {sup 0}C, respectively. The significant decrease of the sum of the free energies of the constituent compounds is the main origin of self-assembling. The reduction of the strain energy is the additional cause of this phenomenon.

  14. One-pot one-cluster synthesis of fluorescent and bio-compatible Ag14 nanoclusters for cancer cell imaging

    Science.gov (United States)

    Yang, Jie; Xia, Nan; Wang, Xinan; Liu, Xianhu; Xu, An; Wu, Zhikun; Luo, Zhixun

    2015-11-01

    Small-molecule-protected silver nanoclusters have smaller hydrodynamic diameter, and thus may hold greater potential in biomedicine application compared with the same core-sized, macromolecule (i.e. DNA)-protected silver nanoclusters. However, the live cell imaging labeled by small-molecule-protected silver nanoclusters has not been reported until now, and the synthesis and atom-precise characterization of silver nanoclusters have been challenging for a long time. We develop a one-pot one-cluster synthesis method to prepare silver nanoclusters capped with GSH which is bio-compatible. The as-prepared silver nanoclusters are identified to be Ag14(SG)11 (abbreviated as Ag14, SG: glutathione) by isotope-resolvable ESI-MS. The structure is probed by 1D NMR spectroscopy together with 2D COSY and HSQC. This cluster species is fluorescent and the fluorescence quantum yield is solvent-dependent. Very importantly, Ag14 was successfully applied to label lung cancer cells (A549) for imaging, and this work represents the first attempt to image live cells with small-molecule-protected silver nanoclusters. Furthermore, it is revealed that the Ag14 nanoclusters exhibit lower cytotoxicity compared with some other silver species (including silver salt, silver complex and large silver nanoparticles), and the explanation is also provided. The comparison of silver nanoclusters to state-of-the-art labeling materials in terms of cytotoxicity and photobleaching lifetime is also conducted.Small-molecule-protected silver nanoclusters have smaller hydrodynamic diameter, and thus may hold greater potential in biomedicine application compared with the same core-sized, macromolecule (i.e. DNA)-protected silver nanoclusters. However, the live cell imaging labeled by small-molecule-protected silver nanoclusters has not been reported until now, and the synthesis and atom-precise characterization of silver nanoclusters have been challenging for a long time. We develop a one-pot one

  15. Atomistic study on mixed-mode fracture mechanisms of ferrite iron interacting with coherent copper and nickel nanoclusters

    Science.gov (United States)

    Al-Motasem, Ahmed Tamer; Mai, Nghia Trong; Choi, Seung Tae; Posselt, Matthias

    2016-04-01

    The effect of copper and/or nickel nanoclusters, generally formed by neutron irradiation, on fracture mechanisms of ferrite iron was investigated by using molecular statics simulation. The equilibrium configuration of nanoclusters was obtained by using a combination of an on-lattice annealing based on Metropolis Monte Carlo method and an off-lattice relaxation by molecular dynamics simulation. Residual stress distributions near the nanoclusters were also calculated, since compressive or tensile residual stresses may retard or accelerate, respectively, the propagation of a crack running into a nanocluster. One of the nanoclusters was located in front of a straight crack in ferrite iron with a body-centered cubic crystal structure. Two crystallographic directions, of which the crack plane and crack front direction are (010)[001] and (111) [ 1 bar 10 ] , were considered, representing cleavage and non-cleavage orientations in ferrite iron, respectively. Displacements corresponding to pure opening-mode and mixed-mode loadings were imposed on the boundary region and the energy minimization was performed. It was observed that the fracture mechanisms of ferrite iron under the pure opening-mode loading are strongly influenced by the presence of nanoclusters, while under the mixed-mode loading the nanoclusters have no significant effect on the crack propagation behavior of ferrite iron.

  16. Energy of the Isolated Metastable Iron-Nickel FCC Nanocluster with a Carbon Atom in the Tetragonal Interstice.

    Science.gov (United States)

    Bondarenko, Natalya V; Nedolya, Anatoliy V

    2017-12-01

    The energy of the isolated iron-nickel nanocluster was calculated by molecular mechanics method using Lennard-Jones potential. The cluster included a carbon atom that drifted from an inside octahedral interstice to a tetrahedral interstice in [Formula: see text] direction and after that in direction to the surface. In addition, one of 14 iron atoms was replaced by a nickel atom, the position of which was changing during simulation.The energy of the nanocluster was estimated at the different interatomic distances. As a result of simulation, the optimal interatomic distances of Fe-Ni-C nanocluster was chosen for the simulation, in which height of the potential barrier was maximal and face-centered cubic (FCC) nanocluster was the most stable.It is shown that there were three main positions of a nickel atom that significantly affected nanocluster's energy.The calculation results indicated that position of the carbon atom in the octahedral interstice was more energetically favorable than tetrahedral interstice in the case of FCC nanocluster. On the other side, the potential barrier was smaller in the direction [Formula: see text] than in the direction .This indicates that there are two ways for carbon atom to drift to the surface of the nanocluster.

  17. MAGNET

    CERN Multimedia

    Benoit Curé

    2013-01-01

    Maintenance work and consolidation activities on the magnet cryogenics and its power distribution are progressing according to the schedules. The manufacturing of the two new helium compressor frame units has started. The frame units support the valves, all the sensors and the compressors with their motors. This activity is subcontracted. The final installation and the commissioning at CERN are scheduled for March–April 2014. The overhauls of existing cryogenics equipment (compressors, motors) are in progress. The reassembly of the components shall start in early 2014. The helium drier, to be installed on the high-pressure helium piping, has been ordered and will be delivered in the first trimester of 2014. The power distribution for the helium compressors in SH5 on the 3.3kV network is progressing. The 3.3kV switches, between each compressor and its hot spare compressor, are being installed, together with the power cables for the new compressors. The 3.3kV electrical switchboards in SE5 will ...

  18. MAGNET

    CERN Multimedia

    Benoit Curé

    The cooling down to the nominal temperature of 4.5 K was achieved at the beginning of August, in conjunction with the completion of the installation work of the connection between the power lines and the coil current leads. The temperature gradient on the first exchanger of the cold box is now kept within the nominal range. A leak of lubricant on a gasket of the helium compressor station installed at the surface was observed and several corrective actions were necessary to bring the situation back to normal. The compressor had to be refilled with lubricant and a regeneration of the filters and adsorbers was necessary. The coil cool down was resumed successfully, and the cryogenics is running since then with all parameters being nominal. Preliminary tests of the 20kA coil power supply were done earlier at full current through the discharge lines into the dump resistors, and with the powering busbars from USC5 to UXC5 without the magnet connected. On Monday evening August 25th, at 8pm, the final commissionin...

  19. MAGNET

    CERN Multimedia

    B. Curé

    The first phase of the commissioning ended in August by a triggered fast dump at 3T. All parameters were nominal, and the temperature recovery down to 4.5K was carried out in two days by the cryogenics. In September, series of ramps were achieved up to 3 and finally 3.8T, while checking thoroughly the detectors in the forward region, measuring any movement of and around the HF. After the incident of the LHC accelerator on September 19th, corrective actions could be undertaken in the forward region. When all these displacements were fully characterized and repetitive, with no sign of increments in displacement at each field ramp, it was possible to start the CRAFT, Cosmic Run at Four Tesla (which was in fact at 3.8T). The magnet was ramped up to 18.16kA and the 3 week run went smoothly, with only 4 interruptions: due to the VIP visits on 21st October during the LHC inauguration day; a water leak on the cooling demineralized water circuit, about 1 l/min, that triggered a stop of the cooling pumps, and resulte...

  20. Magnetic

    Science.gov (United States)

    Aboud, Essam; El-Masry, Nabil; Qaddah, Atef; Alqahtani, Faisal; Moufti, Mohammed R. H.

    2015-06-01

    The Rahat volcanic field represents one of the widely distributed Cenozoic volcanic fields across the western regions of the Arabian Peninsula. Its human significance stems from the fact that its northern fringes, where the historical eruption of 1256 A.D. took place, are very close to the holy city of Al-Madinah Al-Monawarah. In the present work, we analyzed aeromagnetic data from the northern part of Rahat volcanic field as well as carried out a ground gravity survey. A joint interpretation and inversion of gravity and magnetic data were used to estimate the thickness of the lava flows, delineate the subsurface structures of the study area, and estimate the depth to basement using various geophysical methods, such as Tilt Derivative, Euler Deconvolution and 2D modeling inversion. Results indicated that the thickness of the lava flows in the study area ranges between 100 m (above Sea Level) at the eastern and western boundaries of Rahat Volcanic field and getting deeper at the middle as 300-500 m. It also showed that, major structural trend is in the NW direction (Red Sea trend) with some minor trends in EW direction.

  1. Comparison of the magnetic properties of GeMn thin films through Mn L-edge x-ray absorption

    Energy Technology Data Exchange (ETDEWEB)

    Ahlers, S.; Stone, P.R.; Sircar, N.; Arenholz, E.; Dubon, O. D.; Bougeard, D.

    2009-08-04

    X-ray absorption spectroscopy of epitaxial GeMn thin films reveals an experimentally indistinguishable electronic configuration of Mn atoms incorporated in Ge{sub 1?x}Mn{sub x} nanoclusters and in precipitates of the intermetallic compound Mn{sub 5}Ge{sub 3}, respectively. However, the average magnetic response of thin films containing Ge{sub 1?x}Mn{sub x} nanoclusters is lower than the response of films containing Mn{sub 5}Ge{sub 3} precipitates. This reduced magnetic response of Ge{sub 1?x}Mn{sub x} nanoclusters is explained in terms of a fraction of Mn atoms being magnetically inactive due to antiferromagnetic coupling or the presence of structural disorder. A determination of the role of magnetically inactive Mn atoms in the self-assembly of the thermodynamically metastable Ge{sub 1?x}Mn{sub x} nanoclusters seems to be an essential ingredient for an enhanced control of this promising high Curie temperature magnetic semiconductor.

  2. Pressurized polyol synthesis of Al-doped ZnO nanoclusters with high electrical conductivity and low near-infrared transmittance

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Ho-Nyun; Shin, Chi-Ho [Surface Technology R& BD Group, Korea Institute of Industrial Technology (KITECH), Incheon 406-840 (Korea, Republic of); Hwang, Duck Kun [Department of Corporate Diagnosis, Small and Medium Business Corporation, Seoul 150-718 (Korea, Republic of); Kim, Haekyoung [School of Materials Science and Engineering, Yeungnam University, Gyeongsan 712-749 (Korea, Republic of); Oh, Kyeongseok [Department of Chemical and Environmental Technology, Inha Technical College, Incheon 402-752 (Korea, Republic of); Kim, Hyun-Jong, E-mail: hjkim23@kitech.re.kr [Surface Technology R& BD Group, Korea Institute of Industrial Technology (KITECH), Incheon 406-840 (Korea, Republic of)

    2015-09-25

    Highlights: • Low-temperature pressurized polyol method synthesized Al-doped ZnO nanoclusters. • Reaction time affected the doping efficiency, resistivity, and NIR transmittance. • The near-IR blocking efficiency of Al-doped ZnO (AZO) nanoclusters reached 85%. • AZO nanocluster coatings could be used for heat reflectors or artificial glasses. - Abstract: In this study, a novel pressurized polyol method is proposed to synthesize aluminum-doped ZnO (AZO) nanoclusters without utilizing additional thermal treatment to avoid the merging of nanoclusters. The size of the AZO nanoclusters range from 100 to 150 nm with a resistivity of 204 Ω cm. The AZO nanoclusters primarily consist of approximately 10-nm nanocrystals that form a spherically clustered morphology. A two-stage growth model has been proposed based on the results of scanning electron microscopy and transmission electron microscopy images, nanocluster sizes, and X-ray diffraction patterns. The primary AZO nanocrystals first nucleate under pressurized conditions and then spontaneously aggregate into larger nanoclusters. Optically, the AZO nanoclusters exhibit a significant decrease in the near-infrared (NIR) transmittance compared to pure ZnO nanoparticles. The NIR blocking efficiency of AZO nanoclusters reached 85%. Moreover, the doping efficiency, resistivity, and NIR transmittance of AZO nanoclusters are influenced by the reaction time in the pressurized polyol solution. On the other hand, the reaction time has no effect on the particle size and crystallinity. An optically transparent coating for the AZO nanoclusters, which consisted of iso-propanol solvent and ultraviolet-curable acrylic binder, was also demonstrated.

  3. Stabilizing subnanometer Ag(0) nanoclusters by thiolate and diphosphine ligands and their crystal structures

    Science.gov (United States)

    Yang, Huayan; Wang, Yu; Zheng, Nanfeng

    2013-03-01

    The combined use of thiolate and diphosphine as surface ligands helps to stabilize subnanometer Ag(0) nanoclusters, resulting in the successful crystallization of two Ag(0)-containing nanoclusters (Ag16 and Ag32) for X-ray single crystal analysis. Both clusters have core-shell structures with Ag86+ and Ag2212+ as their cores, which are not simply either fragments of face-centered cubic metals or their five-fold twinned counterparts. The clusters display UV-Vis absorption spectra consisting of molecule-like optical transitions.The combined use of thiolate and diphosphine as surface ligands helps to stabilize subnanometer Ag(0) nanoclusters, resulting in the successful crystallization of two Ag(0)-containing nanoclusters (Ag16 and Ag32) for X-ray single crystal analysis. Both clusters have core-shell structures with Ag86+ and Ag2212+ as their cores, which are not simply either fragments of face-centered cubic metals or their five-fold twinned counterparts. The clusters display UV-Vis absorption spectra consisting of molecule-like optical transitions. Electronic supplementary information (ESI) available: Experimental details, more pictures of the structure and XPS spectra of the clusters. CCDC 916463 and 916464. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c3nr34328f

  4. Stabilizing Protein Effects on the Pressure Sensitivity of Fluorescent Gold Nanoclusters

    Science.gov (United States)

    2016-01-13

    and β-sheet structure present in the stabilizing protein. These data support the hypothesis that the pressure -induced fluorescence enhancement...ARL-TR-7572 ● JAN 2016 US Army Research Laboratory Stabilizing Protein Effects on the Pressure Sensitivity of Fluorescent Gold...JAN 2016 US Army Research Laboratory Stabilizing Protein Effects on the Pressure Sensitivity of Fluorescent Gold Nanoclusters by Abby

  5. Modular construction and hierarchical gelation of organooxotin nanoclusters derived from simple building blocks.

    Science.gov (United States)

    Hahn, Uwe; Hirst, Andrew R; Delgado, Juan Luis; Kaeser, Adrien; Delavaux-Nicot, Béatrice; Nierengarten, Jean-Francois; Smith, David K

    2007-12-14

    Mixtures of an appropriate carboxylic acid and n-butylstannoic acid constitute modular gelation systems, in which the formation of a well-defined 'tin-drum' nanocluster subsequently underpins the hierarchical assembly of nanostructured fibres, which form self-supporting gel-phase networks in organic solvents.

  6. High Selective Hydrogenation of Acetophenone Catalyzed by Alumina Supported Platinum Nanoclusters

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A new preparation and reduction method of γ-Al2O3 supported and PVP stabilized platinum nanoclusters was studied.The catalyst exhibited very high activity and selectivity for acetophenone hydrogenation in isopropanol-KOH solution at 25~60°C and P H2=1~5 MPa.

  7. Wavelength-switchable photocurrent in a hybrid TiO2-Ag nanocluster photoelectrode.

    Science.gov (United States)

    Chen, Hongjun; Wang, Qiong; Lyu, Miaoqiang; Zhang, Zhi; Wang, Lianzhou

    2015-08-04

    A hybrid TiO2-Ag nanocluster (NC) photoelectrode demonstrates unique wavelength-switchable photocurrent. By simply tuning the light wavelength from ultraviolet (UV) to visible light, the photocurrent generated on a single electrode can be switched from anodic to cathodic current, in which the Ag NCs behave like a new type of visible light active photocatalyst.

  8. Ge nanoclusters in PECVD-deposited glass caused only by heat treatment

    DEFF Research Database (Denmark)

    Ou, Haiyan; Rørdam, Troels Peter; Rottwitt, Karsten

    2008-01-01

    This paper reports the formation of Ge nanoclusters in a multi-layer structure consisting of alternating thin films of Ge-doped silica glass and SiGe, deposited by plasma-enhanced chemical vapor deposition (PECVD) and post annealed at 1100 °C in N2 atmosphere. We studied the annealed samples by t...

  9. Logic gates scheme based on Coulomb blockade in metallic nanoclusters with organic ligands

    Energy Technology Data Exchange (ETDEWEB)

    Cervera, Javier [Facultat de Fisica, Universitat de Valencia, E-46100 Burjassot (Spain); Ramirez, Patricio [Depto. de Fisica Aplicada, Universidad Politecnica de Valencia, E-46022 Valencia (Spain); Mafe, Salvador, E-mail: smafe@uv.e [Facultat de Fisica, Universitat de Valencia, E-46100 Burjassot (Spain)

    2010-01-11

    We propose a logic gates scheme based on the electron transfer through metallic nanoclusters linked to organic ligands and discuss theoretically the characteristics needed for practical implementation. As a proof-of-the-concept, we demonstrate the OR, AND and NOT gates and study the performance in terms of temperature, applied voltage, and noise.

  10. Self consistent tight binding molecular dynamics study of Ti02 nanoclusters in water.

    Energy Technology Data Exchange (ETDEWEB)

    Erdin, S.; Lin, Y.; Halley, J. W.; Zapol, P.; Redfern, P.; Curtiss, L.; Northern Illinois Univ.; Univ. of Minnesota

    2007-09-01

    Self-consistent tight binding molecular dynamics studies of TiO{sub 2}2 anatase and rutile nanoclusters in dissociable water are reported. It is found that the structure of the particle expands as a result of interaction between the particle's surface and water. Water molecules dissociate at the nanoparticle surface during simulation.

  11. Mechanistic insights from atomically precise gold nanocluster-catalyzed reduction of 4-nitrophenol

    Directory of Open Access Journals (Sweden)

    Shuo Zhao

    2016-10-01

    Full Text Available A trio of thiolate-protected atomically precise gold nanoclusters, [Au23(S-c-C6H1116]–, Au24(SCH2pHtBu20 and [Au25(SCH2CH2pH18]–, are utilized as catalysts for 4-nitrophenol (4-NP reduction to 4-aminophenol (4-AP. Despite nearly identical sizes (~1 nm, the three nanoclusters possess distinctly different atomic packing structures and surface ligand binding modes, which contribute to different catalytic performance. The [Au23(S-c-C6H1116]– nanocluster shows the highest activity with a kinetic rate constant of 0.0370 s−1, which is higher than those of Au24(SCH2pHtBu20 (0.0090 s−1 and [Au25(SCH2CH2pH18]– (0.0242 s−1. Such a trio of gold nanoclusters indicate that the atomic packing mode and electronic structure play a crucial role in determining their catalytic performance.

  12. Photophysical characterization of fluorescent metal nanoclusters sythesized using oligonucleotides, proteins and small reagent moleucles

    Energy Technology Data Exchange (ETDEWEB)

    Yeh, Hsin-chih [Los Alamos National Laboratory; Jaswinder, Sharma K [Los Alamos National Laboratory; Martinez, Jennifer S [Los Alamos National Laboratory; Werner, James H [Los Alamos National Laboratory; Yoo, Hyojong [Los Alamos National Laboratory

    2009-01-01

    The size transition from bulk metals to insulating nanoparticles and eventually to single atoms passes through the relatively unexplored few-atom nanocluster region. With climensions close to the Fermi wavelength, these nanoclusters demonstrate molecule-like properties distinct from bulk metals or atoms, such as discrete and size-tunable electronic transitions which lead to photoluminescence. Current research aims to elucidate the fundamental photophysical properties of the existing metal nanoclusters made by different means and based on different encapsulation agents. Here, we report the study of the photophysical properties, including quantum yields, lifetimes, extinction coefficients, blinking dynamics and sizes, of silver and gold nanoclusters synthesized using oligonucleotides, a protein (bovine serum albumin) and a Good's buffer molecule (MES, 2-(N-morpholino)ethanesulfonic acid) as encapsulation agents. We also investigate the change of photoluminescence under varying conditions (time, temperature and salt). Furthermore, it is demonstrated here that fluorescent metal clusters can be used as a donor in forming resonance energy transfer pairs with a commercial organic quenching dye.

  13. Biophysical mechanism for ras-nanocluster formation and signaling in plasma membrane.

    Directory of Open Access Journals (Sweden)

    Thomas Gurry

    Full Text Available Ras GTPases are lipid-anchored G proteins, which play a fundamental role in cell signaling processes. Electron micrographs of immunogold-labeled Ras have shown that membrane-bound Ras molecules segregate into nanocluster domains. Several models have been developed in attempts to obtain quantitative descriptions of nanocluster formation, but all have relied on assumptions such as a constant, expression-level independent ratio of Ras in clusters to Ras monomers (cluster/monomer ratio. However, this assumption is inconsistent with the law of mass action. Here, we present a biophysical model of Ras clustering based on short-range attraction and long-range repulsion between Ras molecules in the membrane. To test this model, we performed Monte Carlo simulations and compared statistical clustering properties with experimental data. We find that we can recover the experimentally-observed clustering across a range of Ras expression levels, without assuming a constant cluster/monomer ratio or the existence of lipid rafts. In addition, our model makes predictions about the signaling properties of Ras nanoclusters in support of the idea that Ras nanoclusters act as an analog-digital-analog converter for high fidelity signaling.

  14. Probing DNA-stabilized fluorescent silver nanocluster spectral heterogeneity by time-correlated single photon counting

    DEFF Research Database (Denmark)

    Carro, Miguel; Paolucci, Valentina; Hooley, Emma Nicole

    2016-01-01

    DNA-stabilized silver nanoclusters (DNA-AgNCs) are promising fluorophores whose photophysical properties and synthesis procedures have received increased attention in the literature. However, depending on the preparation conditions and the DNA sequence, the DNA-AgNC samples can host a range of di...

  15. Concentrated dispersions of equilibrium protein nanoclusters that reversibly dissociate into active monomers

    Science.gov (United States)

    Truskett, Thomas M.; Johnston, Keith; Maynard, Jennifer; Borwankar, Ameya; Miller, Maria; Wilson, Brian; Dinin, Aileen; Khan, Tarik; Kaczorowski, Kevin

    2012-02-01

    Stabilizing concentrated protein solutions is of wide interest in drug delivery. However, a major challenge is how to reliably formulate concentrated, low viscosity (i.e., syringeable) solutions of biologically active proteins. Unfortunately, proteins typically undergo irreversible aggregation at intermediate concentrations of 100-200 mg/ml. In this talk, I describe how they can effectively avoid these intermediate concentrations by reversibly assembling into nanoclusters. Nanocluster assembly is achieved by balancing short-ranged, cosolute-induced attractions with weak, longer-ranger electrostatic repulsions near the isoelectric point. Theory predicts that native proteins are stabilized by a self-crowding mechanism within the concentrated environment of the nanoclusters, while weak cluster-cluster interactions can result in colloidally-stable dispersions with moderate viscosities. I present experimental results where this strategy is used to create concentrated antibody dispersions (up to 260 mg/ml) comprising nanoclusters of proteins [monoclonal antibody 1B7, polyclonal sheep Immunoglobin G and bovine serum albumin], which upon dilution in vitro or administration in vivo, are conformationally stable and retain activity.

  16. Amine Reactivity with Nanoclusters of Sulfuric Acid and Ammonia

    Science.gov (United States)

    Johnston, M. V.; Bzdek, B. R.; DePalma, J.

    2011-12-01

    Alkyl amines have emerged as key species in new particle formation and growth. This interest is reinforced by ambient measurements of amines (e.g. Smith et al., 2010) and enhanced levels of nitrogen (e.g. Bzdek et al., 2011) during growth of newly formed particles. An important mechanism of amine uptake is aminium salt formation, either by substituting for ammonium ions that already exist in the particle or by opening new channels for salt formation that are not favorable with ammonia. This presentation will focus on recent experimental and computational work in our group to study amine uptake into charged nanoclusters of sulfuric acid and ammonia. In the experimental work, clusters are produced by electrospray of an ammonium sulfate solution and then drawn into a Fourier transform ion cyclotron resonance mass spectrometer where a specific cluster is isolated and exposed to amine vapor. We find that amine reactivity is dependent on the size, composition and charge of the isolated cluster. For small clusters of either polarity, all ammonium ions reside on the surface and amine substitution occurs with near unit reaction probability. As the cluster size increases, an ammonium ion can be encapsulated in the center of the cluster, which provides a steric hindrance to amine substitution. Negatively charged clusters are more likely to be acidic than positively charged clusters. For acidic clusters, incoming amine molecules first substitute for preexisting ammonium ions and then add to the cluster until a "neutralized" aminium bisulfate composition is reached. Computational studies of these clusters provide fundamental insight into the thermodynamics and kinetics of amine uptake.

  17. Reversible Size Control of Silver Nanoclusters via Ligand-exchange

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa

    2015-05-21

    The properties of atomically monodisperse noble metal nanoclusters (NCs) are intricately intertwined with their precise molecular formula. The vast majority of size-specific NC syntheses start from the reduction of the metal salt and thiol ligand mixture. Only in gold was it recently shown that ligand-exchange could induce the growth of NCs from one atomically precise species to another; a process of yet unknown reversibility. Here, we present a process for the ligand-exchange-induced growth of atomically precise silver NCs, in a biphasic liquid-liquid system, which is particularly of interest because of its complete reversibility and ability to occur at room temperature. We explore this phenomenon in-depth using Ag35(SG)18 [SG= glutathionate] and Ag44(4-FTP)30 [4-FTP= 4-fluorothiophenol] as model systems. We show that the ligand-exchange conversion of Ag35(SG)18 into Ag44(4-FTP)30 is rapid (< 5 min) and direct, while the reverse process proceeds slowly through intermediate cluster sizes. We adapt a recently developed theory of reverse Ostwald ripening to model the NCs’ interconvertibility. The model’s predictions are in good agreement with the experimental observations, and they highlight the importance of small changes in the ligand-metal binding energy in determining the final equilibrium NC size. Based on the insight provided by this model, we demonstrated experimentally that by varying the choice of ligands, ligand-exchange can be used to obtain different sized NCs. The findings in this work establish ligand-exchange as a versatile tool for tuning cluster sizes.

  18. Distinct metal-exchange pathways of doped Ag25 nanoclusters

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa

    2016-09-09

    Atomically precise metal nanoclusters (NCs) containing more than one type of metal atom (i.e., doped or alloyed), due to synergistic effects, open new avenues for engineering the catalytic and optical properties of NCs in a manner that homometal NCs cannot. Unfortunately, it is still a major challenge to controllably introduce multimetallic dopants in NCs, understanding the dopants\\' positions, mechanism, and synergistic effects. To overcome these challenges, we designed a metal-exchange approach involving NCs as molecular templates and metal ions as the source of the incoming dopant. In particular, two structurally similar monodoped silver-rich NCs, [MAg24(SR)(18)](2-) (M = Pd/Pt and SR: thiolate), were synthesized as templates to study their mechanistic transformation in response to the introduction of gold atoms. The controllable incorporation of Au atoms into the MAg24 framework facilitated the elucidation of distinct doping pathways through high-resolution mass spectrometry, optical spectroscopy and elemental analysis. Interestingly, gold replaced the central Pd atom of [PdAg24(SR)(18)](2-) clusters to produce predominantly bimetallic [AuAg24(SR)(18)](-) clusters along with a minor product of an [Au2Ag23(SR)(18)](-) cluster. In contrast, the central Pt atom remained intact in [PtAg24(SR)(18)](2-) clusters, and gold replaced the noncentral Ag atoms to form trimetallic [AuxPtAg24-x(SR)(18)](2-) NCs, where x = 1-2, with a portion of the starting [PtAg24(SR)(18)](2-) NCs remaining. This study reveals some of the unusual metal-exchange pathways of doped NCs and the important role played by the initial metal dopant in directing the position of a second dopant in the final product.

  19. A complementary palette of NanoCluster Beacons.

    Science.gov (United States)

    Obliosca, Judy M; Babin, Mark C; Liu, Cong; Liu, Yen-Liang; Chen, Yu-An; Batson, Robert A; Ganguly, Mainak; Petty, Jeffrey T; Yeh, Hsin-Chih

    2014-10-28

    NanoCluster Beacons (NCBs), which use few-atom DNA-templated silver clusters as reporters, are a type of activatable molecular probes that are low-cost and easy to prepare. While NCBs provide a high fluorescence enhancement ratio upon activation, their activation colors are currently limited. Here we report a simple method to design NCBs with complementary emission colors, creating a set of multicolor probes for homogeneous, separation-free detection. By systematically altering the position and the number of cytosines in the cluster-nucleation sequence, we have tuned the activation colors of NCBs to green (C8-8, 460 nm/555 nm); yellow (C5-5, 525 nm/585 nm); red (C3-4, 580 nm/635 nm); and near-infrared (C3-3, 645 nm/695 nm). At the same NCB concentration, the activated yellow NCB (C5-5) was found to be 1.3 times brighter than the traditional red NCB (C3-4). Three of the four colors (green, yellow, and red) were relatively spectrally pure. We also found that subtle changes in the linker sequence (down to the single-nucleotide level) could significantly alter the emission spectrum pattern of an NCB. When the length of linker sequences was increased, the emission peaks were found to migrate in a periodic fashion, suggesting short-range interactions between silver clusters and nucleobases. Size exclusion chromatography results indicated that the activated NCBs are more compact than their native duplex forms. Our findings demonstrate the unique photophysical properties and environmental sensitivities of few-atom DNA-templated silver clusters, which are not seen before in common organic dyes or luminescent crystals.

  20. Switching a Nanocluster Core from Hollow to Non-hollow

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa

    2016-03-24

    Modulating the structure-property relationship in atomically precise nanoclusters (NCs) is vital for developing novel NC materials and advancing their applications. While promising biphasic ligand-exchange (LE) strategies have been developed primarily to attain novel NCs, understanding the mechanistic aspects involved in tuning the core and the ligand-shell of NCs in such biphasic processes is challenging. Here, we design a single phase LE process that enabled us to elucidate the mechanism of how a hollow NC (e.g., [Ag44(SR)30]4-, -SR: thiolate) converts into a non-hollow NC (e.g., [Ag25(SR)18]-), and vice versa. Our study reveals that the complete LE of the hollow [Ag44(SPhF)30]4- NCs (–SPhF: 4-fluorobenzenethiolate) with incoming 2,4-dimethylbenzenethiol (HSPhMe2) induced distortions in the Ag44 structure forming the non-hollow [Ag25(SPhMe2)18]- by a disproportionation mechanism. While the reverse reaction of [Ag25(SPhMe2)18]- with HSPhF prompted an unusual dimerization of Ag25, followed by a rearrangement step that reproduces the original [Ag44(SPhF)30]4-. Remarkably, both the forward and the backward reactions proceed through similar size intermediates that seem to be governed by the boundary conditions set by the thermodynamic and electronic stability of the hollow and non-hollow metal cores. Furthermore, the resizing of NCs highlights the surprisingly long-range effect of the ligands which are felt by atoms far deep in the metal core, thus opening a new path for controlling the structural evolution of nanoparticles.

  1. Optical properties of II-VI semiconductor nanoclusters for use as phosphors

    Science.gov (United States)

    Wilcoxon, Jess P.; Newcomer, Paula

    2002-11-01

    The optical properties of both II-VI (direct gap) and type IV (indirect gap) nanosize semiconductors are significantly affected not only by their size, but by the nature of the chemical interface of the cluster with the embedding medium. This affects the light conversion efficiency and can alter the shape and position (i.e. the color) of the photoluminescence (PL). As the goal of our work is to embed nanoclusters into either organic or inorganic matrices for use as near UV, LED-excited phosphor thin films, understanding and controlling this interface is very important for preserving the high Q.E. of nanoclusters known for dilute solution conditions. We describe a room temperature synthesis of semiconductor nanoclusters which employs inexpensive, less toxic ionic precursors (metal salts), and simple coordinating solvents (e.g. tetrahydrofuran). This allows us to add passivating agents, ions, metal or semiconductor coatings to identical, highly dispersed bare clusters, post-synthesis. We can also increase the cluster size by heterogeneous growth on the seed nanoclusters. One of the most interesting observations for our II-VI nanomaterials is that both the absorbance excitonic features and the photoluminescence (PL) energy and intensity depend on the nature of the surface as well as the average size. In CdS, for example, the presence of electron traps (i.e Cd(II) sites) decreases the exciton absorbance peak amplitude but increases the PL nearly two-fold. Hole traps (i.e. S(II)) have the opposite effect. In the coordinating solvents used for the synthesis, the PL yield for d~2 nm, blue emitting CdSe clusters increases dramatically with sample age as the multiple absorbance features sharpen. Liquid chromatographic (LC) separation of the nanoclusters from other chemicals and different sized clusters is used to investigate the intrinsic optical properties of the purified clusters and identify which clusters are contributing most strongly to the PL. Both LC and dynamic

  2. Visualization of BRI1 and SERK3/BAK1 Nanoclusters in Arabidopsis Roots

    Science.gov (United States)

    van Esse, Wilma; Nolles, Antsje; Bücherl, Christoph A.; de Vries, Sacco C.; Hohlbein, Johannes; Borst, Jan Willem

    2017-01-01

    Brassinosteroids (BRs) are plant hormones that are perceived at the plasma membrane (PM) by the ligand binding receptor BRASSINOSTEROID-INSENSITIVE1 (BRI1) and the co-receptor SOMATIC EMBRYOGENESIS RECEPTOR LIKE KINASE 3/BRI1 ASSOCIATED KINASE 1 (SERK3/BAK1). To visualize BRI1-GFP and SERK3/BAK1-mCherry in the plane of the PM, variable-angle epifluorescence microscopy (VAEM) was employed, which allows selective illumination of a thin surface layer. VAEM revealed an inhomogeneous distribution of BRI1-GFP and SERK3/BAK1-mCherry at the PM, which we attribute to the presence of distinct nanoclusters. Neither the BRI1 nor the SERK3/BAK1 nanocluster density is affected by depletion of endogenous ligands or application of exogenous ligands. To reveal interacting populations of receptor complexes, we utilized selective-surface observation—fluorescence lifetime imaging microscopy (SSO-FLIM) for the detection of Förster resonance energy transfer (FRET). Using this approach, we observed hetero-oligomerisation of BRI1 and SERK3 in the nanoclusters, which did not change upon depletion of endogenous ligand or signal activation. Upon ligand application, however, the number of BRI1-SERK3 /BAK1 hetero-oligomers was reduced, possibly due to endocytosis of active signalling units of BRI1-SERK3/BAK1 residing in the PM. We propose that formation of nanoclusters in the plant PM is subjected to biophysical restraints, while the stoichiometry of receptors inside these nanoclusters is variable and important for signal transduction. PMID:28114413

  3. Homogeneously embedded Pt nanoclusters on amorphous titania matrix as highly efficient visible light active photocatalyst material

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Vipul; Kumar, Suneel; Krishnan, Venkata, E-mail: vkn@iitmandi.ac.in

    2016-08-15

    A novel and facile technique, based on colloidal synthesis route, has been utilized for the preparation of homogeneously embedded Pt nanoclusters on amorphous titania matrix. The material has been thoroughly characterized using high resolution transmission electron microscopy, energy dispersive x-ray analysis, powder x-ray diffraction, optical and Raman spectroscopic techniques to understand the morphology, structure and other physical characteristics. The photocatalytic activity of the material under visible light irradiation was demonstrated by investigations on the degradation of two organic dyes (methylene blue and rhodamine B). In comparison to other Pt−TiO{sub 2} based nanomaterials (core-shell, doped nanostructures, modified nanotubes, decorated nanospheres and binary nanocomposites), the embedded Pt nanoclusters on titania was found to be highly efficient for visible light active photocatalytic applications. The enhanced catalytic performance could be attributed to the efficient charge separation and decreased recombination of the photo generated electrons and holes at the Pt-titania interface and the availability of multiple metal-metal oxide interfaces due to homogeneous embedment of Pt nanoclusters on amorphous titania. In essence, this work illustrates that homogeneous embedment of noble metal nanoparticles/nanoclusters on semiconductor metal oxide matrices can lead to tuning of the photophysical properties of the final material and eventually enhance its photocatalytic activity. - Highlights: • Homogeneously embedded Pt nanoclusters on amorphous titania matrix has been prepared. • Facile low temperature colloidal synthesis technique has been used. • Enhanced catalytic performance could be observed. • Work can pave way for tuning photocatalytic activity of composite materials.

  4. Heterostructure of Au nanocluster tipping on a ZnS quantum rod: controlled synthesis and novel luminescence

    Science.gov (United States)

    Tian, Yang; Wang, Ligang; Yu, Shanshan; Zhou, Weiwei

    2015-08-01

    Heterostructures of metal nanoparticles and semiconductors are widely studied for their unique properties. However, few reports are available on the heterostructure of metal nanoclusters and semiconductors. In the present study, a heterostructure, in which gold nanoclusters selectively locate at ZnS quantum rod (QR) tips, was fabricated using a two-step solvothermal route. The composition, intrinsic crystallography, and junction of the prepared heterostructure were thoroughly investigated, and it was observed to exhibit novel luminescent behaviours. By comparison with the individual components of ZnS QRs and gold clusters, the resultant heterostructure shows an enhanced exciton emission and complete depression of defect emission for the ZnS component, and a pronounced red emission for the gold nanocluster component. The mechanism of these properties and the charge transfer between gold nanoclusters and ZnS QRs were also explored. The size and location of gold in the heterostructure were also controlled during synthesis to study their effects on the luminescence.

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

    Directory of Open Access Journals (Sweden)

    Hiroshi Yao

    2016-10-01

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

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

    Institute of Scientific and Technical Information of China (English)

    Hiroshi Yao

    2016-01-01

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

  7. IMS-MS and IMS-IMS investigation of the structure and stability of dimethylamine-sulfuric acid nanoclusters.

    Science.gov (United States)

    Ouyang, Hui; He, Siqin; Larriba-Andaluz, Carlos; Hogan, Christopher J

    2015-03-12

    Recent studies of new particle formation events in the atmosphere suggest that nanoclusters (i.e, the species formed during the early stages of particle growth which are composed of 10(1)-10(3) molecules) may consist of amines and sulfuric acid. The physicochemical properties of sub-10 nm amine-sulfuric acid clusters are hence of interest. In this work, we measure the density, thermostability, and extent of water uptake of dimethylamine-sulfuric (DMAS) nanoclusters in the gas phase, produced via positive electrospray ionization. Specifically, we employ three systems to investigate DMAS properties: ion mobility spectrometry (IMS, with a parallel-plate differential mobility analyzer) is coupled with mass spectrometry to measure masses and collision cross sections for dimethylamine to sulfuric acid originally present in the electrospray solution. IMS-IMS thermostability studies reveal that partial pressures of DMAS nanoclusters are dependent upon the electrospray solution concentration ratio, R = [H2SO4]/[(CH3)2NH]. Extrapolating measurements, we estimate that dry DMAS nanoclusters have surface vapor pressures of order 10(-4) Pa near 300 K, with the surface vapor pressure increasing with increasing values of R through most of the probed concentration range. This suggests that nanocluster surface vapor pressures are substantially enhanced by capillarity effects (the Kelvin effect). Meanwhile, IMS-IMS water uptake measurements show clearly that DMAS nanoclusters uptake water at relative humidities beyond 10% near 300 K, and that larger clusters uptake water to a larger extent. In total, our results suggest that dry DMAS nanoclusters (in the 5-8.5 nm size range in diameter) would not be stable under ambient conditions; however, DMAS nanoclusters would likely be hydrated in the ambient (in some cases above 20% water by mass), which could serve to reduce surface vapor pressures and stabilize them from dissociation.

  8. Inter-cluster distance dependence of electrical conduction in nanocluster assembled films of silver: a new paradigm for design of nanostructures

    OpenAIRE

    Bansal, Chandrahas; Praveen, S. G.; Kumaran, J. T. T.; Chatterjee, Ashok

    2015-01-01

    The transport properties of films assembled from metal nanoclusters can be significantly different from the metals in their bulk or thin film forms due to quantum confinement effects and several competing energy and length scales. For a film composed of metal nanoclusters as its building blocks, the cluster size and the inter-cluster separation are parameters that can be varied experimentally. Here we show that the electrical conductivity of a film composed of silver nanoclusters can be chang...

  9. Magnetic behavior in Cr2@Gen (1≤n≤12) clusters: A density functional investigation

    Science.gov (United States)

    Dhaka, Kapil; Trivedi, Ravi; Bandyopadhyay, Debashis

    2014-04-01

    With a goal to produce magnetic moment in Cr2 Doped Gen clusters which will be useful for practical applications, we have considered the structure and magnetic properties of Pure Germanium clusters and substitutionally doped it with Cr dimer to produce Cr2@Gen clusters. As the first step of calculation, geometrical optimizations of the nanoclusters have been done. These optimized geometries have been used in calculate the average binding energy per atom (BE), HOMO-LUMO gap and hence the relative stability of the clusters. These parameters have been demonstrated as structural and electronic properties of the clusters. Gap between highest occupied molecular orbital and lowest unoccupied molecular orbital indicate cluster to be a potential motif for generating magnetic cluster assembled materials. Based on these values a comparative study on different sized clusters has been done in order to understand the origin of structures, electronic and magnetic properties of Cr2@Gen nanoclusters.

  10. Improving Performance of InGaN/GaN Light-Emitting Diodes and GaAs Solar Cells Using Luminescent Gold Nanoclusters

    Directory of Open Access Journals (Sweden)

    M. D. Yang

    2009-01-01

    Full Text Available We studied the optoelectronic properties of the InGaN/GaN multiple-quantum-well light emitting diodes (LEDs and single-junction GaAs solar cells by introducing the luminescent Au nanoclusters. The electroluminescence intensity for InGaN/GaN LEDs increases after incorporation of the luminescent Au nanoclusters. An increase of 15.4% in energy conversion efficiency is obtained for the GaAs solar cells in which the luminescent Au nanoclusters have been incorporated. We suggest that the increased light coupling due to radiative scattering from nanoclusters is responsible for improving the performance of the LEDs and solar cells.

  11. Antibacterial silver nanocluster/silica composite coatings on stainless steel

    Science.gov (United States)

    Ferraris, M.; Perero, S.; Ferraris, S.; Miola, M.; Vernè, E.; Skoglund, S.; Blomberg, E.; Odnevall Wallinder, I.

    2017-02-01

    A coating made of silver nanocluster/silica composites has been deposited, via a radio frequency (RF) co-sputtering technique, for the first time onto stainless steel (AISI 304L) with the aim to improve its antibacterial properties. Different thermal treatments after coating deposition have been applied in order to optimize the coating adhesion, cohesion and its antibacterial properties. Its applicability has been investigated at realistic conditions in a cheese production plant. The physico-chemical characteristics of the coatings have been analyzed by means of different bulk and surface analytical techniques. Field emission scanning electron microscopy (FESEM), X-ray Photoelectron Spectroscopy (XPS), contact angle measurements and atomic force microscopy (AFM) were employed to assess coating morphology, composition, surface roughness, wetting properties, size and local distribution of the nanoparticles within the coating. Tape tests were used to determine the adhesion/cohesion properties of the coating. The amount and time-dependence of released silver in solutions of acetic acid, artificial water, artificial tap water and artificial milk were determined by means of Atomic Absorption Spectroscopy (AAS). The antibacterial effect of the coating was evaluated at different experimental conditions using a standard bacterial strain of Staphylococcus aureus in compliance with National Committee for Clinical Laboratory Standards (NCCLS) and AATCC 147 standards. The Ahearn test was performed to measure the adhesion of bacteria to the coated stainless steel surface compared with a control surface. The antibacterial coating retained its antibacterial activity after thermal treatment up to 450 °C and after soaking in common cleaning products for stainless steel surfaces used for e.g. food applications. The antibacterial capacity of the coating remained at high levels for 1-5 days, and showed a good capacity to reduce the adhesion of bacteria up to 30 days. Only a few

  12. Watermelon-like iron nanoparticles: Cr doping effect on magnetism and magnetization interaction reversal

    Energy Technology Data Exchange (ETDEWEB)

    Kaur, Maninder; Dai, Qilin; Bowden, Mark E.; Engelhard, Mark H.; Wu, Yaqiao; Tang, Jinke; Qiang, You

    2013-06-26

    Chromium (Cr) forms a solid solution with iron (Fe) lattice when doped in core-shell iron -iron oxide nanocluster (NC) and shows a mixed phase of sigma (σ) FeCr and bcc Fe. The Cr dopant affects heavily the magnetization and magnetic reversal process, and causes the hysteresis loop to shrink near the zero field axis. Dramatic transformation happens from dipolar interaction (0 at. % Cr) to strong exchange interaction (8 at. % of Cr) is confirmed from the Henkel plot and delta M plot, and is explained by a water-melon model of core-shell NC system.

  13. Order and phase nucleation in non-equilibrium nanocomposite Fe-Pt thin films with perpendicular magnetic anisotropy.

    Energy Technology Data Exchange (ETDEWEB)

    Clavero, C.; Skuza, J. R.; Garcia-Martin, J. M.; Cebollada, A.; Walko, D. A.; Lukaszew, R. A.; Coll. of William and Mary; Inst. de Microelectronica de Madrid

    2009-03-01

    We report on the time evolution of mass transport upon annealing nonequilibrium Fe-Pt nanocomposite films, leading to nucleation of L1{sub 0} chemically ordered phase. The nonequilibrium nanocomposite films were fabricated by applying Fe{sup +} ion implantation to epitaxial Pt films grown on (001) MgO substrates, yielding Fe nanoclusters embedded in a Pt matrix at a tailored penetration depth. Time-resolved x-ray diffraction studies were carried out using synchrotron radiation, allowing determination of the activation energy for nucleation of the FePt L1{sub 0} phase within the segregated nanoclusters during annealing. The growth of the segregated L1{sub 0} ordered phase was modeled using ideal grain-size law and found to be dominated by strain-driven surface nucleation. The activation energies were found to correlate with the nanocluster size. Magnetic characterization of selected annealed samples indicates perpendicular magnetic anisotropy with high coercive field coincident with high value of the chemical order parameter of the ordered phase within the magnetic nanoclusters.

  14. Argon Nanoclusters with Fivefold Symmetry in Supersonic Gas Jets and Superfluid Helium

    Science.gov (United States)

    Danylchenko, O. G.; Boltnev, R. E.; Khmelenko, V. V.; Kiryukhin, V.; Konotop, O. P.; Lee, D. M.; Krainyukova, N. V.

    2017-04-01

    In this study argon nanoclusters (800 to ˜ 6500 atoms) formed in supersonic gas jets are compared to the nanoclusters stabilized in superfluid helium. High-energy electron and X-ray diffraction methods are utilized. Both techniques allow investigation of isolated clusters. It is shown that the theoretical prediction of the so-called multiply twinned particles with fivefold symmetry, such as icosahedra (ico) and decahedra (dec) is valid in the investigated cluster size interval. Around the point of the expected ico-to-dec size-dependent transformation at a cluster size of ˜ 2000 atoms, hexagonal ico and the statistical distribution of structures with a tendency for dec to replace ico are observed. Kinetic reasons, as well as temperature-related effects, could be responsible for the latter observations.

  15. Purine-stabilized green fluorescent gold nanoclusters for cell nuclei imaging applications.

    Science.gov (United States)

    Venkatesh, V; Shukla, Akansha; Sivakumar, Sri; Verma, Sandeep

    2014-02-12

    We report facile one-pot synthesis of water-soluble green fluorescent gold nanoclusters (AuNCs), capped with 8-mercapto-9-propyladenine. The synthesized AuNCs were characterized by Fourier transform infrared (FTIR), powder X-ray diffraction (PXRD), transmission electron microscopy (TEM), (1)H NMR, and matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. These nanoclusters show high photostability and biocompatibility. We observed that AuNCs stain cell nuclei with high specificity, where the mechanism of AuNC uptake was established through pathway-specific uptake inhibitors. These studies revealed that cell internalization of AuNCs occurs via a macropinocytosis pathway.

  16. Mechanism of the formation of metal nanoclusters during pulsed laser deposition

    Energy Technology Data Exchange (ETDEWEB)

    Pushkin, M.A. [Moscow Engineering Physics Institute, 31 Kashirskoe chausse, 115409 Moscow (Russian Federation); Lebid' ko, V.V. [Moscow Engineering Physics Institute, 31 Kashirskoe chausse, 115409 Moscow (Russian Federation); Borman, V.D. [Moscow Engineering Physics Institute, 31 Kashirskoe chausse, 115409 Moscow (Russian Federation); Tronin, V.N. [Moscow Engineering Physics Institute, 31 Kashirskoe chausse, 115409 Moscow (Russian Federation); Troyan, V.I. [Moscow Engineering Physics Institute, 31 Kashirskoe chausse, 115409 Moscow (Russian Federation); Smurov, I. [Ecole Nationale d' Ingenieurs de Saint Etienne, 58 rue Jean Parot, 42023 St-Etienne (France)]. E-mail: smurov@enise.fr

    2006-04-30

    The geometrical structure of Au, Ni, Co and Cr nanoclusters self-assembled on NaCl and HOPG surfaces under pulsed laser deposition (PLD) has been experimentally investigated. The PLD technique is characterized by an extremely high instantaneous deposition rate. Unlike for the thermal evaporation (TE) process, formation of fractal nanoclusters under PLD conditions has been observed with scanning tunneling microscopy (STM). The driving mechanism for this phenomenon occurring at high deposition rate is thought to be the evolution of the initial interacting-adatom states in a system far from thermodynamic equilibrium. The obtained results can be explained by proposing a new mechanism of condensed phase formation under the conditions of strong deviation from thermodynamic equilibrium.

  17. Silver nanocluster/silica composite coatings obtained by sputtering for antibacterial applications

    Science.gov (United States)

    Ferraris, M.; Balagna, C.; Perero, S.; Miola, M.; Ferraris, S.; Baino, F.; Battiato, A.; Manfredotti, C.; Vittone, E.; Vernè, E.

    2012-09-01

    Silver nanocluster silica composite coatings were deposited by radio frequency co-sputtering technique on several substrates. This versatile method allows tailoring of silver content and antibacterial behaviour of coatings deposited on glasses, ceramics, metals and polymers for several applications. Coating morphology and composition as well as nanocluster size were analyzed by means of UV-Visible absorption, X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), electron dispersive spectroscopy (EDS), X-ray Photoelectron Spectroscopy (XPS) and Atomic Force Microscopy (AFM). The antibacterial effect was verified through the inhibition halo test against standard bacterial strain, Staphylococcus aureus, before and after sterilization process. Tape test demonstrated a good adhesion of the coatings to the substrates.

  18. Observation of gold sub-nanocluster nucleation within a crystalline protein cage

    Science.gov (United States)

    Maity, Basudev; Abe, Satoshi; Ueno, Takafumi

    2017-03-01

    Protein scaffolds provide unique metal coordination environments that promote biomineralization processes. It is expected that protein scaffolds can be developed to prepare inorganic nanomaterials with important biomedical and material applications. Despite many promising applications, it remains challenging to elucidate the detailed mechanisms of formation of metal nanoparticles in protein environments. In the present work, we describe a crystalline protein cage constructed by crosslinking treatment of a single crystal of apo-ferritin for structural characterization of the formation of sub-nanocluster with reduction reaction. The crystal structure analysis shows the gradual movement of the Au ions towards the centre of the three-fold symmetric channels of the protein cage to form a sub-nanocluster with accompanying significant conformational changes of the amino-acid residues bound to Au ions during the process. These results contribute to our understanding of metal core formation as well as interactions of the metal core with the protein environment.

  19. Preparation and characterization of Ni/Co bimetallic nano-clusters

    Institute of Scientific and Technical Information of China (English)

    Jinzhang Gao; Fei Guan; Yongjun Ma; Jingwan Kang

    2003-01-01

    Ni/Co bimetallic nano-cluters have been prepared from the aqueous solution by reducing their corresponding metal salts under suitable conditions. The experimental conditions including the type and concentration of protective agent, feeding order and the pH of the solution that influence the average particle size have been studied in detail. Transmission electron microscopy (TEM)indicates that the shape of those bimetallic nano-cluster particles is spheroid. The alloy structure has been shown by X-ray powder diffraction (XRD). The X-ray photoelectron spectroscopic (XPS) data have confirmed that the nickel and cobalt in the bimetallic nano-clusters are in the zero-valence state.

  20. Formation of aligned CrN nanoclusters in Cr-delta-doped GaN

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Y K; Kimura, S; Emura, S; Hasegawa, S; Asahi, H [Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan)], E-mail: zhou21@sanken.osaka-u.ac.jp

    2009-02-11

    Cr-delta-doped GaN layers were grown by radio-frequency plasma-assisted molecular-beam epitaxy on GaN template substrates. Cr flux was supplied without nitrogen flow during Cr-delta-doping. Cr incorporation into a narrow thin layer region was confirmed with the depth profile measured by secondary ion mass spectrometry. Structural properties and Cr atom alignments were studied with transmission electron microscopy. It was found that Cr-delta-doped GaN layers were coherently grown with Cr or CrGa nanoclusters in the delta-doped region for low temperature growth (350, 500 deg. C). It was also found that aligned CrN nanoclusters (approximately 5 nm vertical thickness) with NaCl-type structure were formed in the delta-doped region for the growth at 700 deg. C.

  1. Absorption Spectra of CuGaSe 2 and CuInSe 2 Semiconducting Nanoclusters

    KAUST Repository

    Mokkath, Junais Habeeb

    2015-10-01

    The structural and optical properties of the chalcopyrite CunGanSe2n and CunInnSe2n nanoclusters (n = 2, 4, 6, and 8) are investigated as a function of the size using a combination of basin-hopping global optimization and time-dependent density functional theory. Although the lowest energy structures are found to show almost random geometries, the band gaps and absorption spectra still are subject to systematic blue shifts for decreasing cluster size in the case of CunGanSe2n, indicating strong electron confinement. The applicability of the nanoclusters in photovoltaics is discussed. © 2015 American Chemical Society.

  2. Observation of gold sub-nanocluster nucleation within a crystalline protein cage

    Science.gov (United States)

    Maity, Basudev; Abe, Satoshi; Ueno, Takafumi

    2017-01-01

    Protein scaffolds provide unique metal coordination environments that promote biomineralization processes. It is expected that protein scaffolds can be developed to prepare inorganic nanomaterials with important biomedical and material applications. Despite many promising applications, it remains challenging to elucidate the detailed mechanisms of formation of metal nanoparticles in protein environments. In the present work, we describe a crystalline protein cage constructed by crosslinking treatment of a single crystal of apo-ferritin for structural characterization of the formation of sub-nanocluster with reduction reaction. The crystal structure analysis shows the gradual movement of the Au ions towards the centre of the three-fold symmetric channels of the protein cage to form a sub-nanocluster with accompanying significant conformational changes of the amino-acid residues bound to Au ions during the process. These results contribute to our understanding of metal core formation as well as interactions of the metal core with the protein environment. PMID:28300064

  3. Poly thymine stabilized copper nanoclusters as a fluorescence probe for melamine sensing.

    Science.gov (United States)

    Zhu, Hong-Wei; Dai, Wen-Xia; Yu, Xiao-Dong; Xu, Jing-Juan; Chen, Hong-Yuan

    2015-11-01

    In this work, poly-thymine stabilized copper nanoclusters have been used as a fluorescence probe for melamine sensing for the first time. Melamine can bind to thymine through hydrogen bond, which could dramatically enhance the fluorescence intensity of poly-thymine stabilized copper nanoclusters. The enhancement factors (I-I0)/I0 increase linearly with the lgCmelamine over the melamine concentration range of 0.1 µM to 6 µM. The detection limit of melamine is 95 nM, which is 200 times lower than the US Food and Drug Administration estimate melamine safety limit 20 µM. Melamine in milk was detected with good recovery, which suggested that this novel fluorescence probe has great potential in practical application.

  4. Papain-directed synthesis of luminescent gold nanoclusters and the sensitive detection of Cu2+.

    Science.gov (United States)

    Chen, Yang; Wang, Yan; Wang, Chuanxi; Li, Wenying; Zhou, Huipeng; Jiao, Huping; Lin, Quan; Yu, Cong

    2013-04-15

    Highly fluorescent papain stabilized gold nanoclusters (NCs) have been synthesized through a simple wet chemical route. Papain was used for the first time as an effective capping and reducing agent for these clusters. The optimal conditions for the synthesis of the gold nanoclusters, including the concentrations of papain and NaOH, reaction time and temperature, were investigated. The as-prepared Au clusters show intense red emission at ∼660nm (QY ∼4.3%) and are uniform in size. The clusters are quite stable and the intense red emission remained unchanged at a buffer pH range of 6-12. The fluorescent Au NCs were then used as a label-free probe for the sensitive detection of Cu(2+). A limit of detection of 3nM was obtained. The sensing strategy is also highly selective against the various potential interference ions.

  5. Synthesis, characterization, and growth simulations of Cu–Pt bimetallic nanoclusters

    Directory of Open Access Journals (Sweden)

    Subarna Khanal

    2014-08-01

    Full Text Available Highly monodispersed Cu–Pt bimetallic nanoclusters were synthesized by a facile synthesis approach. Analysis of transmission electron microscopy (TEM and spherical aberration (Cs-corrected scanning transmission electron microscopy (STEM images shows that the average diameter of the Cu–Pt nanoclusters is 3.0 ± 1.0 nm. The high angle annular dark field (HAADF-STEM images, intensity profiles, and energy dispersive X-ray spectroscopy (EDX line scans, allowed us to study the distribution of Cu and Pt with atomistic resolution, finding that Pt is embedded randomly in the Cu lattice. A novel simulation method is applied to study the growth mechanism, which shows the formation of alloy structures in good agreement with the experimental evidence. The findings give insight into the formation mechanism of the nanosized Cu–Pt bimetallic catalysts.

  6. Thermodynamic and magnetocaloric properties of geometrically frustrated Ising nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Žukovič, M., E-mail: milan.zukovic@upjs.sk

    2015-01-15

    Thermodynamic and magnetocaloric properties of geometrically frustrated Ising spin clusters of selected shapes and sizes are studied by exact enumeration. In the ground state the magnetization and the entropy show step-wise variations with an applied magnetic field. The number of steps, their widths and heights depend on the cluster shape and size. While the character of the magnetization plateau heights is always increasing, the entropy is not necessarily decreasing function of the field, as one would expect. For selected clusters showing some interesting ground-state properties, the calculations are extended to finite temperatures by exact enumeration of densities of states in the energy-magnetization space. In zero field the focus is laid on a peculiar behavior of some thermodynamic quantities, such as the entropy, the specific heat and the magnetic susceptibility. In finite fields various thermodynamic functions are studied in the temperature-field parameter plane and particular attention is paid to the cases showing an enhanced magnetocaloric effect. The exact results on the finite clusters are compared with the thermodynamic limit behavior obtained from Monte Carlo simulations. - Highlights: • We study frustrated spin clusters of various shapes and sizes on a triangular lattice. • Ground-state magnetizations and entropies in a field are exactly determined. • Peculiar behavior of some quantities is studied in zero field and finite temperatures. • Enhanced magnetocaloric effect is observed at relatively low temperatures and fields. • Thermodynamic limit behavior is estimated by Monte Carlo simulations.

  7. On the Evolution from Non-Plasmonic Metal Nanoclusters to Plasmonic Nanocrystals

    Science.gov (United States)

    2014-09-24

    OF PAGES 19a. NAME OF RESPONSIBLE PERSON a. REPORT b. ABSTRACT c. THIS PAGE 19b. TELEPHONE NUMBER (include area code ) Standard...structures as well as for thiol binding on extended gold surfaces in self-assembled-monolayer (SAM) systems. Figure 1. Total structure of Au36( SPh ...thiolate ligands (Fig. 2). Remarkably, the Au133(SR)52 nanocluster (where, R = SPh -p-But) exhibits aesthetic orderings in structure from the gold kernel

  8. Light-Emitting Diodes: Phosphorescent Nanocluster Light-Emitting Diodes (Adv. Mater. 2/2016).

    Science.gov (United States)

    Kuttipillai, Padmanaban S; Zhao, Yimu; Traverse, Christopher J; Staples, Richard J; Levine, Benjamin G; Lunt, Richard R

    2016-01-13

    On page 320, R. R. Lunt and co-workers demonstrate electroluminescence from earth-abundant phosphorescent metal halide nanoclusters. These inorganic emitters, which exhibit rich photophysics combined with a high phosphorescence quantum yield, are employed in red and near-infrared light-emitting diodes, providing a new platform of phosphorescent emitters for low-cost and high-performance light-emission applications.

  9. Molecular dynamics simulation study of the melting of Pd-Pt nanoclusters

    Science.gov (United States)

    Sankaranarayanan, Subramanian K. R. S.; Bhethanabotla, Venkat R.; Joseph, Babu

    2005-05-01

    Bimetallic nanoclusters are of interest because of their utility in catalysis and sensors. The thermal characteristics of bimetallic Pt-Pd nanoclusters of different sizes and compositions were investigated through molecular dynamics simulations using quantum Sutton-Chen (QSC) many-body potentials. Monte Carlo simulations employing the bond order simulation model were used to generate minimum energy configurations, which were utilized as the starting point for molecular dynamics simulations. The calculated initial configurations of the Pt-Pd system consisted of surface segregated Pd atoms and a Pt-rich core. Melting characteristics were studied by following the changes in potential energy and heat capacity as functions of temperature. Structural changes accompanying the thermal evolution were studied by the bond order parameter method. The Pt-Pd clusters exhibited a two-stage melting: surface melting of the external Pd atoms followed by homogeneous melting of the Pt core. These transitions were found to depend on the composition and size of the nanocluster. Melting temperatures of the nanoclusters were found to be much lower than those of bulk Pt and Pd. Bulk melting temperatures of Pd and Pt simulated using periodic boundary conditions compare well with experimental values, thus providing justification for the use of QSC potentials in these simulations. Deformation parameters were calculated to characterize the structural evolution resulting from diffusion of Pd and Pt atoms. The results indicate that in Pd-Pt clusters, Pd atoms prefer to remain at the surface even after melting. In addition, Pt also tends to diffuse to the surface after melting due to reduction of its surface energy with temperature. This mixing pattern is different from those reported in some of the earlier studies on melting of bimetallics.

  10. Physical characteristics and optical properties of PbS nanoclusters: DFT simulation and experimental study

    Science.gov (United States)

    Dong, Yanhua; Wen, Jianxiang; Sun, Xiaolan; Shang, Yana; Wang, Tingyun

    2015-08-01

    The physical characteristics and optical properties of PbS nanoclusters are investigated by using density functional theory (DFT) of first-principles. Microstructure models of (PbS)n (n=1-9) nanoclusters and bulk materials are built on Materials Studio platform, and its energy band structures, highest occupied molecular orbital-lowest unoccupied molecular orbital gap (HOMO-LUMO gap), density of state (DOS), and optical properties are calculated, respectively. Compared to PbS bulk materials, PbS nanoclusters show a discrete energy gap as well as the DOS, because of the quantum confinement effect. It is interesting that the HOMO-LUMO gap of (PbS)n (n=1-9) shows oscillates with the increasing of the n number. However, when its size is large enough, the HOMO-LUMO gap is gradually decrease with the increasing of size (>27 atoms). And, the HOMO-LUMO gap of PbS nanoclusters of different sizes is range from 2.575 to 0.58 eV, which covers the low loss communication band of optical communication. In addition, PbS nanomaterials (NMs) with small size are synthesized by using oleylamine as ligands. Sizes of PbS NMs can be accurately controlled through control of the reaction time as well as the growth temperature. The photoluminescence (PL) spectra show strong size dependence, which is large red shift with increasing size of the NMs. This trend is basically in agreement with the theoretical calculation above. Moreover, transmission electron microscopy (TEM) further reveals the morphology of PbS NMs. PbS NMs can be used in optical fiber amplifiers and fiber lasers because of its unique optical properties in optical communication bands.

  11. Simulation of Structure and Energies of NinAlm Nanoclusters (n + m = 13) by Molecular Dynamics

    OpenAIRE

    Rojas T., Justo; Departamento de Física, Instituto Peruano de Energía Nuclear. Lima, Perú Facultad de Ciencias Físicas, Universidad Nacional Mayor de San Marcos. Lima, Perú; Rojas A., Chachi; Facultad de Ciencias Físicas, Universidad Nacional Mayor de San Marcos. Lima, Perú; Arroyo C., Juan; Facultad de Química e Ingeniería Química, Universidad Nacional Mayor de San Marcos. Lima, Perú

    2014-01-01

    By simulation with the Molecular Dynamics method and the thermal temper technique, the more stablegeometric structures and their respective energy were determined in the Nin Alm (n + m = 13)nanoclusters. The atomic interaction in the cluster was modelized with the Embeded Atom Method (EAM)(the Voter & Chen version). The most stable geometric structures of the cluster and their minimal energywere obtained from 200 generating spatial coordinates along the high energy path. The initial inter...

  12. Green synthesis of peptide-templated fluorescent copper nanoclusters for temperature sensing and cellular imaging.

    Science.gov (United States)

    Huang, Hong; Li, Hua; Wang, Ai-Jun; Zhong, Shu-Xian; Fang, Ke-Ming; Feng, Jiu-Ju

    2014-12-21

    A simple and green approach was developed for the preparation of fluorescent Cu nanoclusters (NCs) using the artificial peptide CLEDNN as a template. The as-synthesized Cu NCs exhibited a high fluorescence quantum yield (7.3%) and good stability, along with excitation and temperature dependent fluorescent properties, which could be employed for temperature sensing. Further investigations demonstrated low toxicity of Cu NCs for cellular imaging.

  13. Regulation of EGFR nanocluster formation by ionic protein-lipid interaction

    OpenAIRE

    2014-01-01

    The abnormal activation of epidermal growth factor receptor (EGFR) is strongly associated with a variety of human cancers but the underlying molecular mechanism is not fully understood. By using direct stochastic optical reconstruction microscopy (dSTORM), we find that EGFR proteins form nanoclusters in the cell membrane of both normal lung epithelial cells and lung cancer cells, but the number and size of clusters significantly increase in lung cancer cells. The formation of EGFR clusters is...

  14. Structural Evolution of Core-Shell Gold Nanoclusters: Aun(-) (n = 42-50).

    Science.gov (United States)

    Pande, Seema; Huang, Wei; Shao, Nan; Wang, Lei-Ming; Khetrapal, Navneet; Mei, Wai-Ning; Jian, Tian; Wang, Lai-Sheng; Zeng, Xiao Cheng

    2016-11-22

    Gold nanoclusters have attracted great attention in the past decade due to their remarkable size-dependent electronic, optical, and catalytic properties. However, the structures of large gold clusters are still not well-known because of the challenges in global structural searches. Here we report a joint photoelectron spectroscopy (PES) and theoretical study of the structural evolution of negatively charged core-shell gold nanoclusters (Aun(-)) for n = 42-50. Photoelectron spectra of size-selected Aun(-) clusters are well resolved with distinct spectral features, suggesting a dominating structural type. The combined PES data and density functional calculations allow us to systematically identify the global minimum or candidates of the global minima of these relatively large gold nanoclusters, which are found to possess low-symmetry structures with gradually increasing core sizes. Remarkably, the four-atom tetrahedral core, observed first in Au33(-), continues to be highly robust and is even present in clusters as large as Au42(-). Starting from Au43(-), a five-atom trigonal bipyramidal core appears and persists until Au47(-). Au48(-) possesses a six-atom core, while Au49(-) and Au50(-) feature seven- and eight-atom cores, respectively. Notably, both Au46(-) and Au47(-) contain a pyramidal Au20 motif, which is stacked with another truncated pyramid by sharing a common 10-atom triangular face. The present study sheds light on our understanding of the structural evolution of the medium-sized gold nanoclusters, the shells and core as well as how the core-shell structures may start to embrace the golden pyramid (bulk-like) fragment.

  15. A new strategy for specific imaging of neural cells based on peptide-conjugated gold nanoclusters

    Directory of Open Access Journals (Sweden)

    Zhang E

    2015-03-01

    Full Text Available Enqi Zhang, Ailing Fu School of Pharmaceutical Sciences, Southwest University, Chongqing, People’s Republic of China Abstract: Despite the significant progress in molecular imaging technologies that has been made in recent years, the specific detection of neural cells still remains challenging. Here, we suggest the use of gold nanoclusters (AuNCs modified with a brain-targeting peptide as a potential imaging candidate for detecting neural cells in vitro and in mice. AuNCs of less than 10 nm (dynamic light scattering analysis were first prepared using the “green” synthetic approach, and then a targeting peptide, rabies virus glycoprotein derived peptide (RDP, was conjugated to the AuNCs for improving the efficiency and specificity of neural cell penetration. The conjugate’s mechanism of cellular attachment and entry into neural cells was suggested to be receptor-mediated endocytosis through clathrin-coated pits. Also, noninvasive imaging analysis and animal studies indicated that the RDP-modified nanoclusters could concentrate in the brain and locate in neural cells. This study suggests the feasibility of using targeting peptide-modified nanoclusters for noninvasive imaging brain cells in vivo. Keywords: RDP, targeted delivery, bioimaging, brain 

  16. Spontaneous assembly of perfectly ordered identical-size nanocluster arrays: The theory

    Science.gov (United States)

    Zhang, S. B.; Xue, Qi-Kun

    2002-03-01

    Ordered nanocluster array is a new form of condensed matter that provides unprecedented opportunities for exploring the law of physics that nature rarely provides. It has important immediate applications such as in microelectronics, ultra-high-density recording, and nanocatalysis. Despite many years of intensive studies, however, epitaxial growth of uniform size perfectly ordered nanocluster arrays is prohibited difficult. Recently, Li et al. [1] reported a discovery where Si (111)-7x7 surface can be used to induce size selection and two-dimension ordering. This opens up a new road towards high-quality nanocluster crystals. Interestingly, indium clusters appear to be loosely packed, occupy only half of the 7x7 cell, and the STM images have unusually strong bias voltage dependence. First-principles calculations elucidate the cluster structure, the ordering and size selectivity mechanism, and provide solid foundation for the experiment. This work was supported by the U. S. DOE-SC-BES under contract No. DE-AC36-99GO10337. [1] Li, et al. Phys. Rev. Lett. (in press).

  17. LOW TEMPERATURE OPTICAL PROPERTIES OF AMORPHOUS OXIDE NANOCLUSTERS IN POLYMETHYL METHACRYLATE MATRIX

    Institute of Scientific and Technical Information of China (English)

    V. V. VOLKOV; WANG ZHONG-LIN; Zou BING-SUO; XIE SI-SHEN

    2000-01-01

    We studied the temperature-dependent steady-state and time-resolved fluorescence properties of very small (1-2 nm) ZnO, CdO, and PbO amorphous nanoclusters prepared in AOT reverse micelles and imbedded in polymethyl methacrylate(PMMA) films. X-ray diffraction and electron diffraction and imaging indicate that these structures are amorphous. These amorphous oxide nanoclusters demonstrate similar structural, electronic, and optical properties. Properties of steady-state fluorescence spectra indicate the unique localization of electronic states due to the amorphous structure. ZnO and CdO show double-band fluorescence structure, which is due to the spin-orbital splitting, similar to Cu2O. Time-resolved fluorescence studies of the nanoclusters in the polymer reveal two lifetime components, as found in solution. The slow component reflects relaxation processes from band-tail states while the fast component may be related to high-lying extended states. The temperature dependence of fast fluorescence component reveals the presence of exciton hopping between anharmonic wells at temperatures higher than 200K. We correlate the barrier height between two wells formed around local atoms with the inter-atomic distance and bond ionicity.

  18. Size-selective synthesis of immobilized copper oxide nanoclusters on silica

    Energy Technology Data Exchange (ETDEWEB)

    Lomnicki, Slawo M., E-mail: slomni1@lsu.edu [Louisiana State University, Department of Chemistry, 232 Choppin Hall, Baton Rouge, LA 70803-1804 (United States); Wu, Hongyi; Osborne, Scott N.; Pruett, Jeff M.; McCarley, Robin L.; Poliakoff, Erwin; Dellinger, Barry [Louisiana State University, Department of Chemistry, 232 Choppin Hall, Baton Rouge, LA 70803-1804 (United States)

    2010-11-25

    We report a straightforward route for preparing bulk quantities of size-controlled and low size dispersity copper oxide nanoclusters on amorphous silica. Adsorption of the copper-dendrimer complex on the silica surface minimizes aggregation, which results in previously unachieved low size dispersity of the nanoclusters. Copper oxide nanoclusters with mean diameters of 1-5 nm with size dispersities of only 8-15% were prepared by calcination of silica impregnated with Cu(II)-poly(propylene imine) dendrimer complexes of varying stoichiometry. The size and size distribution of the copper oxide nanoparticles are tunably controlled by the ratio of the Cu(II) to the terminal primary amines in the copper-dendrimer complex, DAB-Am{sub n}-Cu(II){sub x}, the surface coverage of the DAB-Am{sub n}-Cu(II){sub x}, and the impregnation procedure. This method is anticipated to be useful in the preparation of other metal oxide nanoparticles, e.g., Ni and Fe, and with other oxide substrates.

  19. Size-selective synthesis of immobilized copper oxide nanoclusters on silica.

    Science.gov (United States)

    Lomnicki, Slawo M; Wu, Hongyi; Osborne, Scott N; Pruett, Jeff M; McCarley, Robin L; Poliakoff, Erwin; Dellinger, Barry

    2010-11-25

    We report a straightforward route for preparing bulk quantities of size-controlled and low size dispersity copper oxide nanoclusters on amorphous silica. Adsorption of the copper-dendrimer complex on the silica surface minimizes aggregation, which results in previously unachieved low size dispersity of the nanoclusters. Copper oxide nanoclusters with mean diameters of 1-5 nm with size dispersities of only 8-15% were prepared by calcination of silica impregnated with Cu(II)-poly(propylene imine) dendrimer complexes of varying stoichiometry. The size and size distribution of the copper oxide nanoparticles are tunably controlled by the ratio of the Cu(II) to the terminal primary amines in the copper-dendrimer complex, DAB-Am n -Cu(II) x , the surface coverage of the DAB-Am n -Cu(II) x , and the impregnation procedure. This method is anticipated to be useful in the preparation of other metal oxide nanoparticles, e.g., Ni and Fe, and with other oxide substrates.

  20. In-situ Study of Nanostructure and Electrical Resistance of Nanocluster Films Irradiated with Ion Beams

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Weilin; Sundararajan, Jennifer A.; Varga, Tamas; Bowden, Mark E.; Qiang, You; McCloy, John S.; Henager, Charles H.; Montgomery, Robert O.

    2014-08-11

    An in-situ study is reported on the structural evolution in nanocluster films under He+ ion irradiation using an advanced helium ion microscope. The films consist of loosely interconnected nanoclusters of magnetite or iron-magnetite (Fe-Fe3O4) core-shells. The nanostructure is observed to undergo dramatic changes under ion-beam irradiation, featuring grain growth, phase transition, particle aggregation, and formation of nanowire-like network and nano-pores. Studies based on ion irradiation, thermal annealing and election irradiation have indicated that the major structural evolution is activated by elastic nuclear collisions, while both electronic and thermal processes can play a significant role once the evolution starts. The electrical resistance of the Fe-Fe3O4 films measured in situ exhibits a super-exponential decay with dose. The behavior suggests that the nanocluster films possess an intrinsic merit for development of an advanced online monitor for neutron radiation with both high detection sensitivity and long-term applicability, which can enhance safety measures in many nuclear operations.

  1. The fourth crystallographic closest packing unveiled in the gold nanocluster crystal

    Science.gov (United States)

    Gan, Zibao; Chen, Jishi; Wang, Juan; Wang, Chengming; Li, Man-Bo; Yao, Chuanhao; Zhuang, Shengli; Xu, An; Li, Lingling; Wu, Zhikun

    2017-03-01

    Metal nanoclusters have recently attracted extensive interest not only for fundamental scientific research, but also for practical applications. For fundamental scientific research, it is of major importance to explore the internal structure and crystallographic arrangement. Herein, we synthesize a gold nanocluster whose composition is determined to be Au60S6(SCH2Ph)36 by using electrospray ionization mass spectrometry and single crystal X-ray crystallography (SCXC). SCXC also reveals that Au60S6(SCH2Ph)36 consists of a fcc-like Au20 kernel protected by a pair of giant Au20S3(SCH2Ph)18 staple motifs, which contain 6 tetrahedral-coordinate μ4-S atoms not previously reported in the Au-S interface. Importantly, the fourth crystallographic closest-packed pattern, termed 6H left-handed helical (6HLH) arrangement, which results in the distinct loss of solid photoluminescence of amorphous Au60S6(SCH2Ph)36, is found in the crystals of Au60S6(SCH2Ph)36. The solvent-polarity-dependent solution photoluminescence is also demonstrated. Overall, this work provides important insights about the structure, Au-S bonding and solid photoluminescence of gold nanoclusters.

  2. Trends in the adsorption and reactivity of hydrogen on magnesium silicate nanoclusters.

    Science.gov (United States)

    Oueslati, Ichraf; Kerkeni, Boutheïna; Bromley, Stefan T

    2015-04-14

    We study nanoclusters of Mg-rich olivine and pyroxene (having (MgO)6(SiO2)3 and (MgO)4(SiO2)4 compositions) with respect to their reactivity towards hydrogen atoms, using density functional calculations. Ultrasmall silicate particles are fundamental intermediates in cosmic dust grain formation and processing, and are thought to make up a significant mass fraction of the grain population. Due to their nanoscale dimensions and high surface area to bulk ratios, they are likely to also have a disproportionately large influence on surface chemistry in the interstellar medium. This work investigates the potential role of silicate nanoclusters in vital interstellar hydrogen-based chemistry by studying atomic H adsorption and H2 formation. Our extensive set of calculations confirm the generality of a Brønsted-Evans-Polanyi (BEP) relation between the H2 reaction barrier and the 2Hchem binding energy, suggesting it to be independent of silicate dust grain shape, size, crystallinity and composition. Our results also suggest that amorphous/porous grains with forsteritic composition would tend to dissociate H2, but relatively Mg-poor silicate grains (e.g. enstatite composition) and/or more crystalline/compact silicate grains would tend to catalyse H2 formation. The high structural thermostability of silicate nanoclusters with respect to the heat released during exothermic H2 formation reactions is also verified.

  3. First-principles calculated decomposition pathways for LiBH4 nanoclusters

    Science.gov (United States)

    Huang, Zhi-Quan; Chen, Wei-Chih; Chuang, Feng-Chuan; Majzoub, Eric H.; Ozoliņš, Vidvuds

    2016-05-01

    We analyze thermodynamic stability and decomposition pathways of LiBH4 nanoclusters using grand-canonical free-energy minimization based on total energies and vibrational frequencies obtained from density-functional theory (DFT) calculations. We consider (LiBH4)n nanoclusters with n = 2 to 12 as reactants, while the possible products include (Li)n, (B)n, (LiB)n, (LiH)n, and Li2BnHn; off-stoichiometric LinBnHm (m ≤ 4n) clusters were considered for n = 2, 3, and 6. Cluster ground-state configurations have been predicted using prototype electrostatic ground-state (PEGS) and genetic algorithm (GA) based structural optimizations. Free-energy calculations show hydrogen release pathways markedly differ from those in bulk LiBH4. While experiments have found that the bulk material decomposes into LiH and B, with Li2B12H12 as a kinetically inhibited intermediate phase, (LiBH4)n nanoclusters with n ≤ 12 are predicted to decompose into mixed LinBn clusters via a series of intermediate clusters of LinBnHm (m ≤ 4n). The calculated pressure-composition isotherms and temperature-pressure isobars exhibit sloping plateaus due to finite size effects on reaction thermodynamics. Generally, decomposition temperatures of free-standing clusters are found to increase with decreasing cluster size due to thermodynamic destabilization of reaction products.

  4. Kinetic growth mechanisms of sputter-deposited Au films on mica: from nanoclusters to nanostructured microclusters

    Energy Technology Data Exchange (ETDEWEB)

    Ruffino, F.; Grimaldi, M.G. [Universita di Catania, Dipartimento di Fisica e Astronomia, Catania (Italy); CNR-IMM MATIS, Catania (Italy); Torrisi, V.; Marletta, G. [University of Catania and CSGI, Laboratory for Molecular Surface and Nanotechnology (LAMSUN), Department of Chemical Sciences, Catania (Italy)

    2010-07-15

    Au nanostructured film was deposited on mica by room temperature RF sputtering. The growth mechanism of the film was studied analyzing the evolution of the film morphology as a function of its thickness by the atomic force microscopy. In the early stages of a growth the film evolution proceeds by the nucleation and growth of nanoclusters. After a critical thickness the growth of microclusters formed by the joining of nanoclusters in preferential nucleation sites, onto a quasicontinuous film, is observed. We quantified the evolution of the mean nanoclusters height and surface density and of the film roughness. This data were analyzed by the dynamic scaling theory of growing interfaces obtaining the scaling and roughness exponents z and {beta} whose values suggest a conservative growth process. We also quantified the growth of the microclusters showing that it is consistent with a coalescence/impingement dynamic. About the formation of the microclusters, furthermore, we speculate that their origin is strongly correlated to the features of the sputtering technique in connection with the deposition on a high-diffusivity substrate. (orig.)

  5. Enhanced electronic injection in organic light-emitting diodes by incorporating silver nanoclusters and cesium carbonate

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Ying-Chung; Gao, Chia-Yuan [Department of Electrical Engineering, National Sun Yat-Sen University, Kaohsiung, Taiwan (China); Chen, Kan-Lin [Department of Electronic Engineering, Fortune Institute of Technology, Kaohsiung, Taiwan (China); Sze, Po-Wen [Department of Electro-Optical Science and Engineering, Kao Yuan University, Kaohsiung, Taiwan (China); Huang, Chien-Jung, E-mail: chien@nuk.edu.tw [Department of Applied Physics, National University of Kaohsiung, Kaohsiung, Taiwan (China)

    2015-10-01

    Highlights: • The localized electric field around SNCs is enhanced. • When the cesium carbonate/silver nanoclusters/cesium carbonate electron-injection structure replaces the cesium carbonate electron-injection structure, higher electron-injection ability is obtained. • The structure for efficient electron injection is critical to characteristics of the device. - Abstract: The influence of the cesium carbonate/silver nanoclusters/cesium carbonate electron-injection structure (CSC-EIS) on the performance of organic light-emitting diodes is investigated in this study. The silver nanoclusters (SNCs) are introduced between the electron-injection layers by means of thermal evaporation. When the CSC-EIS replaces the cesium carbonate electron-injection structure, higher electron-injection ability is obtained because the electron-injection barrier between the cathode and the electron-transport layer is remarkably reduced from 1.2 to 0 eV. In addition, surface plasmon resonance effect will cause the enhanced localized electric field around the SNCs, resulting that electron-injection ability is further enhanced from the cathode to the emitting layer.

  6. Structural and optical properties of the naked and passivated Al5Au5 bimetallic nanoclusters

    Science.gov (United States)

    Grande-Aztatzi, Rafael; Formoso, Elena; Mercero, Jose M.; Matxain, Jon M.; Grabowski, Slawomir J.; Ugalde, Jesus M.

    2016-03-01

    The structural and optical properties of both the naked and passivated bimetallic Al5Au5 nanoclusters have been analyzed based on data obtained from ab initio density functional theory and quantum molecular dynamics simulations. It has been found that the Al5Au5 nanocluster possesses a hollow shaped minimum energy structure with segregated Al and Au layered domains, the former representing the electrophilic domain and the latter the nucleophilic domain. In particular, it has been shown that alkali metal cations attach in the nucleophilic domain and hop from one Au site to the next one in the picoseconds time scale, while anions are bound tightly to the Al atoms of the electrophilic domain. Simulating annealing studies are very suggestive of the proneness of the nanocluster towards coalescence into large cluster units, when the cluster is left unprotected by appropriate ligands. Further passivation studies with NaF salt suggest, nonetheless, the possibility of the isolation of the Al5Au5 cluster in molten salts or ionic liquids.

  7. Nanoclusters as a new family of high temperature superconductors (Conference Presentation)

    Science.gov (United States)

    Halder, Avik; Kresin, Vitaly V.

    2017-03-01

    Electrons in metal clusters organize into quantum shells, akin to atomic shells in the periodic table. Such nanoparticles are referred to as "superatoms". The electronic shell levels are highly degenerate giving rise to sharp peaks in the density of states, which can enable exceptionally strong electron pairing in certain clusters containing tens to hundreds of atoms. A spectroscopic investigation of size - resolved aluminum nanoclusters has revealed a sharp rise in the density of states near the Fermi level as the temperature decreases towards 100 K. The effect is especially prominent in the closed-shell "magic" cluster Al66 [1, 2]. The characteristics of this behavior are fully consistent with a pairing transition, implying a high temperature superconducting state with Tc metal nanocluster particles are promising building blocks for high-Tc materials, devices, and networks. ---------- 1. Halder, A., Liang, A., Kresin, V. V. A novel feature in aluminum cluster photoionization spectra and possibility of electron pairing at T 100K. Nano Lett 15, 1410 - 1413 (2015) 2. Halder, A., Kresin, V. V. A transition in the density of states of metal "superatom" nanoclusters and evidence for superconducting pairing at T 100K. Phys. Rev. B 92, 214506 (2015).

  8. The efficacy of Raf kinase recruitment to the GTPase H-ras depends on H-ras membrane conformer-specific nanoclustering.

    Science.gov (United States)

    Guzmán, Camilo; Šolman, Maja; Ligabue, Alessio; Blaževitš, Olga; Andrade, Débora M; Reymond, Luc; Eggeling, Christian; Abankwa, Daniel

    2014-04-01

    Solution structures and biochemical data have provided a wealth of mechanistic insight into Ras GTPases. However, information on how much the membrane organization of these lipid-modified proteins impacts on their signaling is still scarce. Ras proteins are organized into membrane nanoclusters, which are necessary for Ras-MAPK signaling. Using quantitative conventional and super-resolution fluorescence methods, as well as mathematical modeling, we investigated nanoclustering of H-ras helix α4 and hypervariable region mutants that have different bona fide conformations on the membrane. By following the emergence of conformer-specific nanoclusters in the plasma membrane of mammalian cells, we found that conformers impart distinct nanoclustering responses depending on the cytoplasmic levels of the nanocluster scaffold galectin-1. Computational modeling revealed that complexes containing H-ras conformers and galectin-1 affect both the number and lifetime of nanoclusters and thus determine the specific Raf effector recruitment. Our results show that mutations in Ras can affect its nanoclustering response and thus allosterically effector recruitment and downstream signaling. We postulate that cancer- and developmental disease-linked mutations that are associated with the Ras membrane conformation may exhibit so far unrecognized Ras nanoclustering and therefore signaling alterations.

  9. Quantitative modelling of the surface plasmon resonances of metal nanoclusters sandwiched between dielectric layers: the influence of nanocluster size, shape and organization

    Energy Technology Data Exchange (ETDEWEB)

    Toudert, J; Babonneau, D; Simonot, L; Camelio, S; Girardeau, T [PHYMAT, UMR CNRS 6630, Batiment SP2MI, Boulevard Marie et Pierre Curie, 86962 Futuroscope Chasseneuil (France)], E-mail: johann.toudert@gmail.com

    2008-03-26

    The effects of size, shape and organization on the surface plasmon resonances of Ag nanoclusters sandwiched between Si{sub 3}N{sub 4} layers are studied by transmission electron microscopy and anisotropic spectroscopic ellipsometry. We present an easy-to-handle model that quantitatively links the nanostructure and optical response of the films, which are considered as dielectric/metal:dielectric/dielectric trilayers, with the central nanocomposite layer being an effective medium whose optical properties are described by an anisotropic dielectric tensor. The components of this tensor are calculated using a generalization of the Yamaguchi theory taking into account the real organization, size and shape distributions of ellipsoidal nanoclusters, whose electronic properties are assumed to reflect shape-dependent finite size effects. Using this model, it is shown that the optical response of the films in the visible range is dominated by the excitation of the surface plasmon resonance of the clusters along their in-plane long axis, while no surface plasmon resonance resulting from an excitation along their in-plane short axis can be observed due to damping effects. Moreover, the spectral position of this resonance appears to be mainly affected by the average shape of the clusters, and weakly by their size, their shape distribution and the electromagnetic interaction between them.

  10. Platinum and Other Transition Metal Nanoclusters (Pd, Rh) Stabilized by PAMAM Dendrimer as Excellent Heterogeneous Catalysts: Application to the Methylcyclopentane (MCP) Hydrogenative Isomerization.

    Science.gov (United States)

    Deraedt, Christophe; Melaet, Gérôme; Ralston, Walter T; Ye, Rong; Somorjai, Gabor A

    2017-03-08

    Pt, Rh, and Pd nanoclusters stabilized by PAMAM dendrimer are used for the first time in a gas flow reactor at high temperature (150-250 °C). Pt nanoclusters show a very high activity for the hydrogenation of the methylcyclopentane (MCP) at 200-225 °C with turnover freqency (TOF) up to 334 h(-1) and selectivity up to 99.6% for the ring opening isomerization at very high conversion (94%). Rh nanoclusters show different selectivity for the reaction, that is, ring opening isomerization at 175 °C and cracking at higher temperature whereas Pd nanoclusters perform ring enlargement plus dehydrogenation, while maintaining a high activity. The difference in these results as compared to unsupported/uncapped nanoparticles, demonstrates the crucial role of dendrimer. The tunability of the selectivity of the reaction as well as the very high activity of the metal nanoclusters stabilized by dendrimer under heterogeneous conditions open a new application for dendrimer catalysts.

  11. Biomedical applications of magneto-plasmonic nanoclusters (Conference Presentation)

    Science.gov (United States)

    Sokolov, Konstantin V.; Wu, Chun-Hsien; Cook, Jason; Zal, Tomasz; Emelianov, Stanislav

    2016-03-01

    Perhaps one of the most intriguing aspects of nanotechnology is the ability to create multimodal and multifunctional nanostructures that can open new venues in solving challenging biomedical problems. Here, we present multimodal magneto-plasmonic nanoparticles (MPNs) with a strong red-NIR absorbance, superparamagnetic properties and a high magnetic moment in an external magnetic field. Our design is based on self-assembly of 6 nm primary particles which consist of 5 nm diameter iron-oxide cores coated with a very thin ca. 0.5 nm gold shell. The assembly results in spherical highly uniform MPNs. We developed antibody targeted MPNs to address two highly challenging applications: (i) development of real-time assays for capture, enumeration and characterization of circulating tumor cells (CTCs), and (ii) enhancement of adoptive cell immunotherapy (ACT). Our results showed that MPNs can be used for simultaneous magnetic capture and photoacoustic (PA) detection of cancer cells in whole blood with no laborious processing steps. Furthermore, we demonstrated that MPNs conjugated with anti-CD8 antibodies, which are specific for cytotoxic T cells used in ATC, label CD8+ T cells with high specificity ex vivo and in vivo. Labeled T cells can be easily manipulated by a small magnet in suspension and under flow conditions. In addition, MPNs generate high contrast in MRI and PA imaging with the potential to detect just few cells per imaging voxel. These results show that immunotargeted MPNs can be explored for simultaneous visualization and magnetic guidance of T cell subsets in vivo for cancer treatment.

  12. Industrial Ziegler-type hydrogenation catalysts made from Co(neodecanoate)2 or Ni(2-ethylhexanoate)2 and AlEt3: evidence for nanoclusters and sub-nanocluster or larger Ziegler-nanocluster based catalysis.

    Science.gov (United States)

    Alley, William M; Hamdemir, Isil K; Wang, Qi; Frenkel, Anatoly I; Li, Long; Yang, Judith C; Menard, Laurent D; Nuzzo, Ralph G; Özkar, Saim; Yih, Kuang-Hway; Johnson, Kimberly A; Finke, Richard G

    2011-05-17

    Ziegler-type hydrogenation catalysts are important for industrial processes, namely, the large-scale selective hydrogenation of styrenic block copolymers. Ziegler-type hydrogenation catalysts are composed of a group 8-10 transition metal precatalyst plus an alkylaluminum cocatalyst (and they are not the same as Ziegler-Natta polymerization catalysts). However, for ∼50 years two unsettled issues central to Ziegler-type hydrogenation catalysis are the nature of the metal species present after catalyst synthesis, and whether the species primarily responsible for catalytic hydrogenation activity are homogeneous (e.g., monometallic complexes) or heterogeneous (e.g., Ziegler nanoclusters defined as metal nanoclusters made from combination of Ziegler-type hydrogenation catalyst precursors). A critical review of the existing literature (Alley et al. J. Mol. Catal. A: Chem. 2010, 315, 1-27) and a recently published study using an Ir model system (Alley et al. Inorg. Chem. 2010, 49, 8131-8147) help to guide the present investigation of Ziegler-type hydrogenation catalysts made from the industrially favored precursors Co(neodecanoate)(2) or Ni(2-ethylhexanoate)(2), plus AlEt(3). The approach and methods used herein parallel those used in the study of the Ir model system. Specifically, a combination of Z-contrast scanning transmission electron microscopy (STEM), matrix assisted laser desorption ionization mass spectrometry (MALDI MS), and X-ray absorption fine structure (XAFS) spectroscopy are used to characterize the transition metal species both before and after hydrogenation. Kinetic studies including Hg(0) poisoning experiments are utilized to test which species are the most active catalysts. The main findings are that, both before and after catalytic cyclohexene hydrogenation, the species present comprise a broad distribution of metal cluster sizes from subnanometer to nanometer scale particles, with estimated mean cluster diameters of about 1 nm for both Co and Ni. The

  13. The Magic Au60 Nanocluster: A New Cluster-Assembled Material with Five Au13 Building Blocks.

    Science.gov (United States)

    Song, Yongbo; Fu, Fangyu; Zhang, Jun; Chai, Jinsong; Kang, Xi; Li, Peng; Li, Shengli; Zhou, Hongping; Zhu, Manzhou

    2015-07-13

    Herein, we report the synthesis and atomic structure of the cluster-assembled [Au60Se2(Ph3P)10(SeR)15](+) material. Five icosahedral Au13 building blocks from a closed gold ring with Au-Se-Au linkages. Interestingly, two Se atoms (without the phenyl tail) locate in the center of the cluster, stabilized by the Se-(Au)5 interactions. The ring-like nanocluster is unprecedented in previous experimental and theoretical studies of gold nanocluster structures. In addition, our optical and electrochemical studies show that the electronic properties of the icosahedral Au13 units still remain unchanged in the penta-twinned Au60 nanocluster, and this new material might be a promising in optical limiting material. This work offers a basis for deep understanding on controlling the cluster-assembled materials for tailoring their functionalities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Effects of doping in 25-atom bimetallic nanocluster catalysts for carbon–carbon coupling reaction of iodoanisole and phenylacetylene

    Directory of Open Access Journals (Sweden)

    Zhimin Li

    2016-10-01

    Full Text Available We here report the catalytic effects of foreign atoms (Cu, Ag, and Pt doped into well-defined 25-gold-atom nanoclusters. Using the carbon-carbon coupling reaction of p-iodoanisole and phenylacetylene as a model reaction, the gold-based bimetallic MxAu25−x(SR18 (–SR=–SCH2CH2Ph nanoclusters (supported on titania were found to exhibit distinct effects on the conversion of p-iodoanisole as well as the selectivity for the Sonogashira cross-coupling product, 1-methoxy-4-(2-phenylethynylbenzene. Compared to Au25(SR18, the centrally doped Pt1Au24(SR18 causes a drop in catalytic activity but with the selectivity retained, while the AgxAu25−x(SR18 nanoclusters gave an overall performance comparable to Au25(SR18. Interestingly, CuxAu25−x(SR18 nanoclusters prefer the Ullmann homo-coupling pathway and give rise to product 4,4′-dimethoxy-1,1′-biphenyl, which is in opposite to the other three nanocluster catalysts. Our overall conclusion is that the conversion of p-iodoanisole is largely affected by the electronic effect in the bimetallic nanoclusters’ 13-atom core (i.e., Pt1Au12, CuxAu13−x, and Au13, with the exception of Ag doping, and that the selectivity is primarily determined by the type of atoms on the MxAu12−x shell (M=Ag, Cu, and Au in the nanocluster catalysts.

  15. Cluster-support interactions and morphology of MoS2 nanoclusters in a graphite-supported hydrotreating model catalyst.

    Science.gov (United States)

    Kibsgaard, Jakob; Lauritsen, Jeppe V; Laegsgaard, Erik; Clausen, Bjerne S; Topsøe, Henrik; Besenbacher, Flemming

    2006-10-25

    Supported MoS(2) nanoparticles constitute the active component of the important hydrotreating catalysts used for industrial upgrading and purification of the oil feedstock for the production of fossil fuels with a low environmental load. We have synthesized and studied a model system of the hydrotreating catalyst consisting of MoS(2) nanoclusters supported on a graphite surface in order to resolve a number of very fundamental questions related to the atomic-scale structure and morphology of the active clusters and in particular the effect of a substrate used in some types of hydrotreating catalysts. Scanning tunneling microscopy (STM) is used to image the atomic-scale structure of graphite-supported MoS(2) nanoclusters in real space. It is found that the pristine graphite (0001) surface does not support a high dispersion of MoS(2), but by introducing a small density of defects in the surface, highly dispersed MoS(2) nanoclusters could be synthesized on the graphite. From high-resolution STM images it is found that MoS(2) nanoclusters synthesized at low temperature in a sulfiding atmosphere preferentially grow as single-layer clusters, whereas clusters synthesized at 1200 K grow as multilayer slabs oriented with the MoS(2)(0001) basal plane parallel to the graphite surface. The morphology of both single-layer and multilayer MoS(2) nanoclusters is found to be preferentially hexagonal, and atom-resolved images of the top facet of the clusters provide new atomic-scale information on the MoS(2)-HOPG bonding. The structure of the two types of catalytically interesting edges terminating the hexagonal MoS(2) nanoclusters is also resolved in atomic detail in STM images, and from these images it is possible to reveal the atomic structure of both edges and the location and coverage of sulfur and hydrogen adsorbates.

  16. Dodecanuclear [Cu(II)6Gd(III)6] nanoclusters as magnetic refrigerants.

    Science.gov (United States)

    Dinca, Alina S; Ghirri, Alberto; Madalan, Augustin M; Affronte, Marco; Andruh, Marius

    2012-04-02

    A novel dodecanuclear complex, [{(HL)(L)(DMF)Cu(II)Gd(III)(DMF)(H(2)O)}(6)]·6DMF (1; DMF = N,N-dimethylformamide), has been obtained using the ligand resulting from the condensation of 3-formylsalicylic acid with hydroxylamine (H(3)L). The exchange interaction between the phenoxo-bridged Cu(II) and Gd(III) ions is weak ferromagnetic (J = +1.01 cm(-1)). The combination of a high-spin ground state with small anisotropy leads to a significant magnetocaloric effect [-ΔS(m)(0-7 T) = 23.5 J K g(-1) K(-1) at ∼2 K].

  17. One-dimensional nanoclustering of the Cu(100) surface under CO gas in the mbar pressure range

    Science.gov (United States)

    Eren, Baran; Zherebetskyy, Danylo; Hao, Yibo; Patera, Laerte L.; Wang, Lin-Wang; Somorjai, Gabor A.; Salmeron, Miquel

    2016-09-01

    The bulk terminated Cu(100) surface becomes unstable in the presence of CO at room temperature when the pressure reaches the mbar range. Scanning tunneling microscopy images show that above 0.25 mbar the surface forms nanoclusters with CO attached to peripheral Cu atoms. At 20 mbar and above 3-atom wide one-dimensional nanoclusters parallel to directions cover the surface, with CO on every Cu atom, increasing in density up to 115 mbar. Density functional theory explains the findings as a result of the detachment of Cu atoms from step edges caused by the stronger binding of CO relative to that on flat terraces.

  18. DNA为模板的铂纳米团簇沉积%DNA-templated Platinum Nanocluster Deposition

    Institute of Scientific and Technical Information of China (English)

    晁洁; 刘霞; 刘洪波; 肖守军

    2007-01-01

    Platinum nanoclusters were deposited along the supercoiled DNA strands after incubation of cis-(trans-1R,2R-diaminocyclohexane)(dl-camphorato)platinum(Ⅱ) (Cdp), an analogue of the anti-tumor drug-carboplatin, with DNA and K2PtCl4 for 600 min and then through reduction of dimethylaminoborane (DMAB). The decrease of absorption of DNA at 260 nm indicates the coordination of Cdp and DNA. TEM and AFM were employed to characterize the morphologies and structures of platinum nanoclusters.

  19. DNA-Templated Silver Nanoclusters Formation at Gold Electrode Surface and Its Application to Hydrogen Peroxide Detection

    Institute of Scientific and Technical Information of China (English)

    许媛媛; 陈阳阳; 杨娜娜; 孙丽洲; 李根喜

    2012-01-01

    In this work, we have prepared Ag nanoclusters (Ag NCs) at gold electrode surface by using thiol-modified oligodeoxynucleotide consisting of eighteen cytosine deoxyribonucleotides (polyC18) as template and NaBH4 as reducing agent. Experimental results show that Ag nanoclusters (Ag NCs) can be formed around the template polyC18, while the formation can be characterized with electrochemical method. Further studies reveal that the fab- ricated Ag NCs may display high catalytic activity for the reduction of hydrogen peroxide (H2O2), which can be further used for the detection of H20〉

  20. Thermodynamics at the nanoscale: phase diagrams of nickel-carbon nanoclusters and equilibrium constants for phase transitions.

    Science.gov (United States)

    Engelmann, Yannick; Bogaerts, Annemie; Neyts, Erik C

    2014-10-21

    Using reactive molecular dynamics simulations, the melting behavior of nickel-carbon nanoclusters is examined. The phase diagrams of icosahedral and Wulff polyhedron clusters are determined using both the Lindemann index and the potential energy. Formulae are derived for calculating the equilibrium constants and the solid and liquid fractions during a phase transition, allowing more rational determination of the melting temperature with respect to the arbitrary Lindemann value. These results give more insight into the properties of nickel-carbon nanoclusters in general and can specifically be very useful for a better understanding of the synthesis of carbon nanotubes using the catalytic chemical vapor deposition method.

  1. Tunable surface plasmon resonance of silver nanoclusters in ion exchanged soda lime glass

    Energy Technology Data Exchange (ETDEWEB)

    Mohapatra, Satyabrata, E-mail: smiuac@gmail.com

    2014-06-15

    Highlights: • Ag-glass nanocomposites were synthesized by silver ion exchange and annealing. • SPR of Ag-glass nanocomposites was tuned from 420 to 596 nm by annealing in air. • Subsequent annealing of nanocomposites in Ar + H{sub 2} reversed back SPR to 398 nm. • Formation/dissolution of Ag{sub 2}O nanoshells around Ag nanoclusters lead to tunable SPR. - Abstract: Silver (Ag) nanoclusters embedded in soda lime glass were synthesized by Ag ion exchange followed by thermal annealing. The effects of annealing temperature, time and atmosphere on the plasmonic response, structural and optical properties of silver-glass nanocomposites have been investigated using UV–visible absorption spectroscopy and X-ray photoelectron spectroscopy (XPS). As exchanged sample exhibits surface plasmon resonance (SPR) band around 420 nm which showed regular red shift with increase in annealing temperature. A significant red shift of 176 nm (from 420 to 596 nm) and broadening of the SPR peak was observed for annealing in air at 450 °C. XPS studies on air annealed samples confirmed the presence of Ag{sub 2}O in addition to Ag. Subsequent annealing at 250 °C in reducing atmosphere resulted in increase in intensity, narrowing and blue shift of the SPR peak to 398 nm. Our observations suggest that SPR tunability is mainly due to the formation and dissolution of Ag{sub 2}O nanoshells around Ag nanoclusters in the near-surface region of glass during annealing in oxidizing and reducing atmosphere, respectively.

  2. Synthesis of ultrastable copper sulfide nanoclusters via trapping the reaction intermediate: potential anticancer and antibacterial applications.

    Science.gov (United States)

    Wang, Hong-Yin; Hua, Xian-Wu; Wu, Fu-Gen; Li, Bolin; Liu, Peidang; Gu, Ning; Wang, Zhifei; Chen, Zhan

    2015-04-01

    Copper-based nanomaterials have broad applications in electronics, catalysts, solar energy conversion, antibiotics, tissue imaging, and photothermal cancer therapy. However, it is challenging to prepare ultrasmall and ultrastable CuS nanoclusters (NCs) at room temperature. In this article, a simple method to synthesize water-soluble, monodispersed CuS NCs is reported based on the strategy of trapping the reaction intermediate using thiol-terminated, alkyl-containing short-chain poly(ethylene glycol)s (HS-(CH2)11-(OCH2CH2)6-OH, abbreviated as MUH). The MUH-coated CuS NCs have superior stability in solutions with varied pH values and are stable in pure water for at least 10 months. The as-prepared CuS NCs were highly toxic to A549 cancer cells at a concentration of higher than 100 μM (9.6 μg/mL), making them be potentially applicable as anticancer drugs via intravenous administration by liposomal encapsulation or by direct intratumoral injection. Besides, for the first time, CuS NCs were used for antibacterial application, and 800 μM (76.8 μg/mL) CuS NCs could completely kill the E. coli cells through damaging the cell walls. Moreover, the NCs synthesized here have strong near-infrared (NIR) absorption and can be used as a candidate reagent for photothermal therapy and photoacoustic imaging. The method of trapping the reaction intermediate for simple and controlled synthesis of nanoclusters is generally applicable and can be widely used to synthesize many metal-based (such as Pt, Pd, Au, and Ag) nanoclusters and nanocrystals.

  3. Separation of the contributions to the magnetization of Tm1 - x Yb x B12 solid solutions in steady and pulsed magnetic fields

    Science.gov (United States)

    Bogach, A. V.; Sluchanko, N. E.; Glushkov, V. V.; Demishev, S. V.; Azarevich, A. N.; Filippov, V. B.; Shitsevalova, N. Yu.; Levchenko, A. V.; Vanacken, J.; Moshchalkov, V. V.; Gabani, S.; Flachbart, K.

    2013-05-01

    The magnetization of substitutional Tm1 - x Yb x B12 solid solutions is studied in the composition range 0 B12 compounds to be separated. These contributions include a Pauli component, which corresponds to the response of the heavy-fermion manybody states that appears in the energy gap in the vicinity of the Fermi level (density of states (3-4) × 1021 cm-3 meV-1), and a contribution with saturation in high magnetic fields attributed to the localized magnetic moments ((0.8-3.7)μB per unit cell) of the nanoclusters formed by rare-earth ions with an antiferromagnetic interaction.

  4. Metal-nanocluster composites made by ion implantation: A novel third-order nonlinear material

    Energy Technology Data Exchange (ETDEWEB)

    Haglund, R.F. Jr.; Yang, L.; Magruder, R.H. III; Becker, K.; Wittig, J.E. [Vanderbilt Univ., Nashville, TN (United States); White, C.W.; Zhur, R.A. [Oak Ridge National Lab., TN (United States); Yang, L.; Dorsinville, R.; Alfano, R.R. [City Univ. of New York, NY (United States)

    1993-03-01

    We describe our recent studies of metal-insulator nanocluster composites made by ion implantation in such substrates as glass and sapphire. The metal clusters have diameters ranging from 3 to 30 nm. The composites exhibit an electronic nonlinear optical response which is fast on the picosecond time scale. In addition to possibilities for technological application, these materials also offer a way of studying unusual properties of composite materials, such as the quantum confinement of conduction-band electrons and the transverse relaxation time T{sub 2} as a function of cluster size.

  5. Metal-nanocluster composites made by ion implantation: A novel third-order nonlinear material

    Energy Technology Data Exchange (ETDEWEB)

    Haglund, R.F. Jr.; Yang, L.; Magruder, R.H. III; Becker, K.; Wittig, J.E. (Vanderbilt Univ., Nashville, TN (United States)); White, C.W.; Zhur, R.A. (Oak Ridge National Lab., TN (United States)); Yang, L.; Dorsinville, R.; Alfano, R.R. (City Univ. of New York, NY (United States))

    1993-03-01

    We describe our recent studies of metal-insulator nanocluster composites made by ion implantation in such substrates as glass and sapphire. The metal clusters have diameters ranging from 3 to 30 nm. The composites exhibit an electronic nonlinear optical response which is fast on the picosecond time scale. In addition to possibilities for technological application, these materials also offer a way of studying unusual properties of composite materials, such as the quantum confinement of conduction-band electrons and the transverse relaxation time T[sub 2] as a function of cluster size.

  6. Oxidative addition of the C-I bond on aluminum nanoclusters

    Science.gov (United States)

    Sengupta, Turbasu; Das, Susanta; Pal, Sourav

    2015-07-01

    Energetics and the in-depth reaction mechanism of the oxidative addition step of the cross-coupling reaction are studied in the framework of density functional theory (DFT) on aluminum nanoclusters. Aluminum metal in its bulk state is totally inactive towards carbon-halogen bond dissociation but selected Al nanoclusters (size ranging from 3 to 20 atoms) have shown a significantly lower activation barrier towards the oxidative addition reaction. The calculated energy barriers are lower than the gold clusters and within a comparable range with the conventional and most versatile Pd catalyst. Further investigations reveal that the activation energies and other reaction parameters are highly sensitive to the geometrical shapes and electronic structures of the clusters rather than their size, imposing the fact that comprehensive studies on aluminum clusters can be beneficial for nanoscience and nanotechnology. To understand the possible reaction mechanism in detail, the reaction pathway is investigated with the ab initio Born Oppenheimer Molecular Dynamics (BOMD) simulation and the Natural Bond Orbital (NBO) analysis. In short, our theoretical study highlights the thermodynamic and kinetic details of C-I bond dissociation on aluminum clusters for future endeavors in cluster chemistry.Energetics and the in-depth reaction mechanism of the oxidative addition step of the cross-coupling reaction are studied in the framework of density functional theory (DFT) on aluminum nanoclusters. Aluminum metal in its bulk state is totally inactive towards carbon-halogen bond dissociation but selected Al nanoclusters (size ranging from 3 to 20 atoms) have shown a significantly lower activation barrier towards the oxidative addition reaction. The calculated energy barriers are lower than the gold clusters and within a comparable range with the conventional and most versatile Pd catalyst. Further investigations reveal that the activation energies and other reaction parameters are highly

  7. Enhanced Tumor Accumulation of Sub-2 nm Gold Nanoclusters for Cancer Radiation Therapy

    CERN Document Server

    Zhang, Xiao-Dong; Luo, Zhentao; Wu, Di; Shen, Xiu; Song, Sha-Sha; Sun, Yuan-Ming; Liu, Pei-Xun; Zhao, Jing; Huo, Shuaidong; Fan, Saijun; Fan, Feiyue; Liang, Xing-Jie; Xie, Jianping

    2013-01-01

    A new type of metabolizable and efficient radiosensitizer for cancer radiotherapy is presented in this study by combining ultrasmall Au nanoclusters (NCs, <2 nm) with biocompatible coating ligands (glutathione, GSH). The new nano-construct (GSH-coated Au25 NCs) inherits attractive features of both the Au core (strong radiosensitizing effect) and GSH shell (good biocompatibility). It can preferentially accumulate in tumor via the improved EPR effect, which leads to strong enhancement for cancer radiotherapy. After the treatment, the small-sized GSH-Au25 NCs can be efficiently cleared by the kidney, minimizing any potential side effects due to the accumulation of Au25 NCs in the body.

  8. A Thomson parabola ion imaging spectrometer designed to probe relativistic intensity ionization dynamics of nanoclusters.

    Science.gov (United States)

    Rajeev, R; Rishad, K P M; Trivikram, T Madhu; Narayanan, V; Krishnamurthy, M

    2011-08-01

    Conventional techniques of probing ionization dynamics at relativistic intensities for extended target systems such as clusters are difficult both due to problems of achieving good charge resolution and signal integration over the focal volume. Simultaneous measurement of arrival time, necessary for these systems, has normally involved complicated methods. We designed and developed a Thomson parabola imaging spectrometer that overcomes these problems. Intensity sampling method evolved in this report is proved to be mandatory for probing ionization dynamics of clusters at relativistic intensities. We use this method to measure charge resolved kinetic energy spectra of argon nanoclusters at intensities of 4 × 10(18) W cm(-2).

  9. Ultrafast static and diffusion-controlled electron transfer at Ag 29 nanocluster/molecular acceptor interfaces

    KAUST Repository

    Aly, Shawkat Mohammede

    2015-10-29

    Efficient absorption of visible light and a long-lived excited state lifetime of silver nanoclusters (Ag29 NCs) are integral properties for these new clusters to serve as light-harvesting materials. Upon optical excitation, electron injection at Ag29 NC/methyl viologen (MV2+) interfaces is very efficient and ultrafast. Interestingly, our femto- and nanosecond time-resolved results demonstrate clearly that both dynamic and static electron transfer mechanisms are involved in photoluminescence quenching of Ag29 NCs. © 2016 The Royal Society of Chemistry.

  10. Atomistic understanding of hydrogen loading phenomenon into palladium cathode: A simple nanocluster approach and electrochemical evidence

    Indian Academy of Sciences (India)

    Mohsen Lashgari; Davood Matloubi

    2015-03-01

    The inherent potency of palladium to sorb hydrogen atoms was examined empirically and theoretically through various electrochemical methods and high-level quantum chemical calculations (HSE06) based on cluster model (CM) and density functional theory (DFT). The CM-DFT approach using QZVP/cc-PV6Z basis sets revealed a strong attraction between Pd nanoclusters and H atoms that generates some charged entities. This atomistically justifies why the electrochemical impedance of the system becomes less by the loading phenomenon. It is concluded that hydrogen atoms enter the palladium subsurface through hollow and bridge sites by diffusing as proton-like species and get loaded predominantly in the octahedral voids.

  11. Radiation Stability of Nanoclusters in Nano-structured Oxide Dispersion Strengthened (ODS) Steels

    Energy Technology Data Exchange (ETDEWEB)

    Certain, Alicia G.; Kuchibhatla, Satyanarayana V N T; Shutthanandan, V.; Hoelzer, D. T.; Allen, T. R.

    2013-03-01

    Nanostructured oxide dispersion strengthened (ODS) steels are considered candidates for nuclear fission and fusion applications at high temperature and dose. The complex oxide nanoclusters in these alloys provide high-temperature strength and are expected to afford better radiation resistance. Proton, heavy ion, and neutron irradiations have been performed to evaluate cluster stability in 14YWT and 9CrODS steel under a range of irradiation conditions. Energy-filtered transmission electron microscopy and atom probe tomography were used in this work to analyze the evolution of the oxide population.

  12. Observation of the fcc-to-hcp transition in ensembles of argon nanoclusters.

    Science.gov (United States)

    Krainyukova, N V; Boltnev, R E; Bernard, E P; Khmelenko, V V; Lee, D M; Kiryukhin, V

    2012-12-14

    Macroscopic ensembles of weakly interacting argon nanoclusters are studied using x-ray diffraction in low vacuum. As the clusters grow by fusion with increasing temperature, their structure transforms from essentially face-centered cubic (fcc) to hexagonal close packed as the cluster size approaches ~10(5) atoms. The transformation involves intermediate orthorhombic phases. These data confirm extant theoretical predictions. They also indicate that growth kinetics and spatial constraints might play an important role in the formation of the fcc structure of bulk rare-gas solids, which still remains puzzling.

  13. Self-assembling nanoclusters in living systems: application for integrated photothermal nanodiagnostics and nanotherapy.

    Science.gov (United States)

    Zharov, Vladimir P; Kim, Jin-Woo; Curiel, David T; Everts, Maaike

    2005-12-01

    Nanotechnologies represent an unprecedented recent advance that may revolutionize many areas of medicine and biology, including cancer diagnostics and treatment. Nanoparticle-based technologies have demonstrated especially high potential for medical purposes, ranging from diagnosing diseases to providing novel therapies. However, to be clinically relevant, the existing nanoparticle-based technologies must overcome several challenges, including selective nanoparticle delivery, potential cytotoxicity, imaging of nanoparticles, and real-time assessment of their therapeutic efficacy. This review addresses these issues by summarizing the recent advances in medical diagnostics and therapy with a focus on the self-assembly of gold nanoparticles into nanoclusters in live cells, in combination with their detection using photothermal (PT) techniques.

  14. Restructuring of hex-Pt(100) under CO gas environments: formation of 2-D nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Tao, Feng; Dag, Sefa; Wang, Lin-Wang; Liu, Zhi; Butcher, Derek; Salmeron, Miquel; Somorjai, Gabor A.

    2009-04-24

    The atomic-scale restructuring of hex-Pt(100) induced by carbon monoxide with a wide pressure range was studied with a newly designed chamber-in-chamber high-pressure STM and theoretical calculations. Both experimental and DFT calculation results show that CO molecules are bound to Pt nanoclusters through a tilted on-top configuration with a separation of {approx}3.7-4.1 {angstrom}. The phenomenon of restructuring of metal catalyst surfaces induced by adsorption, and in particular the formation of small metallic clusters suggests the importance of studying structures of catalyst surfaces under high pressure conditions for understanding catalytic mechanisms.

  15. A Thomson parabola ion imaging spectrometer designed to probe relativistic intensity ionization dynamics of nanoclusters

    Science.gov (United States)

    Rajeev, R.; Rishad, K. P. M.; Trivikram, T. Madhu; Narayanan, V.; Krishnamurthy, M.

    2011-08-01

    Conventional techniques of probing ionization dynamics at relativistic intensities for extended target systems such as clusters are difficult both due to problems of achieving good charge resolution and signal integration over the focal volume. Simultaneous measurement of arrival time, necessary for these systems, has normally involved complicated methods. We designed and developed a Thomson parabola imaging spectrometer that overcomes these problems. Intensity sampling method evolved in this report is proved to be mandatory for probing ionization dynamics of clusters at relativistic intensities. We use this method to measure charge resolved kinetic energy spectra of argon nanoclusters at intensities of 4 × 1018 W cm-2.

  16. Network-Forming Nanoclusters in Binary As-S/Se Glasses: From Ab Initio Quantum Chemical Modeling to Experimental Evidences

    Science.gov (United States)

    Hyla, M.

    2017-01-01

    Network-forming As2(S/Se)m nanoclusters are employed to recognize expected variations in a vicinity of some remarkable compositions in binary As-Se/S glassy systems accepted as signatures of optimally constrained intermediate topological phases in earlier temperature-modulated differential scanning calorimetry experiments. The ab initio quantum chemical calculations performed using the cation-interlinking network cluster approach show similar oscillating character in tendency to local chemical decomposition but obvious step-like behavior in preference to global phase separation on boundary chemical compounds (pure chalcogen and stoichiometric arsenic chalcogenides). The onsets of stability are defined for chalcogen-rich glasses, these being connected with As2Se5 ( Z = 2.29) and As2S6 ( Z = 2.25) nanoclusters for As-Se and As-S glasses, respectively. The physical aging effects result preferentially from global phase separation in As-S glass system due to high localization of covalent bonding and local demixing on neighboring As2Sem+1 and As2Sem-1 nanoclusters in As-Se system. These nanoclusters well explain the lower limits of reversibility windows in temperature-modulated differential scanning calorimetry, but they cannot be accepted as signatures of topological phase transitions in respect to the rigidity theory.

  17. Ultrasmall Glutathione-Protected Gold Nanoclusters as Next Generation Radiotherapy Sensitizers with High Tumor Uptake and High Renal Clearance

    CERN Document Server

    Zhang, Xiao-Dong; Chen, Jie; Song, Shasha; Yuan, Xun; Shen, Xiu; Wang, Hao; Sun, Yuanming; Gao, Kai; Zhang, Lianfeng; Fan, Saijun; Leong, David Tai; Guo, Meili; Xie, Jianping

    2015-01-01

    Radiotherapy is often the most straightforward first line cancer treatment for solid tumors. While it is highly effective against tumors, there is also collateral damage to healthy proximal tissues especially with high doses. The use of radiosensitizers is an effective way to boost the killing efficacy of radiotherapy against the tumor while drastically limiting the received dose and reducing the possible damage to normal tissues. Here, we report the design and application of a good radiosensitizer by using ultrasmall gold nanoclusters with a naturally occurring peptide (e.g., glutathione or GSH) as the protecting shell. The GSH coated gold nanoclusters can escape the RES absorption, leading to a good tumor uptake (8.1% ID/g at 24 h post injection). As a result, the as-designed Au nanoclusters led to a strong enhancement for radiotherapy, as well as a negligible damage to normal tissues. After the treatment, the ultrasmall gold nanoclusters can be efficiently cleared by the kidney, thereby avoiding potential ...

  18. Microwave-Assisted Synthesis of Red-Light Emitting Au Nanoclusters with the Use of Egg White

    Science.gov (United States)

    Tian, Jinghan; Yan, Lei; Sang, Aohua; Yuan, Hongyan; Zheng, Baozhan; Xiao, Dan

    2014-01-01

    We developed a simple, cost-effective, and eco-friendly method to synthesize gold nanoclusters (AuNCs) with red fluorescence. The experiment was performed using HAuCl[subscript 4], egg white, Na[subscript 2]CO[subscript 3] (known as soda ash or washing soda), and a microwave oven. In our experiment, fluorescent AuNCs were prepared within a…

  19. Atomically Precise Gold Nanoclusters Accelerate Hydrogen Evolution over MoS2 Nanosheets: The Dual Interfacial Effect.

    Science.gov (United States)

    Zhao, Shuo; Jin, Renxi; Song, Yongbo; Zhang, Hui; House, Stephen D; Yang, Judith C; Jin, Rongchao

    2017-07-24

    Hydrogen generation via electrocatalytic water splitting holds great promise for future energy revolution. It is desirable to design abundant and efficient catalysts and achieve mechanistic understanding of hydrogen evolution reaction (HER). Here, this paper reports a strategy for improving HER performance of molybdenum disulfide (MoS2 ) via introducing gold nanoclusters as a cocatalyst. Compared to plain MoS2 nanosheets, the Au25 (SR)18 /MoS2 nanocomposite exhibits enhanced HER activity with a small onset potential of -0.20 V (vs reversible hydrogen electrode) and a higher current density of 59.3 mA cm(-2) at the potential of -0.4 V. In addition to the interfacial interaction between nanoclusters and MoS2 , the interface between the Au25 core and the surface ligands (thiolate vs selenolate) is also discovered to distinctly affect the catalytic performance. This work highlights the promise of metal nanoclusters in boosting the HER performance via tailoring the interfacial electronic interactions between gold nanoclusters and MoS2 nanosheets, as well as the interface between metal core and surface ligands. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Systematic Study on the Self-Assembled Hexagonal Au Voids, Nano-Clusters and Nanoparticles on GaN (0001.

    Directory of Open Access Journals (Sweden)

    Puran Pandey

    Full Text Available Au nano-clusters and nanoparticles (NPs have been widely utilized in various electronic, optoelectronic, and bio-medical applications due to their great potentials. The size, density and configuration of Au NPs play a vital role in the performance of these devices. In this paper, we present a systematic study on the self-assembled hexagonal Au voids, nano-clusters and NPs fabricated on GaN (0001 by the variation of annealing temperature and deposition amount. At relatively low annealing temperatures between 400 and 600°C, the fabrication of hexagonal shaped Au voids and Au nano-clusters are observed and discussed based on the diffusion limited aggregation model. The size and density of voids and nano-clusters can systematically be controlled. The self-assembled Au NPs are fabricated at comparatively high temperatures from 650 to 800°C based on the Volmer-Weber growth model and also the size and density can be tuned accordingly. The results are symmetrically analyzed and discussed in conjunction with the diffusion theory and thermodynamics by utilizing AFM and SEM images, EDS maps and spectra, FFT power spectra, cross-sectional line-profiles and size and density plots.

  1. Investigation of helium at a Y2Ti2O7 nanocluster embedded in a BCC Fe matrix.

    Science.gov (United States)

    Danielson, Thomas; Tea, Eric; Hin, Celine

    2016-11-02

    Nanostructured ferritic alloys (NFAs) are prime candidates for structural and first wall components of fission and fusion reactors. The main reason for this is their ability to effectively withstand high concentrations of the transmutation product helium. A high number density of oxide nanoclusters dispersed throughout a BCC Fe matrix act as trapping sites for helium and prevent its eventual delivery to high risk nucleation sites. The current study uses density functional theory to investigate the helium trapping mechanisms at the boundary between BCC iron and Y2Ti2O7, a common stoichiometry of the oxide nanoclusters in NFAs. The investigation is carried out on a structure matched oxide nanocluster that is embedded within a BCC Fe supercell. Investigation of the electronic structure and a mapping of the potential energy landscape reveals that the localized iono-covalent bonds present within the oxides create a potential energy-well within the metallically bonded BCC Fe matrix, so that trapping of helium at the oxide nanocluster is thermodynamically and kinetically favorable.

  2. Microwave-Assisted Synthesis of Red-Light Emitting Au Nanoclusters with the Use of Egg White

    Science.gov (United States)

    Tian, Jinghan; Yan, Lei; Sang, Aohua; Yuan, Hongyan; Zheng, Baozhan; Xiao, Dan

    2014-01-01

    We developed a simple, cost-effective, and eco-friendly method to synthesize gold nanoclusters (AuNCs) with red fluorescence. The experiment was performed using HAuCl[subscript 4], egg white, Na[subscript 2]CO[subscript 3] (known as soda ash or washing soda), and a microwave oven. In our experiment, fluorescent AuNCs were prepared within a…

  3. Dehydrogenation characteristics of MgnH2n (n = 1-32) nanoclusters: A first-principles DFT study

    Science.gov (United States)

    Banerjee, P.; Chandrakumar, K. R. S.; Das, G. P.

    2015-06-01

    Ground state structures and dehydrogenation characteristics of MgnH2n (n = 1-32) nanoclusters have been investigated using first principles DFT approach. Dehydrogenation temperature gets reduced compared to the bulk rutile phase of MgH2, indicating its favorable usage for hydrogen storage.

  4. Detecting element specific electrons from a single cobalt nanocluster with synchrotron x-ray scanning tunneling microscopy

    Science.gov (United States)

    Kersell, Heath; Shirato, Nozomi; Cummings, Marvin; Chang, Hao; Miller, Dean; Rosenmann, Daniel; Hla, Saw-Wai; Rose, Volker

    2017-09-01

    We use a nanofabricated scanning tunneling microscope tip as a detector to investigate local X-ray induced tunneling and electron emission from a single cobalt nanocluster on a Au(111) surface. The tip-detector is positioned a few angstroms above the nanocluster, and ramping the incident X-ray energy across the Co photoabsorption K-edge enables the detection of element specific electrons. Atomic-scale spatial dependent changes in the X-ray absorption cross section are directly measured by taking the X-ray induced current as a function of X-ray energy. From the measured sample and tip currents, element specific X-ray induced current components can be separated and thereby the corresponding yields for the X-ray induced processes of the single cobalt nanocluster can be determined. The detection of element specific synchrotron X-ray induced electrons of a single nanocluster opens an avenue for materials characterization on a one particle at-a-time basis.

  5. Correlation between the energy shell structure and geometry in metallic nanoclusters: quasi-resonance states, isotope effect

    CERN Document Server

    Kresin, Vladimir

    2008-01-01

    Metallic nanoclusters displaying electronic shell structure exhibit the special feature of a correlation between their geometry and the number of delocalized electrons . Their shape evolution can be described as a quantum oscillation between quasi-resonant states (prolate and oblate configurations) whose amplitudes depend upon the degree of shell filling. The picture explains the evolution of absorption spectra and predicts a peculiar isotope effect .

  6. Magnetism of CoPd self-organized alloy clusters on Au(111)

    Science.gov (United States)

    Ohresser, P.; Otero, E.; Wilhelm, F.; Rogalev, A.; Goyhenex, C.; Joly, L.; Bulou, H.; Romeo, M.; Speisser, V.; Arabski, J.; Schull, G.; Scheurer, F.

    2013-12-01

    Magnetic properties of gold-encapsulated CoxPd1-x self-organized nano-clusters on Au(111) are analyzed by x-ray magnetic circular dichroism for x = 0.5, 0.7, and 1.0. The clusters are superparamagnetic with a blocking temperature decreasing with increasing Pd concentration, due to a reduction of the out-of-plane anisotropy strength. No magnetic moment is detected on Pd in these clusters, within the detection limit, contrary to thick CoPd films. Both reduction of anisotropy and vanishing Pd moment are attributed to strain.

  7. Assembly of large purely inorganic Ce-stabilized/bridged selenotungstates: from nanoclusters to layers.

    Science.gov (United States)

    Chen, Wei-Chao; Qin, Chao; Li, Yang-Guang; Zang, Hong-Ying; Shao, Kui-Zhan; Su, Zhong-Min; Wang, En-Bo

    2015-05-01

    A versatile one-pot strategy was used to synthesize two large, purely inorganic selenotungstates, nanocluster K(6)Na(16) [Ce(6)Se(6)W(67)O(230) (OH)(6) (H(2)O)(17)]⋅47 H(2)O (1) and layer K(9)Na(5) Ce(H(2)O)(4) [Ce(6)Se(10)W(51)O(187) (OH)(7) (H(2)O)(18)]⋅45H(2)O(2), by combining cerium centers and SeO(3) (2-) heteroanion templates. Compound 1 displays a Ce-stabilized hexameric nanocluster with one rhombus-like {W(4)O(15) (OH)(3)} unit in the center, whereas compound 2 is the first example of a Ce-bridged layer selenotungstate network based on linkage of the unusual {Ce(6)Se(10)W(51)O(187) (OH)(7) (H(2)O)(18)} clusters and additional Ce(H(2)O)(4) fragments via Ce-O-Se bridges. The compounds were characterized by elemental analyses, IR spectroscopy, thermogravimetric analyses, powder and single-crystal X-ray diffraction, and electrospray ionization mass spectrometry. Moreover, the electrochemical property of compound 1 was also investigated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Facile synthesis of fluorescent Au/Ce nanoclusters for high-sensitive bioimaging.

    Science.gov (United States)

    Ge, Wei; Zhang, Yuanyuan; Ye, Jing; Chen, Donghua; Rehman, Fawad Ur; Li, Qiwei; Chen, Yun; Jiang, Hui; Wang, Xuemei

    2015-02-03

    Tumor-target fluorescence bioimaging is an important means of early diagnosis, metal nanoclusters have been used as an excellent fluorescent probe for marking tumor cells due to their targeted absorption. We have developed a new strategy for facile synthesis of Au/Ce nanoclusters (NCs) by doping trivalent cerium ion into seed crystal growth process of gold. Au/Ce NCs have bright fluorescence which could be used as fluorescent probe for bioimaging. In this study, we synthesized fluorescent Au/Ce NCs through two-step hydrothermal reaction. The concentration range of 25-350 μM, Au/Ce NCs have no obvious cell cytotoxicity effect on HeLa, HepG2 and L02 cells. Furthermore, normal cells (L02) have no obvious absorption of Au/Ce NCs. Characterization of synthesized Au/Ce NCs was done by using TEM, EDS and XPS. Then these prepared Au/Ce NCs were applied for in vitro/in vivo tumor-target bioimaging due to its prolonged fluorescence lifetime and bright luminescence properties. The glutathione stabilized Au/Ce NCs synthesized through hydrothermal reaction possess stable and bright fluorescence that can be readily utilized for high sensitive fluorescence probe. Our results suggest that Au/Ce NCs are useful candidate for in vitro/in vivo tumor bioimaging in potential clinical application.

  9. Photoconductivity, photoluminescence and optical Kerr nonlinear effects in zinc oxide films containing chromium nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Torres-Torres, C., E-mail: crstorres@yahoo.com.mx [Seccion de Estudios de Posgrado e Investigacion, ESIME-Z, Instituto Politecnico Nacional, Mexico, DF 07738 (Mexico); Garcia-Cruz, M.L. [Centro de Investigacion en Dispositivos Semiconductores, Benemerita Universidad Autonoma de Puebla, A. P. J-48, Puebla 72570, Mexico (Mexico); Castaneda, L., E-mail: luisca@sirio.ifuap.buap.mx [Instituto de Fisica, Benemerita Universidad Autonoma de Puebla, A. P. J-48, Puebla 72570, Mexico (Mexico); Rangel Rojo, R. [CICESE/Depto. de Optica, A. P. 360, Ensenada, BC 22860 (Mexico); Tamayo-Rivera, L. [Instituto de Fisica, Universidad Nacional Autonoma de Mexico, Mexico, DF 01000 (Mexico); Maldonado, A. [Depto. de Ing. Electrica, CINVESTAV IPN-SEES, A. P. 14740, Mexico DF 07000 (Mexico); Avendano-Alejo, M., E-mail: imax_aa@yahoo.com.mx [Centro de Ciencias Aplicadas y Desarrollo Tecnologico, Universidad Nacional Autonoma de Mexico, A. P. 70-186, 04510, DF (Mexico); and others

    2012-04-15

    Chromium doped zinc oxide thin solid films were deposited on soda-lime glass substrates. The photoconductivity of the material and its influence on the optical behavior was evaluated. A non-alkoxide sol-gel synthesis approach was used for the preparation of the samples. An enhancement of the photoluminescence response exhibited by the resulting photoconductive films with embedded chromium nanoclusters is presented. The modification in the photoconduction induced by a 445 nm wavelength was measured and then associated with the participation of the optical absorptive response. In order to investigate the third order optical nonlinearities of the samples, a standard time-resolved Optical Kerr Gate configuration with 80 fs pulses at 830 nm was used and a quasi-instantaneous pure electronic nonlinearity without the contribution of nonlinear optical absorption was observed. We estimate that from the inclusion of Cr nanoclusters into the sample results a strong optical Kerr effect originated by quantum confinement. The large photoluminescence response and the important refractive nonlinearity of the photoconductive samples seem to promise potential applications for the development of multifunctional all-optical nanodevices. - Highlights: Black-Right-Pointing-Pointer Enhancement in photoluminescence for chromium doped zinc oxide films is presented. Black-Right-Pointing-Pointer A strong and ultrafast optical Kerr effect seems to result from quantum confinement. Black-Right-Pointing-Pointer Photoconductive properties for optical and optoelectronic functions were observed.

  10. Formation of silver nanoclusters in transparent polyimides by Ag-K ion-exchange process

    Science.gov (United States)

    Carturan, S.; Quaranta, A.; Bonafini, M.; Vomiero, A.; Maggioni, G.; Mattei, G.; de Julián Fernández, C.; Bersani, M.; Mazzoldi, P.; Della Mea, G.

    2007-05-01

    Silver nanoclusters embedded in two transparent fluorinated polyimides, 4,4'-hexafluoroisopropylidene diphthalic anhydride 2,3,5,6-tetramethyl paraphenylene diamine (6FDA-DAD) and 3,3',4,4' biphenyltetracarboxylic acid dianhydride 1,1-bis(4-aminophenyl)-1-phenyl-2,2,2-trifluoroethane (BPDA-3F), have been produced by surface modification with KOH aqueous solution followed by K-assisted Ag doping and thermal reduction in hydrogen atmosphere. The reaction rate of the nucleophilic hydrolysis in KOH, studied by Fourier transform infrared spectroscopy (FT-IR) and Rutherford backscattering spectrometry (RBS), depends on the polyimide chemical structure. After ion-exchange in AgNO{3} solution and subsequent annealing, the polyimide structure recovery was monitored by FT-IR whereas the characteristic surface plasmon absorption band of silver nanoparticles was evidenced by optical absorption measurements. The structure of silver nanoclusters as related to size and size distribution in the different polyimide matrices was thoroughly investigated by Transmission electron microscopy (TEM) and X-ray diffraction (XRD). The collected data evidenced a uniform distribution of Ag clusters of nanometric size after thermal treatment at 300 circC in both polyimides. For the same ion-exchange treatment parameters and annealing temperature, XRD analyses evidenced the presence of crystallites with similar sizes.

  11. Unique Bonding Properties of the Au36(SR)24 Nanocluster with FCC-Like Core.

    Science.gov (United States)

    Chevrier, Daniel M; Chatt, Amares; Zhang, Peng; Zeng, Chenjie; Jin, Rongchao

    2013-10-03

    The recent discovery on the total structure of Au36(SR)24, which was converted from biicosahedral Au38(SR)24, represents a surprising finding of a face-centered cubic (FCC)-like core structure in small gold-thiolate nanoclusters. Prior to this finding, the FCC feature was only expected for larger (nano)crystalline gold. Herein, we report results on the unique bonding properties of Au36(SR)24 that are associated with its FCC-like core structure. Temperature-dependent X-ray absorption spectroscopy (XAS) measurements at the Au L3-edge, in association with ab initio calculations, show that the local structure and electronic behavior of Au36(SR)24 are of more molecule-like nature, whereas its icosahedral counterparts such as Au38(SR)24 and Au25(SR)18 are more metal-like. Moreover, site-specific S K-edge XAS studies indicate that the bridging motif for Au36(SR)24 has different bonding behavior from the staple motif from Au38(SR)24. Our findings highlight the important role of "pseudo"-Au4 units within the FCC-like Au28 core in interpreting the bonding properties of Au36(SR)24 and suggest that FCC-like structure in gold thiolate nanoclusters should be treated differently from its bulk counterpart.

  12. High Performance Electrocatalytic Reaction of Hydrogen and Oxygen on Ruthenium Nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Ruquan; Liu, Yuanyue; Peng, Zhiwei; Wang, Tuo; Jalilov, Almaz S.; Yakobson, Boris I.; Wei, Su-Huai; Tour, James M.

    2017-01-18

    The development of catalytic materials for the hydrogen oxidation, hydrogen evolution, oxygen reduction or oxygen evolution reactions with high reaction rates and low overpotentials are key goals for the development of renewable energy. We report here Ru(0) nanoclusters supported on nitrogen-doped graphene as high-performance multifunctional catalysts for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), showing activities similar to that of commercial Pt/C in alkaline solution. For HER performance in alkaline media, sample Ru/NG-750 reaches 10 mA cm-2 at an overpotential of 8 mV with a Tafel slope of 30 mV dec-1. The high HER performance in alkaline solution is advantageous because most catalysts for ORR and oxygen evolution reaction (OER) also prefer alkaline solution environment whereas degrade in acidic electrolytes. For ORR performance, Ru/NG effectively catalyzes the conversion of O2 into OH- via a 4e process at a current density comparable to that of Pt/C. The unusual catalytic activities of Ru(0) nanoclusters reported here are important discoveries for the advancement of renewable energy conversion reactions.

  13. First-principles structure search for the stable isomers of stoichiometric WS2 nano-clusters

    CERN Document Server

    Hafizi, Roohollah; Alaei, Mojtaba; Jangrouei, MohammadReza; Akbarzadeh, Hadi

    2016-01-01

    In this paper, we employ evolutionary algorithm along with the full-potential density functional theory (DFT) computations to perform a comprehensive search for the stable structures of stoichiometric (WS2)n nano-clusters (n=1-9), within three different exchange-correlation functionals. Our results suggest that n=3, 5, 8 are possible candidates for the low temperature magic sizes of WS2 nano-clusters while at temperatures above 600 Kelvin, n=5 and 7 exhibit higher relative stability among the studied systems. The electronic properties and energy gap of the lowest energy isomers were computed within several schemes, including semilocal PBE and BLYP functionals, hybrid B3LYP functional, many body based DFT+GW approach, and time dependent DFT calculations. Vibrational spectra of the lowest lying isomers, computed by the force constant method, are used to address IR spectra and thermal free energy of the clusters. Time dependent density functional calculation in real time domain is applied to determine the full a...

  14. DNA/RNA Detection Using DNA-Templated Few-Atom Silver Nanoclusters

    Directory of Open Access Journals (Sweden)

    Hsin-Chih Yeh

    2013-04-01

    Full Text Available DNA-templated few-atom silver nanoclusters (DNA/Ag NCs are a new class of organic/inorganic composite nanomaterials whose fluorescence emission can be tuned throughout the visible and near-IR range by simply programming the template sequences. Compared to organic dyes, DNA/Ag NCs can be brighter and more photostable. Compared to quantum dots, DNA/Ag NCs are smaller, less prone to blinking on long timescales, and do not have a toxic core. The preparation of DNA/Ag NCs is simple and there is no need to remove excess precursors as these precursors are non-fluorescent. Our recent discovery of the fluorogenic and color switching properties of DNA/Ag NCs have led to the invention of new molecular probes, termed NanoCluster Beacons (NCBs, for DNA detection, with the capability to differentiate single-nucleotide polymorphisms by emission colors. NCBs are inexpensive, easy to prepare, and compatible with commercial DNA synthesizers. Many other groups have also explored and taken advantage of the environment sensitivities of DNA/Ag NCs in creating new tools for DNA/RNA detection and single-nucleotide polymorphism identification. In this review, we summarize the recent trends in the use of DNA/Ag NCs for developing DNA/RNA sensors.

  15. Spin relaxation in Si nanoclusters embedded in free-standing SiGe nanocolumns

    Science.gov (United States)

    Stepina, N. P.; Zinovieva, A. F.; Dvurechenskii, A. V.; Noda, Shuichi; Molla, Md. Zaman; Samukawa, Seiji

    2017-05-01

    Separated nanocolumns (NCs) with embedded Si nanoclusters were prepared using the top-down technique that combines a bio-template and the defect-free neutral beam etching of Si0.75Ge0.25/Si/Si0.75Ge0.25 double-quantum-well layers. The electron spin resonance (ESR) was studied in the dark and under illumination for the structures with different lateral sizes of NCs. For the structure with a NC diameter in the range of 20-25 nm, the ESR signal is characterized by the isotropic line width. The spatial separation of nanoclusters results in the suppression of the Dyakonov-Perel mechanism of spin relaxation. A decrease in the NC diameter down to 13-14 nm leads to electron localization under the bottom of NCs, making the orientation dependence of the ESR line width anisotropic. Illumination results in the increase in spin lifetimes in both the types of NC structures, relocating the electrons to the center of NCs in the narrow NC structure, and making electron localization stronger in the thick NCs.

  16. One-pot synthesis of aptamer-functionalized silver nanoclusters for cell-type-specific imaging.

    Science.gov (United States)

    Li, Jingjing; Zhong, Xiaoqin; Cheng, Fangfang; Zhang, Jian-Rong; Jiang, Li-Ping; Zhu, Jun-Jie

    2012-05-01

    As an emerging category of fluorescent metal nanoclusters, oligonucleotide-templated silver nanoclusters (Ag NCs) have attracted a lot of interest and have shown wide application in biorelated disciplines. However, the weak fluorescence emission and poor permeability to cell membranes tethered further intracellular applications of Ag NCs. AS1411 is an antiproliferative G-rich phosphodiester oligonucleotide and currently an anticancer agent under phase II clinical trials. Herein, we present a strategy to synthesize AS1411-functionalized Ag NCs with excellent fluorescence through a facile one-pot process. Confocal laser scanning microscopy and Z-axis scanning confirmed that the AS1411-functionalized Ag NCs could be internalized into MCF-7 human breast cancer cells and were able to specifically stain nuclei with red color. To our surprise, 3-[4,5-dimethylthiazol-z-yl]-2,5-diphenyltetrazolium bromide (MTT) assay demonstrated the Ag NCs were cytocompatible and showed better inhibition effects than pure AS1411 on MCF-7 human breast cancer cells. In addition, a universal design of the oligonucleotide scaffold for synthesis of Ag NCs was extended to other aptamers, such as Sgc8c and mucin 1 aptamer. Due to the facile synthesis procedure and capability of specific target recognition, this fluorescent platform will potentially broaden the applications of Ag NCs in biosensing and biological imaging.

  17. Hybrid Nanomaterials Based on Graphene and Gold Nanoclusters for Efficient Electrocatalytic Reduction of Oxygen

    Science.gov (United States)

    Wang, Changhong; Li, Na; Wang, Qiannan; Tang, Zhenghua

    2016-07-01

    Nanocomposites based on gold nanoclusters (AuNCs) with polyvinyl pyrrolidone as ligand and reduced graphene oxide (RGO) have been prepared and employed as efficient electrocatalysts for oxygen reduction reaction (ORR). AuNCs were synthesized through a wet chemical approach and then loaded onto the RGO. The as-prepared hybrid materials were pyrolyzed to remove the organic ligands. The composites were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) as well as other techniques. Electrochemical tests demonstrated that the hybrid materials exhibited effective ORR activity in alkaline media. Among a series of samples tested, the pyrolyzed sample with 50 % AuNCs mass loading exhibited the best activity, superior than AuNCs alone, RGO alone, and the others, in terms of onset potential and kinetic current density as well as durability. The method here may provide a generic approach to prepare supported noble metal nanoclusters with excellent reactivity and robust stability for ORR.

  18. Luminescent golden silk and fabric through in situ chemically coating pristine-silk with gold nanoclusters.

    Science.gov (United States)

    Zhang, Pu; Lan, Jing; Wang, Yi; Xiong, Zu Hong; Huang, Cheng Zhi

    2015-01-01

    Silk is an excellent natural material and has been used for a variety of applications. Modification of the pristine silk is usually needed depending on the intended purpose. The technical treatments involved in the modification not only should be easy, rapid, environmentally friendly, and cheap but should also retain the features of the pristine silk. Herein, we demonstrate that luminescent silk and fabric can be produced through nanotechnology. The surface of the natural silk fiber is chemically coated with luminescent gold nanoclusters (AuNCs) composed of tens to hundreds of Au atoms through a redox reaction between the protein-based silk and an Au salt precursor. The luminescent silk coated with AuNCs (called golden silk) possesses good optical properties, including a relatively long wavelength emission, high quantum yields, a long fluorescent lifetime, and photostability. Moreover, golden silk prepared this way has better mechanical properties than pristine silk, is better able to inhibit UV, and has lower toxicity in vitro. This work not only provides an effective strategy for in situ preparation of luminescent metal nanoclusters on a solid substrate but also paves the way for large-scale and industrialized production of novel silk-based materials or fabrics through nanotechnology.

  19. An intermetallic Au24Ag20 superatom nanocluster stabilized by labile ligands.

    Science.gov (United States)

    Wang, Yu; Su, Haifeng; Xu, Chaofa; Li, Gang; Gell, Lars; Lin, Shuichao; Tang, Zichao; Häkkinen, Hannu; Zheng, Nanfeng

    2015-04-01

    An intermetallic nanocluster containing 44 metal atoms, Au24Ag20(2-SPy)4(PhC≡C)20Cl2, was successfully synthesized and structurally characterized by single-crystal analysis and density funtional theory computations. The 44 metal atoms in the cluster are arranged as a concentric three-shell Au12@Ag20@Au12 Keplerate structure having a high symmetry. For the first time, the co-presence of three different types of anionic ligands (i.e., phenylalkynyl, 2-pyridylthiolate, and chloride) was revealed on the surface of metal nanoclusters. Similar to thiolates, alkynyls bind linearly to surface Au atoms using their σ-bonds, leading to the formation of two types of surface staple units (PhC≡C-Au-L, L = PhC≡C(-) or 2-pyridylthiolate) on the cluster. The co-presence of three different surface ligands allows the site-specific surface and functional modification of the cluster. The lability of PhC≡C(-) ligands on the cluster was demonstrated, making it possible to keep the metal core intact while removing partial surface capping. Moreover, it was found that ligand exchange on the cluster occurs easily to offer various derivatives with the same metal core but different surface functionality and thus different solubility.

  20. Plasmon Resonance in A-С : Н Films Modified with Platinum Nanoclusters

    Directory of Open Access Journals (Sweden)

    O. Prikhodko

    2014-07-01

    Full Text Available Optical density spectra of amorphous diamond-like films of hydrogenated carbon modified with platinum impurity (a-C : HPt have been investigated. a-C : HPt films were prepared by the method of ion plasma magnetron co-sputtering of graphite and platinum in argon-hydrogen atmosphere. Platinum content in the films was varied from 0 to 9 at. %. In the optical spectra of a-C : HPt films with different Pt content the peaks of resonance absorption in the range from 496 to 501 nm were found, whilst in the spectrum of a-C : H films the absorption peak is absent. The appearance of these absorption peaks in a-C : HPt films is explained by resonance plasmon vibrations of free electrons in platinum nanoclusters. The average diameter of the Pt nanoclusters was estimated using electromagnetic theory of Mie, and it is ~ 5 nm.

  1. Effect of helium nanoclusters on the spectroscopic properties of embedded SF6: Ionization, excitation and vibration

    Science.gov (United States)

    Dehdashti-Jahromi, M.; Farrokhpour, H.

    2017-02-01

    Ionization and excitation energies, IR and Raman spectra of sulfur hexafluoride (SF6), located inside helium (He) nanoclusters with different sizes (SF6@Hen; n = 20, 40, 60), were calculated. The effect of the cluster size on the spectroscopic properties of the SF6 was investigated and found that the Hen-SF6 interaction in the He clusters with large number of atoms is small so that the ionization and absorption energies of SF6 are not affected while for small He nanoclusters the Hen-SF6 interaction is more important. The effect of Hen-SF6 interaction and deformation of the fragments on the photoelectron and absorption spectra of SF6@Hen were separated theoretically and discussed in details. It was deduced that the effect of the cluster size on the IR and Raman vibrational frequencies of the SF6 is negligible for the cluster size range considered in this work. Density functional theory (DFT) employing M06-2X functional and 6-31 + G(df) basis set were used for optimizing the structures of SF6@Hen. Symmetry adapted cluster-configuration interaction (SAC-CI) methodology, with the same basis set, were used to calculate the ionization and excitation energies of the SF6@Hen structures. Using the calculated ionization and absorption energies and their intensities, the photoelectron and absorption spectra of the considered SF6@Hen structures were simulated and compared with the experiment.

  2. A theoretical investigation of the structural and electronic properties of 55-atom nanoclusters: The examples of Y–Tc and Pt

    Energy Technology Data Exchange (ETDEWEB)

    Batista, Krys E. A.; Piotrowski, Maurício J., E-mail: mauriciomjp@gmail.com [Department of Physics, Federal University of Pelotas, P.O. Box 354, 96010 − 900, Pelotas, RS (Brazil); Chaves, Anderson S.; Da Silva, Juarez L. F., E-mail: juarez-dasilva@iqsc.usp.br [São Carlos Institute of Chemistry, University of São Paulo, P.O. Box 780, 13560 − 970, São Carlos, SP (Brazil)

    2016-02-07

    Several studies have found that the Pt{sub 55} nanocluster adopts a distorted reduced core structure, DRC{sub 55}, in which there are 8–11 atoms in the core and 47–44 atoms in the surface, instead of the compact and high-symmetry icosahedron structure, ICO{sub 55}, with 13 and 42 atoms in the core and surface, respectively. The DRC structure has also been obtained as the putative global minimum configuration (GMC) for the Zn{sub 55} (3d), Cd{sub 55} (4d), and Au{sub 55} (5d) systems. Thus, the DRC{sub 55} structure has been reported only for systems with a large occupation of the d-states, where the effects of the occupation of the valence anti-bonding d-states might play an important role. Can we observe the DRC structure for 55-atom transition-metal systems with non-occupation of the anti-bonding d-states? To address this question, we performed a theoretical investigation of the Y {sub 55}, Zr{sub 55}, Nb{sub 55}, Mo{sub 55}, Tc{sub 55}, and Pt{sub 55} nanoclusters, employing density functional theory calculations. For the putative GMCs, we found that the Y {sub 55} adopts the ICO{sub 55} structure, while Nb{sub 55} and Mo{sub 55} adopt a bulk-like fragment based on the hexagonal close-packed structure and Tc{sub 55} adopts a face-centered cubic fragment; however, Zr{sub 55} adopts a DRC{sub 55} structure, like Zn{sub 55}, Cd{sub 55}, Pt{sub 55}, and Au{sub 55}. Thus we can conclude that the preference for DRC{sub 55} structure is not related to the occupation of the anti-bonding d-states, but to a different effect, in fact, a combination of structural and electronic effects. Furthermore, we obtained that the binding energy per atom follows the occupation of the bonding and anti-bonding model, i.e., the stability of the studied systems increases from Y to Tc with a small oscillation for Mo, which also explains the equilibrium bond lengths. We obtained a larger magnetic moment for Y {sub 55} (31 μ{sub B}) which can be explained by the localization of the d

  3. A model for the ethylene and acetylene adsorption on the surface of Cun(n = 10-15) nanoclusters: A theoretical study

    Science.gov (United States)

    Farmanzadeh, Davood; Abdollahi, Tahereh

    2016-11-01

    In this work, we report the results of density functional theory calculations of ethylene and acetylene adsorption on the most stable Cun (n = 10-15) nanoclusters, in two π and di- σ adsorption modes. Both the hydrocarbons molecularly adsorbed on the surface. Our results show that the quality of interaction of ethylene and acetylene with odd copper nanoclusters (n = 11, 13, 15) is different from what is found on even copper nanoclusters (n = 10, 12, 14). One of the interesting features of this adsorption is that acetylene never orient toward di-σ mode for Cusbnd Cu bond in odd copper nanoclusters. Also, for di- σ-CunC2H4, no stable structure is identified. The highest interaction and deformation energies are seen for the adsorption of acetylene and ethylene on Cu11 in π-mode.

  4. Investigation of nanoscale magnetic materials and devices

    Science.gov (United States)

    Rench, David William

    A host of fundamentally and technologically intriguing phenomena can be observed in ferromagnetic systems, ranging from Giant Magnetoresistance (GMR) to spin structures that approximate the non-zero entropy state of water ice. In this dissertation, we consider systems of self-assembled MnAs nanoclusters in a doped GaAs matrix, a magnetically-doped topological insulator material, and magnetotransport devices constructed as artificial spin ices. We performed magnetic, structural, and electronic measurements in each of the projects herein to discover unique materials properties that range from new phase diagrams to electronic structure breaking and intriguing electrical characteristics that seem to defy the symmetry of the system that manifests them. We first explore the impact of co-doping a GaAs semiconductor matrix with magnetic and non-magnetic dopant ions (Mn and Be, respectively) and forcing phase separation to occur during the sample growth stage. The result of this phase-separated co-doped growth was the identification of two distinct materials classes: Type I materials, in which the phase separation produces ferromagnetic zinc blende (Mn,Ga)As nanoclusters with a narrow distribution of small diameters within a weakly Be-doped GaAs matrix, and Type II materials, in which an abrupt mixing of large NiAs-type MnAs nanoclusters and the small (Mn,Ga)As nanoclusters occurs. These two states are shown to also have accessible intermediate states in the case of a doped substrate and buffer layer. Magnetic measurements are performed to determine the dynamics of the unmixed Type I and the mixed Type II materials. Structural characteristization is done at the nanoscale in a variety of instruments to precisely determine the likely growth dynamics during sample synthesis and the resultant structures. The materials are found to be superparamagnetic with 10 K (Type I) and approximately 313 K (Type II) blocking temperatures with a strong dependence on Mn content during growth

  5. A model for the ethylene and acetylene adsorption on the surface of Cu{sub n}(n = 10–15) nanoclusters: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Farmanzadeh, Davood, E-mail: d.farmanzad@umz.ac.ir; Abdollahi, Tahereh

    2016-11-01

    Highlights: • The most stable structures of Cu{sub n} (n = 10–15) were structures with C{sub S} symmetry. • It is expected that even clusters are better electron donors than the odd clusters. • Acetylene and ethylene adsorb molecularly on the Cu nanoclusters surface. • Acetylene never orient toward di-σ mode for Cu−Cu bond in odd copper nanoclusters. • For di- σ-Cu{sub n}C{sub 2}H{sub 4}, no stable structure is identified. - Abstract: In this work, we report the results of density functional theory calculations of ethylene and acetylene adsorption on the most stable Cu{sub n} (n = 10–15) nanoclusters, in two π and di- σ adsorption modes. Both the hydrocarbons molecularly adsorbed on the surface. Our results show that the quality of interaction of ethylene and acetylene with odd copper nanoclusters (n = 11, 13, 15) is different from what is found on even copper nanoclusters (n = 10, 12, 14). One of the interesting features of this adsorption is that acetylene never orient toward di-σ mode for Cu−Cu bond in odd copper nanoclusters. Also, for di- σ-Cu{sub n}C{sub 2}H{sub 4}, no stable structure is identified. The highest interaction and deformation energies are seen for the adsorption of acetylene and ethylene on Cu{sub 11} in π-mode.

  6. Investigating the adsorption of H2O on ZnO nanoclusters by first principle calculations

    KAUST Repository

    Al-Sunaidi, Abdullah A.

    2011-04-01

    The interaction of a single H2O molecule on selected ZnO nanoclusters is investigated by carrying out calculations based on the density-functional theory at the hybrid-GGA (B97-2) level. These clusters have ring, drum, tube and bubble shapes and their physical properties like the binding energy and the band gap energy depend strongly on the shape and size of the cluster. Depending on the stability of the cluster, H2O show both chemisorption and dissociation on the surfaces of the clusters. We analyzed the effect of H2O adsorption on the properties of clusters of size n = 12 via the density of state, HOMO-LUMO orbitals and the changes in the IR frequencies. © 2011 Elsevier B.V. All rights reserved.

  7. Facile Synthesis and Characterization of Au Nanoclusters-Silica Fluorescent Composite Nanospheres

    Directory of Open Access Journals (Sweden)

    Huiping Wang

    2013-01-01

    Full Text Available We developed a novel method for the synthesis of Au nanoclusters (NCs silica fluorescent composite nanospheres by mixing the as-prepared bovine serum albumin (BSA protected Au NCs with amino-modified silica spheres in acetate buffer solution. The products were characterized by high-resolution transmission electron microscopy (HRTEM, X-ray photoelectron spectroscopy (XPS, fluorescent microscope imaging (FLMI, and dynamic light scattering (DLS measurements. The proposed method was simple, efficient, and inexpensive. In addition, the composite nanospheres exhibited favorable water-dispersible, stable, and fluorescent properties, potentially leading to further applications in chemical and biological sensors. A reasonable mechanism was also proposed for the formation of composite nanospheres.

  8. Gold Doping of Silver Nanoclusters: A 26-Fold Enhancement in the Luminescence Quantum Yield

    KAUST Repository

    Soldan, Giada

    2016-04-10

    A high quantum yield (QY) of photoluminescence (PL) in nanomaterials is necessary for a wide range of applications. Unfortunately, the weak PL and moderate stability of atomically precise silver nanoclusters (NCs) suppress their utility. Herein, we accomplished a ≥26-fold PL QY enhancement of the Ag29(BDT)12(TPP)4 cluster (BDT: 1,3-benzenedithiol; TPP: triphenylphosphine) by doping with a discrete number of Au atoms, producing Ag29-xAux(BDT)12(TPP)4, x=1-5. The Au-doped clusters exhibit an enhanced stability and an intense red emission around 660nm. Single-crystal XRD, mass spectrometry, optical, and NMR spectroscopy shed light on the PL enhancement mechanism and the probable locations of the Au dopants within the cluster.

  9. Photoluminescence of oxidized silicon nanoclusters deposited on the basal plane of graphite

    Energy Technology Data Exchange (ETDEWEB)

    Dinh, L.N. (Chemistry and Materials Science Department, and Department of Applied Science, University of California, Lawrence Livermore National Laboratory, Livermore, California 94551 (United States)); Chase, L.L.; Balooch, M.; Terminello, L.J. (Chemistry and Materials Science Department, University of California, Lawrence Livermore National Laboratory, Livermore, California 94551 (United States)); Wooten, F. (Department of Applied Science, University of California, Davis/Livermore, California 94551 (United States))

    1994-12-12

    Silicon (Si) nanoclusters, with an average size of 3--5 nm in diameter, have been deposited on the basal plane of highly oriented pyrolytic graphite in an ultrahigh vacuum chamber, and investigated by scanning tunneling microscopy. Clusters passivated [ital in] [ital situ] with hydrogen or oxygen showed no detectable visible photoluminescence (PL). Prolonged exposure of the clusters to ambient air, however, resulted in strong stable red to green-blue PL spectra. Further study of these clusters by x-ray photoelectron spectroscopy and Auger electron spectroscopy revealed the existence of only SiO[sub 2] for the prolonged air-exposed samples, and the existence of SiO[sub [ital x

  10. Photoluminescence of oxidized silicon nanoclusters deposited on the basal plane of graphite

    Science.gov (United States)

    Dinh, L. N.; Chase, L. L.; Balooch, M.; Terminello, L. J.; Wooten, F.

    1994-12-01

    Silicon (Si) nanoclusters, with an average size of 3-5 nm in diameter, have been deposited on the basal plane of highly oriented pyrolytic graphite in an ultrahigh vacuum chamber, and investigated by scanning tunneling microscopy. Clusters passivated in situ with hydrogen or oxygen showed no detectable visible photoluminescence (PL). Prolonged exposure of the clusters to ambient air, however, resulted in strong stable red to green-blue PL spectra. Further study of these clusters by x-ray photoelectron spectroscopy and Auger electron spectroscopy revealed the existence of only SiO2 for the prolonged air-exposed samples, and the existence of SiOx (x ranged from 0 to 2) for the in situ oxidized samples which did not exhibit any detectable visible PL. We believe that the observed visible PL originated from defects in SiO2.

  11. Fast electronic relaxation in metal nanoclusters via excitation of coherent shape deformations: Circumventing a bottleneck

    CERN Document Server

    Kresin, V V; Kresin, Vitaly V.; Ovchinnikov, Yu. N.

    2006-01-01

    Electron-phonon relaxation in size-quantized systems may become inhibited when the spacing of discrete electron energy levels exceeds the magnitude of the phonon frequency. We show, however, that nanoclusters can support a fast nonradiative relaxation channel which derives from their distinctive ability to undergo Jahn-Teller shape deformations. Such a deformation represents a collective and coherent vibrational excitation and enables electronic transitions to occur without a multiphonon bottleneck. We analyze this mechanism for a metal cluster within the analytical framework of a three-dimensional potential well undergoing a spheroidal distortion. An expression for the time evolution of the distortion parameter is derived, the electronic level crossing condition formulated, and the probability of electronic transition at a level crossing is evaluated. An application to electron-hole recombination in a closed-shell aluminum cluster with 40 electrons shows that the short (~250 fs) excitation lifetime observed ...

  12. Contribution of Metal Defects in the Assembly Induced Emission of Cu Nanoclusters

    KAUST Repository

    Wu, Zhennan

    2017-03-20

    Aggregation/assembly induced emission (AIE) has been observed for metal nanoclusters (NCs), but the origin of the enhanced emission is not fully understood, yet. In this work, the significant contribution of metal defects on AIE is revealed by engineering the self-assembly process of Cu NCs using ethanol. The presence of ethanol leads to a rapid assembly of NCs into ultrathin nanosheets, promoting the formation of metal defects-rich surface. Detailed studies and computer simulation confirm that the metal defects-rich nanosheets possess increased Cu(I)-to-Cu(0) ratio, which greatly influences ligand-to-metal-metal charge transfer and therewith facilitates the radiative relaxation of excitons. Consequently, the Cu NCs self-assembly nanosheets exhibit obvious emission enhancement.

  13. Growth of PbS nanoclusters on specific sites of programmed oligodeoxynucleotides

    Science.gov (United States)

    Lu, Ying; Teng, Cui-Juan; Li, Ying; Wang, Hui; Xu, Chun-Hua; Hu, Shu-Xin; Li, Ming

    2015-01-01

    We develope a method to synthesize PbS nanoclusters (NCs) using guanine-containing oligodeoxynucleotides (ODNs) as templates. The NCs on the ODNs are ultra small (ranging from ˜ 0.5 nm to 2.1 nm) and luminescent in the visible region. They are characterized by photoluminescence (PL) spectra, transmission electron microscopy (TEM), and X-ray powder diffraction (XRD). The ODN-NC complexes can be used as customer-designed fluorophores which do not have the problem of multiple conjugations. The same method enables us to fabricate PbS quantum dot molecules and connect them into nanowires, expanding their potential applications in molecule electronics and quantum computing. Project supported by the National Natural Science Foundation of China (Grant Nos. 11104328, 10904164, and 11004234) and the Knowledge Innovation Program of Chinese Academy of Sciences (Grant No. kjcx3.syw.n8).

  14. Ceria nanoclusters on graphene/Ru(0001): A new model catalyst system

    Science.gov (United States)

    Novotny, Z.; Netzer, F. P.; Dohnálek, Z.

    2016-10-01

    The growth of ceria nanoclusters on single-layer graphene on Ru(0001) has been examined, with a view towards fabricating a stable system for model catalysis studies. The surface morphology and cluster distribution as a function of oxide coverage and substrate temperature has been monitored by scanning tunneling microscopy (STM), whereas the chemical composition of the cluster deposits has been determined by Auger electron spectroscopy (AES). The ceria nanoparticles are of the CeO2(111)-type and are anchored at the intrinsic defects of the graphene surface, resulting in a variation of the cluster densities across the macroscopic sample surface. The ceria clusters on graphene display a remarkable stability against reduction in ultrahigh vacuum up to 900 K, but some sintering of clusters is observed for temperatures > 450 K. The evolution of the cluster size distribution suggests that the sintering proceeds via a Smoluchowski ripening mechanism, i.e. diffusion and aggregation of entire clusters.

  15. Characterization of submonolayer film composed of soft-landed copper nanoclusters on HOPG

    Energy Technology Data Exchange (ETDEWEB)

    Mondal, Shyamal, E-mail: shyamal.mondal@saha.ac.in; Das, Pabitra; Chowdhury, Debasree; Bhattacharyya, S. R. [Saha Institute of Nuclear Physics, 1/AF Bidhan Nagar, Kolkata-700 064 (India)

    2015-06-24

    Preformed Copper nanoclusters are deposited on highly oriented pyrolytic graphite (HOPG) at very low energy. For the study of chemical composition X-ray Photoelectron Spectroscopy (XPS) is performed for a wide range of binding energy without exposing the sample in the ambient. Morphological aspects of the supported clusters are characterized employing high resolution scanning electron microscope (SEM). Different types of morphology are observed depending on the nature of the substrate surface. Big fractal islands are formed on terraces while at the step edges small islands are found to form. Ex-situ cathodoluminescence (CL) measurement shows peak at 558 nm wavelength which corresponds to the band gap of 2.22 eV which is due to Cu{sub 2}O nanocrystals formed due to oxidation of the deposited film in ambient.

  16. Search Directions for Direct H2O2 Synthesis Catalysts Starting from Au-12 Nanoclusters

    DEFF Research Database (Denmark)

    Grabow, Lars; Larsen, Britt Hvolbæk; Falsig, Hanne

    2012-01-01

    We present density functional theory calculations on the direct synthesis of H2O2 from H-2 and O-2 over an Au-12 corner model of a gold nanoparticle. We first show a simple route for the direct formation of H2O2 over a gold nanocatalyst, by studying the energetics of 20 possible elementary...... that the rate of H2O2 and H2O formation can be determined from a single descriptor, namely, the binding energy of oxygen (E-O). Our model predicts the search direction starting from an Au-12 nanocluster for an optimal catalyst in terms of activity and selectivity for direct H2O2 synthesis. Taking also stability...

  17. ZnAl-Hydrotalcite-Supported Au25 Nanoclusters as Precatalysts for Chemoselective Hydrogenation of 3-Nitrostyrene.

    Science.gov (United States)

    Tan, Yuan; Liu, Xiao Yan; Zhang, Leilei; Wang, Aiqin; Li, Lin; Pan, Xiaoli; Miao, Shu; Haruta, Masatake; Wei, Haisheng; Wang, Hua; Wang, Fangjun; Wang, Xiaodong; Zhang, Tao

    2017-03-01

    Chemoselective hydrogenation of 3-nitrostyrene to 3-vinylaniline is quite challenging because of competitive activation of the vinyl group and the nitro group over most supported precious-metal catalysts. A precatalyst comprised of thiolated Au25 nanoclusters supported on ZnAl-hydrotalcite yielded gold catalysts of a well-controlled size (ca. 2.0 nm)-even after calcination at 500 °C. The catalyst showed excellent selectivity (>98 %) with respect to 3-vinylaniline, and complete conversion of 3-nitrostyrene over broad reaction duration and temperature windows. This result is unprecedented for gold catalysts. In contrast to traditional catalysts, the gold catalyst is inert with respect to the vinyl group and is only active with regard to the nitro group, as demonstrated by the results of the control experiments and attenuated total reflection infrared spectra. The findings may extend to design of gold catalysts with excellent chemoselectivity for use in the synthesis of fine chemicals.

  18. Theoretical study of water-gas shift reaction on the silver nanocluster

    Science.gov (United States)

    Arab, Ali; Sharafie, Darioush; Fazli, Mostafa

    2017-10-01

    The kinetics of water gas shift reaction (WGSR) on the silver nanocluster was investigated using density functional theory according to the carboxyl associative mechanism. The hybrid B3PW91 functional along with the 6-31+G* and LANL2DZ basis sets were used throughout the calculations. It was observed that CO and H2O molecules adsorb physically on the Ag5 cluster without energy barrier as the initial steps of WGSR. The next three steps including H2Oads dissociation, carboxyl (OCOHads) formation, and CO2(ads) formation were accompanied by activation barrier. Transition states, as well as energy profiles of these three steps, were determined and analyzed. Our results revealed that the carboxyl and CO2(ads) formation were fast steps whereas H2Oads dissociation was the slowest step of WGSR.

  19. Antibacterial Activity of DNA-Stabilized Silver Nanoclusters Tuned by Oligonucleotide Sequence.

    Science.gov (United States)

    Javani, Siamak; Lorca, Romina; Latorre, Alfonso; Flors, Cristina; Cortajarena, Aitziber L; Somoza, Álvaro

    2016-04-27

    Silver nanoclusters (AgNCs) stabilized by DNA are promising materials with tunable fluorescent properties, which have been employed in a plethora of sensing systems. In this report, we explore their antimicrobial properties in Gram-positive and Gram-negative bacteria. After testing 9 oligonucleotides with different sequence and length, we found that the antibacterial activity depends on the sequence of the oligonucleotide employed. The sequences tested yielded fluorescent AgNCs, which can be grouped in blue, yellow, and red emitters. Interestingly, blue emitters yielded poor antibacterial activity, whereas yellow and red emitters afforded an activity similar to silver nitrate. Furthermore, structural studies using circular dichroism indicate the formation of complexes with different stability and structure, which might be one of the factors that modulate their activity. Finally, we prepared a trimeric structure containing the sequence that afforded the best antimicrobial activity, which inhibited the growth of Gram-positive and negative bacteria in the submicromolar range.

  20. Doping of magic nanoclusters in the submonolayer In/Si(100) system.

    Science.gov (United States)

    Kotlyar, V G; Zotov, A V; Saranin, A A; Chukurov, E N; Kasyanova, T V; Cherevik, M A; Pisarenko, I V; Okado, H; Katayama, M; Oura, K; Lifshits, V G

    2003-07-11

    Si(100)4 x 3-In reconstruction is essentially a superlattice of magic (identical-size) Si7In6 nanoclusters. Using scanning tunneling microscopy (STM) observations, we have found that under appropriate growth conditions up to 35% of these clusters can be modified; namely, two Si atoms in the cluster can be replaced by two In atoms, thus forming a Si5In8 cluster. This modification can be considered as a doping of the magic cluster, as it changes the electronic properties of the cluster from semiconducting towards metallic. The doped cluster is less rigid than the ordinary one and swings in the electrical field of the STM tip. The atomic structure and stability of the doped magic cluster have been examined using first-principles total-energy calculations.

  1. Intrinsically patterned two-dimensional materials for selective adsorption of molecules and nanoclusters

    Science.gov (United States)

    Lin, X.; Lu, J. C.; Shao, Y.; Zhang, Y. Y.; Wu, X.; Pan, J. B.; Gao, L.; Zhu, S. Y.; Qian, K.; Zhang, Y. F.; Bao, D. L.; Li, L. F.; Wang, Y. Q.; Liu, Z. L.; Sun, J. T.; Lei, T.; Liu, C.; Wang, J. O.; Ibrahim, K.; Leonard, D. N.; Zhou, W.; Guo, H. M.; Wang, Y. L.; Du, S. X.; Pantelides, S. T.; Gao, H.-J.

    2017-07-01

    Two-dimensional (2D) materials have been studied extensively as monolayers, vertical or lateral heterostructures. To achieve functionalization, monolayers are often patterned using soft lithography and selectively decorated with molecules. Here we demonstrate the growth of a family of 2D materials that are intrinsically patterned. We demonstrate that a monolayer of PtSe2 can be grown on a Pt substrate in the form of a triangular pattern of alternating 1T and 1H phases. Moreover, we show that, in a monolayer of CuSe grown on a Cu substrate, strain relaxation leads to periodic patterns of triangular nanopores with uniform size. Adsorption of different species at preferred pattern sites is also achieved, demonstrating that these materials can serve as templates for selective self-assembly of molecules or nanoclusters, as well as for the functionalization of the same substrate with two different species.

  2. Assembly of nanoions via electrostatic interactions: ion-like behavior of charged noble metal nanoclusters.

    Science.gov (United States)

    Yao, Qiaofeng; Luo, Zhentao; Yuan, Xun; Yu, Yue; Zhang, Chao; Xie, Jianping; Lee, Jim Yang

    2014-01-24

    The assembly of ultrasmall metal nanoclusters (NCs) is of interest to both basic and applied research as it facilitates the determination of cluster structures and the customization of cluster physicochemical properties. Here we present a facile and general approach to assemble noble metal NCs by selectively inducing electrostatic interactions between negatively-charged metal NCs and divalent cations. The charged metal NCs, which have well-defined sizes, charges and structures; and behave similarly to multivalent anions, can be considered as nanoions. These nanoions exhibit step-like assembly behavior when interacting with the counter cations - assembly only occurs when the solubility product (Ksp) between the carboxylate ions on the NC surface and the divalent cations is exceeded. The assembly here is distinctively different from the random aggregation of colloidal particles by counter ions. The nanoions would assemble into fractal-like monodisperse spherical particles with a high order of regularity that mimic the assembly of ionic crystals.

  3. Highly fluorescent silver nanoclusters in alumina-silica composite optical fiber

    Energy Technology Data Exchange (ETDEWEB)

    Halder, A.; Chattopadhyay, R.; Majumder, S.; Paul, M. C.; Das, S.; Bhadra, S. K., E-mail: skbhadra@cgcri.res.in [Fiber Optics and Photonics Division, CSIR-Central Glass and Ceramic Research Institute, 196, Raja S. C. Mullick Road, Kolkata 700032 (India); Bysakh, S.; Unnikrishnan, M. [Material Characterization Division, CSIR-Central Glass and Ceramic Research Institute, 196, Raja S. C. Mullick Road, Kolkata 700032 (India)

    2015-01-05

    An efficient visible fluorescent optical fiber embedded with silver nanoclusters (Ag-NCs) having size ∼1 nm, uniformly distributed in alumina-silica composite core glass, is reported. Fibers are fabricated in a repetitive controlled way through modified chemical vapour deposition process associated with solution doping technique. Fibers are drawn from the transparent preforms by conventional fiber drawing process. Structural characteristics of the doped fibers are studied using transmission electron microscopy and electron probe micro analysis. The oxidation state of Ag within Ag-NCs is investigated by X-ray photo electron spectroscopy. The observed significant fluorescence of the metal clusters in fabricated fibers is correlated with electronic model. The experimentally observed size dependent absorption of the metal clusters in fabricated fibers is explained with the help of reported results calculated by ab-initio density functional theory. These optical fibers may open up an opportunity of realizing tunable wavelength fiber laser without the help of rare earth elements.

  4. Light emitting devices based on Si nanoclusters: the integration with a photonic crystal and electroluminescence properties

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    We present the properties and potentialities of light emitting devices based on amorphous Si nanoclusters. Amorphous nanostructures may constitute an interesting alternative to Si nanocrystals for the monolithic integration of optical and electrical functions in Si technology. In fact, they exhibit an intense room temperature electroluminescence (EL). The EL properties of these devices have been studied as a function of current and of temperature. Moreover, to improve the extraction efficiency of the light, we have integrated the emitting system with a 2D photonic crystal structure opportunely fabricated by using conventional optical lithography to reduce the total internal reflection of the emitted light. The extraction efficiency in such devices increases by a factor of 4 at a resonance wavelength.

  5. Modeling of metal nanocluster growth on patterned substrates and surface pattern formation under ion bombardment

    Energy Technology Data Exchange (ETDEWEB)

    Numazawa, Satoshi

    2012-11-01

    This work addresses the metal nanocluster growth process on prepatterned substrates, the development of atomistic simulation method with respect to an acceleration of the atomistic transition states, and the continuum model of the ion-beam inducing semiconductor surface pattern formation mechanism. Experimentally, highly ordered Ag nanocluster structures have been grown on pre-patterned amorphous SiO{sub 2} surfaces by oblique angle physical vapor deposition at room temperature. Despite the small undulation of the rippled surface, the stripe-like Ag nanoclusters are very pronounced, reproducible and well-separated. The first topic is the investigation of this growth process with a continuum theoretical approach to the surface gas condensation as well as an atomistic cluster growth model. The atomistic simulation model is a lattice-based kinetic Monte-Carlo (KMC) method using a combination of a simplified inter-atomic potential and experimental transition barriers taken from the literature. An effective transition event classification method is introduced which allows a boost factor of several thousand compared to a traditional KMC approach, thus allowing experimental time scales to be modeled. The simulation predicts a low sticking probability for the arriving atoms, millisecond order lifetimes for single Ag monomers and {approx}1 nm square surface migration ranges of Ag monomers. The simulations give excellent reproduction of the experimentally observed nanocluster growth patterns. The second topic specifies the acceleration scheme utilized in the metallic cluster growth model. Concerning the atomistic movements, a classical harmonic transition state theory is considered and applied in discrete lattice cells with hierarchical transition levels. The model results in an effective reduction of KMC simulation steps by utilizing a classification scheme of transition levels for thermally activated atomistic diffusion processes. Thermally activated atomistic movements

  6. Role of catalysts in dehydrogenation of MgH2 nanoclusters.

    Science.gov (United States)

    Larsson, Peter; Araújo, C Moysés; Larsson, J Andreas; Jena, Puru; Ahuja, Rajeev

    2008-06-17

    A fundamental understanding of the role of catalysts in dehydrogenation of MgH(2) nanoclusters is provided by carrying out first-principles calculations based on density functional theory. It is shown that the transition metal atoms Ti, V, Fe, and Ni not only lower desorption energies significantly but also continue to attract at least four hydrogen atoms even when the total hydrogen content of the cluster decreases. In particular, Fe is found to migrate from the surface sites to the interior sites during the dehydrogenation process, releasing more hydrogen as it diffuses. This diffusion mechanism may account for the fact that a small amount of catalysts is sufficient to improve the kinetics of MgH(2), which is essential for the use of this material for hydrogen storage in fuel-cell applications.

  7. Linear and Nonlinear Optical Response in Silver Nanoclusters: Insight from a Computational Investigation (Postprint)

    Science.gov (United States)

    2016-01-05

    u( ) 8 ( ) ( ) ( , )f0 1 2 4 2 1 2 1 2 f0 1 2 2 (1) where g is a line width function, |Sf0(u1, u2 )| 2 is the two-photon probability corresponding to a...i N i i i i i i i i 1 2 2 1 f0 1 2 2 0 f 1 0 f 2 2 (2) where E1 and E2 are the energies of the two photons with unit polarization vectors u1 and u2 ...Ashenfelter et al.,19 labeled “ band 6”, and identified as the nanocluster Ag32(SG)19. In the TDDFT calculations of Bertorelle et al.,20 where the SG

  8. Algorithm based on the Thomson problem for determination of equilibrium structures of metal nanoclusters

    Science.gov (United States)

    Arias, E.; Florez, E.; Pérez-Torres, J. F.

    2017-06-01

    A new algorithm for the determination of equilibrium structures suitable for metal nanoclusters is proposed. The algorithm performs a stochastic search of the minima associated with the nuclear potential energy function restricted to a sphere (similar to the Thomson problem), in order to guess configurations of the nuclear positions. Subsequently, the guessed configurations are further optimized driven by the total energy function using the conventional gradient descent method. This methodology is equivalent to using the valence shell electron pair repulsion model in guessing initial configurations in the traditional molecular quantum chemistry. The framework is illustrated in several clusters of increasing complexity: Cu7, Cu9, and Cu11 as benchmark systems, and Cu38 and Ni9 as novel systems. New equilibrium structures for Cu9, Cu11, Cu38, and Ni9 are reported.

  9. A New Class of Atomically Precise, Hydride-Rich Silver Nanoclusters Co-Protected by Phosphines

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa

    2016-10-10

    Thiols and phosphines are the most widely used organic ligands to attain atomically precise metal nanoclusters (NCs). Here, we used simple hydrides (e.g., H–) as ligands along with phosphines, such as triphenylphosphine (TPP), 1,2-bis(diphenylphosphino)ethane [DPPE], and tris(4-fluorophenyl)phosphine [TFPP] to design and synthesize a new class of hydride-rich silver NCs. This class includes [Ag18H16(TPP)10]2+, [Ag25H22(DPPE)8]3+, and [Ag26H22(TFPP)13]2+. Our work reveals a new family of atomically precise NCs protected by H– ligands and labile phosphines, with potentially more accessible active metal sites for functionalization and provides a new set of stable NC sizes with simpler ligand–metal bonding for researchers to explore both experimentally and computationally.

  10. Size and Structure of Cytochrome-c bound to Gold nano-clusters: Effect of Ethanol

    Indian Academy of Sciences (India)

    CATHERINE GHOSH; M D ASIF AMIN; BIMAN JANA; KANKAN BHATTACHARYYA

    2017-07-01

    Size and structure of cytochrome c (Cyt C) bound to gold nano-clusters (AuNC) were studied using fluorescence correlation spectroscopy (FCS) and circular dichroism (CD) spectroscopy. The CD spectra of Cyt C indicate that the ellipticity is almost completely lost on binding to AuNC which indicates unfolding.Addition of ethanol causes partial restoration of ellipticity and hence, structure of Cyt C. FCS data indicate that size (hydrodynamic radius, rH) of free Cyt C is 17Å which increases to 24Å on binding to AuNC. This too suggests unfolding of Cyt C upon binding to AuNCs. Both the size and conformational relaxation time of Cyt C bound to AuNC vary non-monotonically with increase in ethanol content.

  11. Microscopic Fuel Particles Produced by Self-Assembly of Actinide Nanoclusters on Carbon Nanomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Na, Chongzheng [Univ. of Notre Dame, IN (United States)

    2016-10-17

    Many consider further development of nuclear power to be essential for sustained development of society; however, the fuel forms currently used are expensive to recycle. In this project, we sought to create the knowledge and knowhow that are needed to produce nanocomposite materials by directly depositing uranium nanoclusters on networks of carbon-­ based nanomaterials. The objectives of the proposed work were to (1) determine the control of uranium nanocluster surface chemistry on nanocomposite formation, (2) determine the control of carbon nanomaterial surface chemistry on nanocomposite formation, and (3) develop protocols for synthesizing uranium-­carbon nanomaterials. After examining a wide variety of synthetic methods, we show that synthesizing graphene-­supported UO2 nanocrystals in polar ethylene glycol compounds by polyol reduction under boiling reflux can enable the use of an inexpensive graphene precursor graphene oxide in the production of uranium-carbon nanocomposites in a one-­pot process. We further show that triethylene glycol is the most suitable solvent for producing nanometer-­sized UO2 crystals compared to monoethylene glycol, diethylene glycol, and polyethylene glycol. Graphene-­supported UO2 nanocrystals synthesized with triethylene glycol show evidence of heteroepitaxy, which can be beneficial for facilitating heat transfer in nuclear fuel particles. Furthermore, we show that graphene-supported UO2 nanocrystals synthesized by polyol reduction can be readily stored in alcohols, preventing oxidation from the prevalent oxygen in air. Together, these methods provide a facile approach for preparing and storing graphene-supported UO nanocrystals for further investigation and development under ambient conditions.

  12. Fabrication of highly catalytic silver nanoclusters/graphene oxide nanocomposite as nanotag for sensitive electrochemical immunoassay

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jiamian; Wang, Xiuyun; Wu, Shuo, E-mail: wushuo@dlut.edu.cn; Song, Jie; Zhao, Yanqiu; Ge, Yanqiu; Meng, Changgong

    2016-02-04

    Silver nanoclusters and graphene oxide nanocomposite (AgNCs/GRO) is synthesized and functionalized with detection antibody for highly sensitive electrochemical sensing of carcinoembryonic antigen (CEA), a model tumor marker involved in many cancers. AgNCs with large surface area and abundant amount of low-coordinated sites are synthesized with DNA as template and exhibit high catalytic activity towards the electrochemical reduction of H{sub 2}O{sub 2}. GRO is employed to assemble with AgNCs because it has large specific surface area, super electronic conductivity and strong π-π stacking interaction with the hydrophobic bases of DNA, which can further improve the catalytic ability of the AgNCs. Using AgNCs/GRO as signal amplification tag, an enzyme-free electrochemical immunosensing protocol is designed for the highly sensitive detection of CEA on the capture antibody functionalized immunosensing interface. Under optimal conditions, the designed immunosensor exhibits a wide linear range from 0.1 pg mL{sup −1} to 100 ng mL{sup −1} and a low limit of detection of 0.037 pg mL{sup −1}. Practical sample analysis reveals the sensor has good accuracy and reproducibility, indicating the great application prospective of the AgNCs/GRO in fabricating highly sensitive immunosensors, which can be extended to the detection of various kinds of low abundance disease related proteins. - Highlights: • An enzyme-free electrochemical immunosensor is reported for detecting proteins. • A silver nanocluster/graphene oxide composite is synthesized as nanotag. • The nanotags exhibit highly catalytic activity to the electro-reduction of H{sub 2}O{sub 2}. • The as-fabricated immunosensor could detect protein in serum samples.

  13. Resonance energy transfer between fluorescent BSA protected Au nanoclusters and organic fluorophores.

    Science.gov (United States)

    Raut, Sangram; Rich, Ryan; Fudala, Rafal; Butler, Susan; Kokate, Rutika; Gryczynski, Zygmunt; Luchowski, Rafal; Gryczynski, Ignacy

    2014-01-01

    Bovine serum albumin (BSA) protected nanoclusters (Au and Ag) represent a group of nanomaterials that holds great promise in biophysical applications due to their unique fluorescence properties and lack of toxicity. These metal nanoclusters have utility in a variety of disciplines including catalysis, biosensing, photonics, imaging and molecular electronics. However, they suffer from several disadvantages such as low fluorescence quantum efficiency (typically near 6%) and broad emission spectrum (540 nm to 800 nm). We describe an approach to enhance the apparent brightness of BSA Au clusters by linking them with a high extinction donor organic dye pacific blue (PB). In this conjugate PB acts as a donor to BSA Au clusters and enhances its brightness by resonance energy transfer (RET). We found that the emission of BSA Au clusters can be enhanced by a magnitude of two-fold by resonance energy transfer (RET) from the high extinction donor PB, and BSA Au clusters can act as an acceptor to nanosecond lifetime organic dyes. By pumping the BSA Au clusters using a high extinction donor, one can increase the effective brightness of less bright fluorophores like BSA Au clusters. Moreover, we prepared another conjugate of BSA Au clusters with the near infrared (NIR) dye Dylight 750 (Dy750), where BSA Au clusters act as a donor to Dy750. We observed that BSA Au clusters can function as a donor, showing 46% transfer efficiency to the NIR dye Dy750 with a long lifetime component in the acceptor decay through RET. Such RET-based probes can be used to prevent the problems of a broad emission spectrum associated with the BSA Au clusters. Moreover, transferring energy from BSA Au clusters to Dy750 will result in a RET probe with a narrow emission spectrum and long lifetime component which can be utilized in imaging applications.

  14. Glucose oxidase-functionalized fluorescent gold nanoclusters as probes for glucose

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-04-15

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

  15. Novel synthesis of gold nanoclusters templated with L-tyrosine for selective analyzing tyrosinase

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Xiaoming, E-mail: ming4444@swu.edu.cn; Luo, Yawen; Zhuo, Yan; Feng, Yuanjiao; Zhu, Shanshan

    2014-08-20

    Graphical abstract: One-pot and novel synthesized fluorescent gold nanoclusters templated with L-tyrosine (AuNCs@Tyr) were employed for investigating tyrosinase activity on the basis of aggregations of AuNCs@Tyr on its active sites during the catalysis reactions, thus leading to the fluorescence quenching of AuNCs@Tyr. - Highlights: • A novel, one-pot strategy for synthesizing fluorescent AuNCs@Tyr was proposed. • A selective and cost-effective assay for TR activity has been well established. • This AuNCs@Tyr here may broaden avenues for detecting TR in clinical applications. - Abstract: L-Tyrosine (Tyr), playing roles as both a reducing reagent and a protecting ligand, has been first employed for synthesizing fluorescent gold nanoclusters (AuNCs@Tyr) via a novel one-pot strategy. The as-prepared AuNCs@Tyr exhibited a fluorescence emission at 470 nm with a quantum yield of approximately 2.5%. Subsequently, the AuNCs@Tyr described here was applied for detections of tyrosinase (TR) activity, which was based on the mechanism of aggregations of AuNCs@Tyr occurring on the active sites of TR since TR was introduced, thus leading to the fluorescence quenching of AuNCs@Tyr. Accordingly, TR was analyzed in a linear range of 0.5–200 u mL{sup −1} with a detection limit of 0.08 u mL{sup −1} at a signal-to-noise ratio of 3. Significantly, TR has been considered as a critical marker for melanoma owing to its specifically expressing in melanoma cells. Therefore, this analytical method towards investigating TR activity may broaden avenues for meaningfully clinical applications.

  16. Green emission and Ag+ sensing of hydroxy double salt supported gold nanoclusters

    Science.gov (United States)

    Lu, Jinyang; Xu, Chunxiang; Tian, Zhengshan; Lu, Junfeng; Lin, Yi; Shi, Zengliang

    2016-02-01

    In this paper, a complex of Zn-containing hydroxy double salt (Zn-HDS) supported gold nanoclusters (AuNCs) has been synthesized. The formation of the complex (denoted as the AuNCs/Zn-HDS complex) has been analyzed by Transmission Electron Microscopy (TEM), IR spectroscopy and X-ray Photoelectron Spectroscopy (XPS). It is noteworthy that the AuNCs/Zn-HDS complex emits green fluorescence and the quantum yield is 7.6%. Based on the fluorescence quenching effect, the AuNCs/Zn-HDS complex has been employed for the sensitive detection of Ag+ and the limit of detection is 2.32 nM. The mechanisms of fluorescence generation and quenching are discussed in detail.In this paper, a complex of Zn-containing hydroxy double salt (Zn-HDS) supported gold nanoclusters (AuNCs) has been synthesized. The formation of the complex (denoted as the AuNCs/Zn-HDS complex) has been analyzed by Transmission Electron Microscopy (TEM), IR spectroscopy and X-ray Photoelectron Spectroscopy (XPS). It is noteworthy that the AuNCs/Zn-HDS complex emits green fluorescence and the quantum yield is 7.6%. Based on the fluorescence quenching effect, the AuNCs/Zn-HDS complex has been employed for the sensitive detection of Ag+ and the limit of detection is 2.32 nM. The mechanisms of fluorescence generation and quenching are discussed in detail. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07029e

  17. One-Step Synthesis of Zeolite Membranes Containing Catalytic Metal Nanoclusters.

    Science.gov (United States)

    Kim, Seok-Jhin; Tan, Shuai; Taborga Claure, Micaela; Briones Gil, Laura; More, Karren L; Liu, Yujun; Moore, Jason S; Dixit, Ravindra S; Pendergast, John G; Sholl, David S; Jones, Christopher W; Nair, Sankar

    2016-09-21

    Metal-loaded zeolitic membranes are promising candidates as catalytic membrane reactors. We report a one-step synthesis method to synthesize zeolite membranes containing metal nanoclusters, that has advantages in comparison to multistep methods such as impregnation and ion exchange. Pure-silica MFI zeolite-Pt hybrid membranes were prepared by hydrothermal synthesis with addition of 3-mercaptopropyl-trimethoxysilane (MPS) and a platinum precursor. Composition analysis and mapping by energy-dispersive X-ray spectroscopy (EDX) reveal that Pt ions/clusters are uniformly distributed along the membrane cross-section. High-magnification scanning transmission electron microscopy (STEM) analysis shows that Pt metal clusters in the hybrid zeolite membrane have a diameter distribution in the range of 0.5-2.0 nm. In contrast, a pure-silica MFI membrane synthesized from an MPS-free solution shows negligible incorporation of Pt metal clusters. To characterize the properties of the hybrid (zeolite/metal) membrane, it was used as a catalytic membrane reactor (CMR) for high-temperature propane dehydrogenation (PDH) at 600 °C and 1 atm. The results indicate that Pt metal clusters formed within the MFI zeolite membrane can serve as effective catalysts for high-temperature PDH reaction along with H2 removal via membrane permeation, thereby increasing both conversion and selectivity in relation to a conventional membrane reactor containing an equivalent amount of packed Pt catalyst in contact with an MFI membrane. The hybrid zeolite-Pt CMR also showed stable conversion and selectivity upon extended high-temperature operation (12 h), indicating that encapsulation in the zeolite allowed thermal stabilization of the Pt nanoclusters and reduced catalyst deactivation.

  18. Crystal structure of Au₂₅(SePh)₁₈ nanoclusters and insights into their electronic, optical and catalytic properties.

    Science.gov (United States)

    Song, Yongbo; Zhong, Juan; Yang, Sha; Wang, Shuxin; Cao, Tiantian; Zhang, Jun; Li, Peng; Hu, Daqiao; Pei, Yong; Zhu, Manzhou

    2014-11-21

    The crystal structure of selenolate-capped Au25(SePh)18(-) nanoclusters has been unambiguously determined for the first time, and provides a solid basis for a deeper understanding of the structure-property relationships. The selenolate-capped Au25 cluster shows noticeable differences from the previously reported Au25(SCH2CH2Ph)18(-) counterpart, albeit both share the icosahedral Au13 core and semi-ring Au2(SeR)3 or Au2(SR)3 motifs. Distinct differences in the electronic structure and optical, catalytic and electrochemical properties are revealed by the coupling experiments with density functional theory (TD-DFT) calculations. Overall, the successful determination of the Au25(SePh)18(-) structure removes any ambiguity about its structure, and comparison with the thiolated Au25 counterpart helps us to further understand how the ligands affect the properties of the nanocluster.

  19. Synthesis, Growing Processes and Physical Properties of CdS Nanoclusters in Y-Zeolite Studied by Positron Annihilation

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    Direct synthesis of CdS nanoclusters within the pore structure of Y zeolite was made. The location of CdS nanoclusters inside Y zeolite hosts was confirmed by the blue-shifted reflection absorption spectra with respected to that of bulk CdS materials. In this paper, we conducted Positron Annihilation Lifetime Spectrum (PALS) measurements on a series of CdS/Y zeolite samples and concluded that CdS clusters were not located in supercages but in smaller sodalite cages; as the CdS loading concentration increases to 5 wt%, the discrete CdS cubes begin to form bigger superclusters through interaction. The stability of CdS clusters inside the so- dalite units is due to the coordination of Cd atoms with the framework oxygen atoms of the double six-ring windows. Moreover, PALS reveals some important information of surface states existing on the interfacial layers between CdS clusters and Y zeolite.

  20. Shell effect on the electron and hole reorganization energy of core-shell II-VI nanoclusters

    Science.gov (United States)

    Cui, Xianhui; Wang, Xinqin; Yang, Fang; Cui, Yingqi; Yang, Mingli

    2017-09-01

    Density functional theory calculations were performed to study the effect of shell encapsulation on the geometrical and electronic properties of pure and hybrid core-shell CdSe nanoclusters. The CdSe cores are distorted by the shells, and the shells exhibit distinct surface activity from the cores, which leads to remarkable changes in their electron transition behaviors. Although the electron and hole reorganization energies, which are related to the formation and recombination of electron-hole pairs, vary in a complicated way, their itemized contributions, potentials of electron extraction, ionization and affinity, and hole extraction (HEP), are dependent on the cluster size, shell composition and/or solvent. Our calculations suggest that the behaviors of charge carriers, free electrons and holes, in the semiconductor core-shell nanoclusters can be modulated by selecting appropriate cluster size and controlling the chemical composition of the shells.

  1. Photocatalytic reduction of CO2 by CuxO nanocluster loaded SrTiO3 nanorod thin film

    Science.gov (United States)

    Shoji, Shusaku; Yin, Ge; Nishikawa, Masami; Atarashi, Daiki; Sakai, Etsuo; Miyauchi, Masahiro

    2016-08-01

    Photocatalytic carbon dioxide (CO2) conversion into carbon monoxide (CO) using H2O as an electron donor was achieved by the strontium titanate (SrTiO3: STO) nanorod thin films loaded with amorphous copper oxide (CuxO) nanoclusters. The loading of the CuxO-cocatalysts onto STO nanorods clearly improved the photocatalytic activity compared to bare STO nanorods. The CuxO-cocatalysts are composed of abundant and non-toxic elements, and can be loaded by using a simple and economical method. Our findings demonstrate that CuxO nanoclusters function as a general cocatalyst and can be used in combination with various semiconductors to construct low-cost and efficient photocatalytic CO2 reduction systems.

  2. Thermodynamics, kinetics, and catalytic effect of dehydrogenation from MgH2 stepped surfaces and nanocluster: a DFT study

    Science.gov (United States)

    Reich, Jason; Wang, Linlin; Johnson, Duane

    2013-03-01

    We detail the results of a Density Functional Theory (DFT) based study of hydrogen desorption, including thermodynamics and kinetics with(out) catalytic dopants, on stepped (110) rutile and nanocluster MgH2. We investigate competing configurations (optimal surface and nanoparticle configurations) using simulated annealing with additional converged results at 0 K, necessary for finding the low-energy, doped MgH2 nanostructures. Thermodynamics of hydrogen desorption from unique dopant sites will be shown, as well as activation energies using the Nudged Elastic Band algorithm. To compare to experiment, both stepped structures and nanoclusters are required to understanding and predict the effects of ball milling. We demonstrate how these model systems relate to the intermediary sized structures typically seen in ball milling experiments.

  3. Absorption and fluorescence characteristics of photo-activated adenylate cyclase nano-clusters from the amoeboflagellate Naegleria gruberi NEG-M strain

    Energy Technology Data Exchange (ETDEWEB)

    Penzkofer, A., E-mail: alfons.penzkofer@physik.uni-regensburg.de [Fakultaet fuer Physik, Universitaet Regensburg, Universitaetsstrasse 31, D-93053 Regensburg (Germany); Stierl, M.; Hegemann, P. [Institut fuer Biologie/Experimentelle Biophysik, Humboldt Universitaet zu Berlin, Invalidenstrasse 42, D-10115 Berlin (Germany); Kateriya, S. [Department of Biochemistry, University of Delhi South Campus, Benito Juarez Road, New Delhi 110021 (India)

    2012-01-02

    Graphical abstract: Protein color center emissions were observed in the wavelength range from 340 nm to 900 nm from nano-clusters of the photo-activated adenylate cyclase (nPAC) from the amoeboflagellate Naegleria gruberi. Highlights: Black-Right-Pointing-Pointer Adenylyl cyclase nPAC in aqueous pH 7.5 buffer dissolved only to nano-clusters. Black-Right-Pointing-Pointer Nano-cluster size was determined by light attenuation (scattering) measurements. Black-Right-Pointing-Pointer The size of the nano-clusters was growing by coalescing during observation period. Black-Right-Pointing-Pointer In nPAC nano-clusters color centers were present in emission range of 360-900 nm. Black-Right-Pointing-Pointer The nPAC color center emission is compared with fluorescent protein emission. - Abstract: The spectroscopic characteristics of BLUF (BLUF = sensor of blue light using flavin) domain containing soluble adenylate cyclase (nPAC = Naegleria photo-activated cyclase) samples from the amoeboflagellate Naegleria gruberi NEG-M strain is studied at room temperature. The absorption and fluorescence spectroscopic development in the dark was investigated over two weeks. Attenuation coefficient spectra, fluorescence quantum distributions, fluorescence quantum yields, and fluorescence excitation distributions were measured. Thawing of frozen nPAC samples gave solutions with varying protein nano-cluster size and varying flavin, tyrosine, tryptophan, and protein color-center emission. Protein color-center emission was observed in the wavelength range of 360-900 nm with narrow emission bands of small Stokes shift and broad emission bands of large Stokes shift. The emission spectra evolved in time with protein nano-cluster aging.

  4. pH-Sensitive gold nanoclusters: preparation and analytical applications for urea, urease, and urease inhibitor detection.

    Science.gov (United States)

    Deng, Hao-Hua; Wu, Gang-Wei; Zou, Zhi-Qiang; Peng, Hua-Ping; Liu, Ai-Lin; Lin, Xin-Hua; Xia, Xing-Hua; Chen, Wei

    2015-05-07

    Herein, we reported for the first time a facile synthetic process of gold nanoclusters (AuNCs) by using N-acetyl-L-cysteine both as a reducing agent and as a protection ligand. Based on the pH stimuli-responsive properties of the as-prepared AuNCs, we constructed a pH-sensing platform for the detection of urea, urease, and urease inhibitors.

  5. Electrophoretic deposition of ZnO nanostructures: Au nanoclusters on Si substrates induce self-assembled nanowire growth

    Energy Technology Data Exchange (ETDEWEB)

    Sandoval, Claudia [Laboratorio de Nanomateriales y Propiedades Dieléctricas, Facultad de Ciencias Exactas y Tecnología, Universidad Nacional de Tucumán, San Miguel de Tucumán (Argentina); Marin, Oscar [CONICET – LAFISO, Facultad de Ciencias Exactas y Tecnología, Universidad Nacional de Tucumán, San Miguel de Tucumán (Argentina); Real, Silvina [Laboratorio de Nanomateriales y Propiedades Dieléctricas, Facultad de Ciencias Exactas y Tecnología, Universidad Nacional de Tucumán, San Miguel de Tucumán (Argentina); Comedi, David [CONICET – LAFISO, Facultad de Ciencias Exactas y Tecnología, Universidad Nacional de Tucumán, San Miguel de Tucumán (Argentina); Tirado, Mónica, E-mail: mtirado@herrera.unt.edu.ar [Laboratorio de Nanomateriales y Propiedades Dieléctricas, Facultad de Ciencias Exactas y Tecnología, Universidad Nacional de Tucumán, San Miguel de Tucumán (Argentina)

    2014-09-15

    Highlights: • ZnO nanowires were grown on silicon substrate by electrophoretic deposition technique without use a porous template. • The growth was induced by Au nanoclusters and was performed at room temperature. • The photoluminescence spectrum for the nanowires obtained shows a broad UV-blue excitonic emission peak and a low emission in the green region. - Abstract: The present work reports the self-assembled growth of ZnO nanowires on silicon substrate with nanometer sized Au clusters using electrophoretic deposition technique at room temperature without a sacrificial template. A colloidal suspension of ≈5 nm sized ZnO nanoparticles dispersed in 2-propanol was used (nanoparticle bandgap of 3.47 eV as determined from absorbance measurements). The results show that the Au nanoclusters on the silicon substrate induce the self-assembly of the ZnO nanoparticles into vertically aligned ZnO nanowires. This effect is tentatively explained as being due to increased electric field intensities near the Au nanoclusters during the electrophoretic deposition. Photoluminescence measurements reveal the presence of quantum confined excitons and a relatively low concentration of deep defects in the nanowires. The electric field guided growth of semiconductor nanostructures at room temperature has great industrial potential as it minimizes production costs and enables the use of substrate materials not withstanding high temperatures.

  6. Modification of Deposited, Size-Selected MoS2 Nanoclusters by Sulphur Addition: An Aberration-Corrected STEM Study

    Directory of Open Access Journals (Sweden)

    Yubiao Niu

    2016-12-01

    Full Text Available Molybdenum disulphide (MoS2 is an earth-abundant material which has several industrial applications and is considered a candidate for platinum replacement in electrochemistry. Size-selected MoS2 nanoclusters were synthesised in the gas phase using a magnetron sputtering, gas condensation cluster beam source with a lateral time-of-flight mass selector. Most of the deposited MoS2 nanoclusters, analysed by an aberration-corrected scanning transmission electron microscope (STEM in high-angle annular dark field (HAADF mode, showed poorly ordered layer structures with an average diameter of 5.5 nm. By annealing and the addition of sulphur to the clusters (by sublimation in the cluster source, the clusters were transformed into larger, crystalline structures. Annealing alone did not lead to crystallization, only to a cluster size increase by decomposition and coalescence of the primary clusters. Sulphur addition alone led to a partially crystalline structure without a significant change in the size. Thus, both annealing and sulphur addition processes were needed to obtain highly crystalline MoS2 nanoclusters.

  7. Silver Nanoclusters Beacon as Stimuli-Responsive Versatile Platform for Multiplex DNAs Detection and Aptamer-Substrate Complexes Sensing.

    Science.gov (United States)

    Liu, Guoliang; Li, Jingjing; Feng, Da-Qian; Zhu, Jun-Jie; Wang, Wei

    2017-01-03

    An activatable silver nanoclusters beacon (ASNCB) was synthesized through a facile one-pot approach and applied for multiplex DNAs, small molecule, and protein sensing. Multifunctional single-stranded DNA sequences are rationally designed and used for ASNCB in situ synthesis. Via target-responsive structure transformation of ASNCB, target recognition induced ASNCB conformational transition and lit up the fluorescent signal of silver nanoclusters. By further implementing two different color ASNCBs (520 and 600 nm), the parallel multiplexed analysis of two target genes (Influenza A virus genes H1N1 and H5N1) is achieved. Additionally, with the introduction of aptamer for the design of the molecular beacon, the detections of small molecule adenosine triphosphate (ATP) and biomacromolecule thrombin have also been realized. This is the first time that an activatable fluorescent silver nanoclusters (Ag NCs)-based probe and the target recognition have been integrated into a single process, which provides a versatile platform for different analytes in a facile way. The successful application of our proposed ASNCB in real sample analysis and ATP imaging in living cells further displayed its promising potential for fluorescence sensing.

  8. Polyelectrolyte-assisted preparation of gold nanocluster-doped silica particles with high incorporation efficiency and improved stability

    Science.gov (United States)

    Wang, Haonan; Huang, Zhenzhen; Guo, Zilong; Yang, Wensheng

    2017-07-01

    In this paper, we reported an approach for efficient incorporation of glutathione-capped gold nanoclusters (GSH-Au NCs) into silica particles with the assistance of a polyelectrolyte, poly-diallyldimethyl-ammoniumchloride (PDDA). In this approach, the negatively charged GSH-Au NCs were firstly mixed with the positively charged PDDA to form PDDA-Au NC complexes. Then, the complexes were added into a pre-hydrolyzed Stöber system to get the Au NCs-doped silica particles. With increased ratio of PDDA in the complexes, the negative charges on surface of the Au NCs were neutralized gradually and finally reversed to positive in presence of excess PDDA, which facilitated the incorporation of the Au NCs into the negatively charged silica matrix. Under the optimal amount of PDDA in the complexes, the incorporation efficiency of Au NCs could be as high as 88%. After being incorporated into the silica matrix, the Au NCs become much robust against pH and heavy metal ions attributed to the protection effect of silica and PDDA. This approach was also extendable to highly efficient incorporation of other negatively charged metal nanoclusters, such as bovine serum albumin-capped Cu nanoclusters, into silica matrix.

  9. Exploring adsorption and desorption characteristics of molecular hydrogen on neutral and charged Mg nanoclusters: A first principles study

    Science.gov (United States)

    Banerjee, Paramita; Chandrakumar, K. R. S.; Das, G. P.

    2016-05-01

    To surmount the limitations of bulk MgH2 for the purpose of hydrogen storage, we report here, a detailed first principles density functional theory (DFT) based study on the structure and stability of neutral (Mgm) and positively charged (Mgm+) Mg nanoclusters of different sizes (m = 2, 4, 8 and 12) and their interaction with molecular hydrogen (H2). Our results demonstrate that H2 is weakly bound to the Mg nanoclusters through van der Waals interactions. Incorporation of Grimme's dispersion correction (D3) in the DFT based exchange-correlation functionals leads to improved accuracy of H2 interaction energy (IE) values that fall within an energy window (between physisorption and chemisorption) desirable for hydrogen storage. Energy decomposition analysis reveals the significance of polarization energy for these Mg-H2 binding. Ab-initio molecular dynamics simulation shows that complete dehydrogenation from these Mg nanoclusters occur at ∼100 °C which is a significant improvement over bulk MgH2 (∼300 °C).

  10. Ab initio study of the structural, magnetic, and electronic properties of copper and silver clusters and their alloys with one palladium atom

    Directory of Open Access Journals (Sweden)

    S. J Hashemifar

    2015-01-01

    Full Text Available In this paper, the structural, magnetic, and electronic properties of two- to nine-atom copper and silver clusters and their alloys with one palladium atom are investigated by using full-potential all-electron density functional computations. After calculating minimized energy of several structural isomers of every nanocluster, it is argued that the small size nanoclusters (up to size of 6, ‎ prefer planar structures, while by increasing size a 2D-3D structural transformation is observed. The structural transformation of pure and copper-palladium clusters occurs in the size of seven and that of silver-palladium cluster in happens at the size of six. The calculated second difference and dissociation energies confirm that the two- and eight- atom pure clusters and three- and seven- atom alloyed clusters are magic clusters. The electronic and magnetic properties of stable isomers are calculated and considered after applying many body based GW correction.

  11. Fabrication of peptide stabilized fluorescent gold nanocluster/graphene oxide nanocomplex and its application in turn-on detection of metalloproteinase-9.

    Science.gov (United States)

    Nguyen, Phuong-Diem; Cong, Vu Thanh; Baek, Changyoon; Min, Junhong

    2017-03-15

    This study introduces the double-ligands stabilizing gold nanoclusters and the fabrication of gold nanocluster/graphene nanocomplex as a "turn-on" fluorescent probe for the detection of cancer-related enzyme matrix metalloproteinase-9. A facile, one-step approach was developed for the synthesis of fluorescent gold nanoclusters using peptides and mercaptoundecanoic acid as co-templating ligands. The peptide was designed to possess a metalloproteinase-9 cleavage site and to act not only as a stabilizer but also as a targeting ligand for the enzyme detection. The prepared gold nanoclusters show an intense red fluorescence with a broad adsorption spectrum. In the presence of the enzyme, due to the excellent quenching properties and the negligible background of graphene oxide, the developed peptide-gold nanocluster/graphene nanocomplex yielded an intense "turn-on" fluorescent response, which strongly correlated with the enzyme concentration. The limit of detection of the nanocomplex was 0.15nM. The sensor was successfully applied for "turn-on" detection of metalloproteinase-9 secreted from human breast adenocarcinoma MCF-7 cells with high sensitivity, selectivity, significant improvement in terms of detection time and simplicity. Copyright © 2015 Elsevier B.V. All rights reserved.

  12. A DFT study on the formaldehyde (H2CO and (H2CO)2) monitoring using pristine B12N12 nanocluster

    Science.gov (United States)

    Shakerzadeh, Ehsan

    2016-04-01

    The interaction between formaldehyde monomer (H2CO) as well as dimer ((H2CO)2) and pristine B12N12 nanocluster is investigated at B3LYP/6-311++G(d,p) level of theory. It is found that in contrary to the pristine boron nitride nanotube and nanosheet, formaldehyde adsorption induce considerable variation in the electronic properties of the B12N12 nanocluster. Also it is shown that the pristine B12N12 cluster could adsorb up to four monomer and three dimer of formaldehyde molecules in which the HOMO-LUMO gap decreased about 38-55%. Since the conductivity of the B12N12 nanocluster changes by the adsorption of formaldehyde molecules, the presence of this toxic gas could be detected. The Bader theory of atoms in molecules (AIM) is also applied to analyze the interaction of formaldehyde with nanocluster. It is suggested pristine B12N12 nanocluster could be a promising candidate for detecting formaldehyde molecule. The results indicate that B12N12 may be a promising chemical sensor for detection of formaldehyde molecule.

  13. Influence of the ion synthesis and ion doping regimes on the effect of sensitization of erbium emission by silicon nanoclusters in silicon dioxide films

    Science.gov (United States)

    Korolev, D. S.; Kostyuk, A. B.; Belov, A. I.; Mikhaylov, A. N.; Dudin, Yu. A.; Bobrov, A. I.; Malekhonova, N. V.; Pavlov, D. A.; Tetelbaum, D. I.

    2013-11-01

    The photoluminescence spectra of erbium centers in SiO2 films with ion-synthesized silicon nanoclusters under nonresonant excitation were investigated. Erbium was introduced into thermal SiO2 films by ion implantation. The dependences of photoluminescence intensity on the dose, the order of ion implantation of Si and Er, the annealing temperature, and additional Ar+ and P+ ion irradiation regimes, i.e., factors determining the influence of radiation damage and doping on sensitization of erbium luminescence by silicon nanoclusters, were determined. It was found that the sensitization effect and its amplification due to doping with phosphorus are most pronounced under the conditions where nanoclusters are amorphous. The quenching of photoluminescence due to radiation damage in this case manifests itself to a lesser extent than for crystalline nanoclusters. The role of various factors in the observed regularities was discussed in the framework of the existing concepts of the mechanisms of light emission and energy exchange in the system of silicon nanoclusters and erbium centers.

  14. Hybrid magnetic – Semiconductor nanocomposites: optical, magnetic and nanosecond dynamical properties

    Energy Technology Data Exchange (ETDEWEB)

    Emam, A.N.; Girgis, E.; Mostafa, A.A. [National Research Center, Dokki, Giza (Egypt); Guirguis, O.W. [Biophysics Department, Faculty of Science, Cairo University, Giza (Egypt); Mohamed, M.B., E-mail: monabmohamed@gmail.com [National Institute of Laser Enhanced Science, Cairo University, Giza (Egypt); NanoTech Egypt for Photoelectronics, Dreamland, Giza (Egypt)

    2015-07-15

    A series of colloidal CdSe quantum dots doped with different concentration of cobalt ions has been prepared via organometallic pyrolysis of a mixture of cadmium stearate and cobalt dithiocarbazate. The conditions required for successful doping depend on the source of cobalt ions and the dopant concentration. The structure and morphology of the prepared nanocrystals have been characterized using X-Ray Diffraction (XRD), and Transmission Electron Microscope (TEM). Slight shift in the interplaner space was observed in the XRD pattern of the doped nanocrystals. Formation of separate cobalt nanoclusters has been observed in the TEM images upon increasing the cobalt concentration more than 2% of the original cadmium concentration. This was confirmed by magnetic measurements of the prepared samples. Room-temperature ferromagnetism has been observed, in which the switching field increases as the cobalt ratio increases. Increasing the cobalt ratio more than 5% increases the coercivity due to formation of Co{sup 0} nanoclusters. Moreover, the presence of localized magnetic ions in semiconductor QDs leads to strong exchange interactions between sp band electrons and the magnetic ions d electrons. This would influence the optical properties such as absorption, emission, as well as nanosecond relaxation dynamics. - Graphical abstract: Display Omitted - Highlights: • Hybrid semiconductor-magnetic nanostructure was prepared via chemical method. • Room-temperature ferromagnetism for hybrid CdSe–Co quantum dots has been observed. • Co{sup +2} ions induces slight shift in the interplaner space distance of the doped QDs. • Hybrid CdSe–Co QDs have better quantum yield than pure CdSe QDs. • Hybrid CdSe–Co nanocrystals have faster electron-hole dynamics than pure CdSe QDs.

  15. Interplay Between Optical Bianisotropy and Magnetism in Plasmonic Metamolecules.

    Science.gov (United States)

    Sun, Liuyang; Ma, Tzuhsuan; Yang, Seung-Cheol; Kim, Dong-Kwan; Lee, Gaehang; Shi, Jinwei; Martinez, Irving; Yi, Gi-Ra; Shvets, Gennady; Li, Xiaoqin

    2016-07-13

    The smallness of natural molecules and atoms with respect to the wavelength of light imposes severe limits on the nature of their optical response. For example, the well-known argument of Landau and Lifshitz and its recent extensions that include chiral molecules show that the electric dipole response dominates over the magneto-electric (bianisotropic) and an even smaller magnetic dipole optical response for all natural materials. Here, we experimentally demonstrate that both these responses can be greatly enhanced in plasmonic nanoclusters. Using atomic force microscopy nanomanipulation technique, we assemble a plasmonic metamolecule that is designed for strong and simultaneous optical magnetic and magneto-electric excitation. Angle-dependent scattering spectroscopy is used to disentangle the two responses and to demonstrate that their constructive/destructive interplay causes strong directional scattering asymmetry. This asymmetry is used to extract both magneto-electric and magnetic dipole responses and to demonstrate their enhancement in comparison to ordinary atomistic materials.

  16. Formation and vibrational structure of Si nano-clusters in ZnO matrix

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Serrano, J. [Universidad Autonoma del Estado de Hidalgo, Hidalgo (Mexico); Pal, U. [Universidad Autonoma de Puebla, Puebla (Mexico); Koshizaki, N.; Sasaki, T. [National Institute of Materials and Chemical Research, Ibaraki (Japan)

    2001-02-01

    We have studied the formation and vibrational structure of Si nano-clusters in ZnO matrix prepared by radio-frequency (r.f.) co-sputtering, and characterized by Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS) and Infrared (IR) spectroscopy techniques. The composite films of Si/ZnO were grown o quartz substrates by co-sputtering of Si and ZnO targets. TEM images show a homogeneous distribution of clusters in the matrix with average size varied from 3.7 nm to 34 nm depending on the temperature of annealing. IR absorption measurements revealed the bands correspond to the modes of vibrations of Si{sub 3} in its triangular geometrical structure. By analysing the IR absorption and XPS spectra we found that the nano-clusters consist of a Si{sub 3} core and a SiO{sub x} cap layer. With the increase of annealing temperature, the vibrational states of Si changed from the triplet {sup 3}B1(C2{sub v}) and {sup 3}A'{sub 2}(D{sub 3h}) states to its singlet ground state {sup 1}A{sub 1}(C2{sub v}) and the oxidation state of Si in SiO{sub x} increased. The evolution of the local atomic structure of the Si nano-clusters with the variation of Si content in the film and with the variation of the temperature of annealing are discussed. [Spanish] Se estudia la formacion y estructura vibracional de nano-cumulos de Si en matriz de ZnO preparados por la tecnica de radio-frecuencia (r.f.) co-sputtering, y caracterizados por Microscopia Electronica de Transmision (TEM), Espectroscopia Fotoelectronica de rayos X (XPS) y Espectroscopia de Infrarrojo (IR). Las peliculas compositas de Si/ZnO fueron crecidas sobre sustratos de cuarzo mediante el co-sputtering de blancos de Si y ZnO. Las imagenes de TEM mostraron una distribucion homogenea de cumulos en la matriz con un tamano promedio de 3.7 nm a 34 nm dependiendo de la temperatura de tratamiento. Las mediciones de IR relevaron las bandas correspondientes a los modos de vibracion de Si{sub 3} en su estructura

  17. Ultrasensitive electroanalysis of low-level free microRNAs in blood by maximum signal amplification of catalytic silver deposition using alkaline phosphatase-incorporated gold nanoclusters.

    Science.gov (United States)

    Si, Yanmei; Sun, Zongzhao; Zhang, Ning; Qi, Wei; Li, Shuying; Chen, Lijun; Wang, Hua

    2014-10-21

    An ultrasensitive sandwich-type analysis method has been initially developed for probing low-level free microRNAs (miRNAs) in blood by a maximal signal amplification protocol of catalytic silver deposition. Gold nanoclusters (AuNCs) were first synthesized and in-site incorporated into alkaline phosphatase (ALP) to form the ALP-AuNCs. Unexpectedly, the so incorporated AuNCs could dramatically enhance the catalysis activities of ALP-AuNCs versus native ALP. A sandwiched hybridization protocol was then proposed using ALP-AuNCs as the catalytic labels of the DNA detection probes for targeting miRNAs that were magnetically caught from blood samples by DNA capture probes, followed by the catalytic ligation of two DNA probes complementary to the targets. Herein, the ALP-AuNC labels could act as the bicatalysts separately in the ALP-catalyzed substrate dephosphorylation reaction and the AuNCs-accelerated silver deposition reaction. The signal amplification of ALP-AuNCs-catalyzed silver deposition was thereby maximized to be measured by the electrochemical outputs. The developed electroanalysis strategy could allow for the ultrasensitive detection of free miRNAs in blood with the detection limit as low as 21.5 aM, including the accurate identification of single-base mutant levels in miRNAs. Such a sandwich-type analysis method may circumvent the bottlenecks of the current detection techniques in probing short-chain miRNAs. It would be tailored as an ultrasensitive detection candidate for low-level free miRNAs in blood toward the diagnosis of cancer and the warning or monitoring of cancer metastasis in the clinical laboratory.

  18. Gold nanocluster-based vaccines for dual-delivery of antigens and immunostimulatory oligonucleotides

    Science.gov (United States)

    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

  19. NanoCluster Beacons as reporter probes in rolling circle enhanced enzyme activity detection

    Science.gov (United States)

    Juul, Sissel; Obliosca, Judy M.; Liu, Cong; Liu, Yen-Liang; Chen, Yu-An; Imphean, Darren M.; Knudsen, Birgitta R.; Ho, Yi-Ping; Leong, Kam W.; Yeh, Hsin-Chih

    2015-04-01

    As a newly developed assay for the detection of endogenous enzyme activity at the single-catalytic-event level, Rolling Circle Enhanced Enzyme Activity Detection (REEAD) has been used to measure enzyme activity in both single human cells and malaria-causing parasites, Plasmodium sp. Current REEAD assays rely on organic dye-tagged linear DNA probes to report the rolling circle amplification products (RCPs), the cost of which may hinder the widespread use of REEAD. Here we show that a new class of activatable probes, NanoCluster Beacons (NCBs), can simplify the REEAD assays. Easily prepared without any need for purification and capable of large fluorescence enhancement upon hybridization, NCBs are cost-effective and sensitive. Compared to conventional fluorescent probes, NCBs are also more photostable. As demonstrated in reporting the human topoisomerases I (hTopI) cleavage-ligation reaction, the proposed NCBs suggest a read-out format attractive for future REEAD-based diagnostics.As a newly developed assay for the detection of endogenous enzyme activity at the single-catalytic-event level, Rolling Circle Enhanced Enzyme Activity Detection (REEAD) has been used to measure enzyme activity in both single human cells and malaria-causing parasites, Plasmodium sp. Current REEAD assays rely on organic dye-tagged linear DNA probes to report the rolling circle amplification products (RCPs), the cost of which may hinder the widespread use of REEAD. Here we show that a new class of activatable probes, NanoCluster Beacons (NCBs), can simplify the REEAD assays. Easily prepared without any need for purification and capable of large fluorescence enhancement upon hybridization, NCBs are cost-effective and sensitive. Compared to conventional fluorescent probes, NCBs are also more photostable. As demonstrated in reporting the human topoisomerases I (hTopI) cleavage-ligation reaction, the proposed NCBs suggest a read-out format attractive for future REEAD-based diagnostics. Electronic

  20. G-quadruplex enhanced fluorescence of DNA-silver nanoclusters and their application in bioimaging

    Science.gov (United States)

    Zhu, Jinbo; Zhang, Libing; Teng, Ye; Lou, Baohua; Jia, Xiaofang; Gu, Xiaoxiao; Wang, Erkang

    2015-07-01

    Guanine proximity based fluorescence enhanced DNA-templated silver nanoclusters (AgNCs) have been reported and applied for bioanalysis. Herein, we studied the G-quadruplex enhanced fluorescence of DNA-AgNCs and gained several significant conclusions, which will be helpful for the design of future probes. Our results demonstrate that a G-quadruplex can also effectively stimulate the fluorescence potential of AgNCs. The major contribution of the G-quadruplex is to provide guanine bases, and its special structure has no measurable impact. The DNA-templated AgNCs were further analysed by native polyacrylamide gel electrophoresis and the guanine proximity enhancement mechanism could be visually verified by this method. Moreover, the fluorescence emission of C3A (CCCA)4 stabilized AgNCs was found to be easily and effectively enhanced by G-quadruplexes, such as T30695, AS1411 and TBA, especially AS1411. Benefiting from the high brightness of AS1411 enhanced DNA-AgNCs and the specific binding affinity of AS1411 for nucleolin, the AS1411 enhanced AgNCs can stain cancer cells for bioimaging.Guanine proximity based fluorescence enhanced DNA-templated silver nanoclusters (AgNCs) have been reported and applied for bioanalysis. Herein, we studied the G-quadruplex enhanced fluorescence of DNA-AgNCs and gained several significant conclusions, which will be helpful for the design of future probes. Our results demonstrate that a G-quadruplex can also effectively stimulate the fluorescence potential of AgNCs. The major contribution of the G-quadruplex is to provide guanine bases, and its special structure has no measurable impact. The DNA-templated AgNCs were further analysed by native polyacrylamide gel electrophoresis and the guanine proximity enhancement mechanism could be visually verified by this method. Moreover, the fluorescence emission of C3A (CCCA)4 stabilized AgNCs was found to be easily and effectively enhanced by G-quadruplexes, such as T30695, AS1411 and TBA, especially

  1. Photoinduced 2-way electron transfer in composites of metal nanoclusters and semiconductor quantum dots

    Science.gov (United States)

    Mondal, Navendu; Paul, Sneha; Samanta, Anunay

    2016-07-01

    In order to explore the potential of nanocomposites comprising semiconductor quantum dots (QDs) and metal nanoclusters (NCs) in photovoltaic and catalytic applications, the interaction between CdTe QDs and gold NCs, Au10 and Au25, stabilized by histidine, bovine serum albumin (BSA) and glutathione, is studied by an ultrafast transient absorption (TA) technique. Temporal and spectral studies of the transients reveal photoinduced 2-way electron transfer between the two constituents of the nanocomposites, where Au NCs, which generally act as electron donors when used as photosensitizers, perform the role of the efficient electron acceptor. Interestingly, it is found that the electron transfer dynamics in these composites is governed not by the distance of separation of the constituents but by the nature of the surface capping ligands. Despite a large separation between the QDs and NCs in a giant BSA-capped system, a higher electron transfer rate in this composite suggests that unlike other smaller capping agents, which act more like insulators, BSA allows much better electron conduction, as indicated previously.In order to explore the potential of nanocomposites comprising semiconductor quantum dots (QDs) and metal nanoclusters (NCs) in photovoltaic and catalytic applications, the interaction between CdTe QDs and gold NCs, Au10 and Au25, stabilized by histidine, bovine serum albumin (BSA) and glutathione, is studied by an ultrafast transient absorption (TA) technique. Temporal and spectral studies of the transients reveal photoinduced 2-way electron transfer between the two constituents of the nanocomposites, where Au NCs, which generally act as electron donors when used as photosensitizers, perform the role of the efficient electron acceptor. Interestingly, it is found that the electron transfer dynamics in these composites is governed not by the distance of separation of the constituents but by the nature of the surface capping ligands. Despite a large separation

  2. Doping effect on the Janus-like structure of a copper-iron bimetallic nanocluster and its solid-liquid phase transition

    Science.gov (United States)

    Taherkhani, Farid; Seresht, Pegah Freshteh

    2015-04-01

    A molecular dynamics simulation with a new-application potential model has been explored for melting temperature, radial distribution of iron-copper bimetallic nanoclusters, and their bulk for the first time. At low copper weight percentages, the melting temperature changes a little for the bulk structures; however, for nanostructures, the variation of melting temperature is significant. At medium copper-doping values, there is a melting-temperature plateau in bimetallic nanoclusters. For many catalysis applications, Janus-like structures are considered, which occur at around 53% iron weight in copper at room temperature, when copper-iron bimetallic nanoclusters clearly consist of two distinct faces. Our result for the melting temperature of the bulk alloy confirms the experimental result.

  3. Water soluble laurate-stabilized ruthenium(0) nanoclusters catalyst for hydrogen generation from the hydrolysis of ammonia-borane: High activity and long lifetime

    Energy Technology Data Exchange (ETDEWEB)

    Durap, Feyyaz; Zahmakiran, Mehmet; Oezkar, Saim [Department of Chemistry, Middle East Technical University, 06531 Ankara (Turkey)

    2009-09-15

    The simplest amine-borane, considered as solid hydrogen storage material, ammonia-borane (H{sub 3}NBH{sub 3}) can release hydrogen gas upon catalytic hydrolysis under mild conditions. Herein, we report the preparation of a novel catalyst, water dispersible laurate-stabilized ruthenium(0) nanoclusters from the dimethylamine-borane reduction of ruthenium(III) chloride in sodium laurate solution at room temperature. The ruthenium nanoclusters in average size of 2.6 {+-} 1.2 nm were isolated from the solution and well characterized by using TEM, XPS, FTIR, and UV-visible electronic absorption spectroscopy. The water dispersible laurate-stabilized ruthenium(0) nanoclusters were found to be highly active and long-live catalyst with a TOF of 75 mol H{sub 2}/mol Ru.min and TTO value of 5900 mol H{sub 2}/mol Ru in the hydrolysis of ammonia-borane at 25.0 {+-} 0.1 C. (author)

  4. A molecule-like PtAu24(SC6H13)18 nanocluster as an electrocatalyst for hydrogen production

    Science.gov (United States)

    Kwak, Kyuju; Choi, Woojun; Tang, Qing; Kim, Minseok; Lee, Yongjin; Jiang, De-En; Lee, Dongil

    2017-03-01

    The theoretically predicted volcano plot for hydrogen production shows the best catalyst as the one that ensures that the hydrogen binding step is thermodynamically neutral. However, the experimental realization of this concept has suffered from the inherent surface heterogeneity of solid catalysts. It is even more challenging for molecular catalysts because of their complex chemical environment. Here, we report that the thermoneutral catalyst can be prepared by simple doping of a platinum atom into a molecule-like gold nanocluster. The catalytic activity of the resulting bimetallic nanocluster, PtAu24(SC6H13)18, for the hydrogen production is found to be significantly higher than reported catalysts. It is even better than the benchmarking platinum catalyst. The molecule-like bimetallic nanocluster represents a class of catalysts that bridge homogeneous and heterogeneous catalysis and may provide a platform for the discovery of finely optimized catalysts.

  5. Fluorescence analysis of 6-mercaptopurine with the use of a nano-composite consisting of BSA-capped Au nano-clusters and core-shell Fe3O4-SiO2 nanoparticles.

    Science.gov (United States)

    Li, Zhuo; Wang, Yong; Ni, Yongnian; Kokot, Serge

    2015-08-15

    A magnetic and fluorescent nano-composite was prepared. It comprised of a core of Fe3O4 nanoparticles (NPs), a silica shell and satellitic Au nano-clusters (AuNCs) capped with bovine serum albumin (BSA). This nano-composite has many desirable properties, e.g. magnetism, red emission, high water solubility, and high resistance to photo-bleaching. On addition of the analyte, 6-mercaptopurine (6-MP) or indeed other similar thiols, AuNCs formed aggregates because the existing cross-links within the Fe3O4 NPs@SiO2 and AuNC structure were broken in favor of the gold-thiol bonds. On suitable irradiation of such aggregates, red fluorescence was emitted at 613 nm. It decreased significantly as a function of the added 6-MP concentration, and the quenching ratio (F0 - F) / F0 was related linearly to the concentration of 6-MP in the range of 0.01 to 0.5 μmol L(-1). The detection limit was 0.004 μmol L(-1) (S/N=3). The method was strongly selective for 6-MP in the presence of oxidants, phenols, heavy-metal ions, and especially bio-thiols.

  6. Quenched Assembly of NIR-Active Gold Nanoclusters Capped with Strongly Bound Ligands by Tuning Particle Charge via pH and Salinity.

    Science.gov (United States)

    Stover, Robert J; Murthy, Avinash K; Nie, Golay D; Gourisankar, Sai; Dear, Barton J; Truskett, Thomas M; Sokolov, Konstantin V; Johnston, Keith P

    2014-07-03

    Gold nanospheres coated with a binary monolayer of bound citrate and cysteine ligands were assembled into nanoclusters, in which the size and near-infrared (NIR) extinction were tuned by varying the pH and concentration of added NaCl. During full evaporation of an aqueous dispersion of 4.5 ± 1.8 nm Au primary particles, the nanoclusters were formed and quenched by the triblock copolymer polylactic acid (PLA)(1K)-b-poly(ethylene glycol) (PEG)(10K)-b-PLA(1K), which also provided steric stabilization. The short-ranged depletion and van der Waals attractive forces were balanced against longer ranged electrostatic repulsion to tune the nanocluster diameter and NIR extinction. Upon lowering the pH from 7 to 5 at a given salinity, the magnitude of the charge on the primary particles decreased, such that the weaker electrostatic repulsion increased the hydrodynamic diameter and, consequently, NIR extinction of the clusters. At a given pH, as the concentration of NaCl was increased, the NIR extinction decreased monotonically. Furthermore, the greater screening of the charges on the nanoclusters weakened the interactions with PLA(1K)-b-PEG(10K)-b-PLA(1K) and thus lowered the amount of adsorbed polymer on the nanocluster surface. The generalization of the concept of self-assembly of small NIR-active nanoclusters to include a strongly bound thiol and the manipulation of the morphologies and NIR extinction by variation of pH and salinity not only is of fundamental interest but also is important for optical biomedical imaging and therapy.

  7. Near infrared Ag/Au alloy nanoclusters: tunable photoluminescence and cellular imaging.

    Science.gov (United States)

    Wang, Chuanxi; Xu, Lin; Xu, Xiaowei; Cheng, Hao; Sun, Hongchen; Lin, Quan; Zhang, Chi

    2014-02-15

    The fluorescent nanomaterials play an important role in cellular imaging. Although the synthesis of fluorescent metal nanoclusters (NCs) have been developing rapidly, there are many technical issues in preparing metal alloy NCs. Herein, we used a facile galvanic replacement reaction to prepare Ag/Au alloy NCs. The characterizations of UV, PL, HRTEM, EDX and XPS confirm one fact the Ag/Au alloy NCs are carried out. As-prepared Ag/Au alloy NCs display near-infrared (NIR) fluorescence centered at 716 nm and show tunable luminescence from visible red (614 nm) to NIR (716 nm) by controlling the experimental Ag/Au ratios. Moreover, as-prepared Ag/Au alloy NCs are protected by glutathione (GSH) whose some functional groups including thiol, carboxyl and amino groups make the as-prepared alloy NCs exhibit good dispersion in aqueous solution, high physiological stability and favorable biocompatibility. Together with NIR fluorescence, these advantages make alloy NCs be promising candidate in biological labeling.

  8. Organic nanoclusters for nonlinear optics: from model systems to cooperative nanoassemblies with enhanced NLO responses

    Science.gov (United States)

    Terenziani, Francesca; Parthasarathy, Venkatakrishnan; Ghosh, Sampa; Pandey, Ravindra; Das, Puspendu K.; Blanchard-Desce, Mireille

    2009-08-01

    While structure-properties relationships are quite actively and successfully investigated at the molecular level of engineering of optical nonlinear responses, supramolecular structure-property relationships are an appealing field. The realization that interchromophoric interactions between strongly polar/polarizable NLO chromophores can significantly affect the NLO response of each chromophoric unit as well as promote associations has opened new dimensions for molecular design. Several elegant routes have been implemented to hinder or counterbalance dipole-dipole interactions between dipolar NLO chromophores for the elaboration of second-order materials (for SHG or electro-optical modulation). At opposite, we have implemented a reverse strategy by confining discrete numbers of NLO push-pull chromophores in close proximity within covalent organic nanoclusters with the aim to exploit interchromophoric interactions in order to achieve enhanced NLO responses. As a proof of concept, we present here the investigation of two-series of multichromophoric covalent assemblies built from NLO push-pull chromophores showing that cooperative enhancement can be achieved both for second-order optical responses (first hyperpolarizabilities) or third-order responses (two-photon absorption cross-sections).

  9. Facile Synthesis of Gd-Functionalized Gold Nanoclusters as Potential MRI/CT Contrast Agents

    Directory of Open Access Journals (Sweden)

    Wenjun Le

    2016-04-01

    Full Text Available Multi-modal imaging plays a key role in the earlier detection of disease. In this work, a facile bioinspired method was developed to synthesize Gd-functionalized gold nanoclusters (Gd-Au NCs. The Gd-Au NCs exhibit a uniform size, with an average size of 5.6 nm in dynamic light scattering (DLS, which is a bit bigger than gold clusters (3.74 nm, DLS, while the fluorescent properties of Gd-Au NCs are almost the same as that of Au NCs. Moreover, the Gd-Au NCs exhibit a high longitudinal relaxivity value (r1 of 22.111 s−1 per mM of Gd in phosphate-buffered saline (PBS, which is six times higher than that of commercial Magnevist (A complex of gadolinium with a chelating agent, diethylenetriamine penta-acetic acid, Gd-DTPA, r1 = 3.56 mM−1·s−1. Besides, as evaluated by nano single photon emission computed tomography (SPECT and computed tomography (CT the Gd-Au NCs have a potential application as CT contrast agents because of the Au element. Finally, the Gd-Au NCs show little cytotoxicity, even when the Au concentration is up to 250 μM. Thus, the Gd-Au NCs can act as multi-modal imaging contrast agents.

  10. Synthesis and optical properties of ZnO nanocluster porous films deposited by modified SILAR method

    Science.gov (United States)

    Gao, X. D.; Li, X. M.; Yu, W. D.

    2004-05-01

    Ultrasonic rinsing procedure was introduced to successive ionic layer adsorption and reaction (SILAR) method. ZnO nanocluster porous films were successfully deposited on glass substrate using zinc-ammonia complexed precursor. The crystallinity, microstructure, optical properties and photoluminescence were measured and analyzed for both as-deposited and annealed films. Effects of experimental parameters and heat treatment on the structural and optical properties were discussed. Results show that as-deposited ZnO film exhibits excellent crystallinity with the preferential orientation of (0 0 2) plane. A porous feature with interconnected particles of 200-400 nm in ZnO films was observed, with each ZnO particle formed by the aggregation of many crystallites in size of 30-50 nm. The low transmittance due to scattering losses over the porous ZnO layer down to 16% was detected. The annealing at 400 °C can promote the preferential orientation along (1 0 0) plane, the interfusion of adjacent particles and the reduction of scattering loss. Intense and sharp ultraviolet emission peaks at 392 nm dominates the PL spectra for both as-deposited and annealed samples, indicating the good optical quality of ZnO layer.

  11. Bio-NCs - the marriage of ultrasmall metal nanoclusters with biomolecules

    Science.gov (United States)

    Goswami, Nirmal; Zheng, Kaiyuan; Xie, Jianping

    2014-10-01

    Ultrasmall metal nanoclusters (NCs) have attracted increasing attention due to their fascinating physicochemical properties. Today, functional metal NCs are finding growing acceptance in biomedical applications. To achieve a better performance in biomedical applications, metal NCs can be interfaced with biomolecules, such as proteins, peptides, and DNA, to form a new class of biomolecule-NC composites (or bio-NCs in short), which typically show synergistic or novel physicochemical and physiological properties. This feature article focuses on the recent studies emerging at the interface of metal NCs and biomolecules, where the interactions could impart unique physicochemical properties to the metal NCs, as well as mutually regulate biological functions of the bio-NCs. In this article, we first provide a broad overview of key concepts and developments in the novel biomolecule-directed synthesis of metal NCs. A special focus is placed on the key roles of biomolecules in metal NC synthesis. In the second part, we describe how the encapsulated metal NCs affect the structure and function of biomolecules. Followed by that, we discuss several unique synergistic effects observed in the bio-NCs, and illustrate them with examples highlighting their potential biomedical applications. Continued interdisciplinary efforts are required to build up in-depth knowledge about the interfacial chemistry and biology of bio-NCs, which could further pave their ways toward biomedical applications.

  12. Fluorescent Gold Nanoclusters for Selective Detection of Dopamine in Cerebrospinal fluid

    Science.gov (United States)

    Govindaraju, Saravanan; Ankireddy, Seshadri Reddy; Viswanath, Buddolla; Kim, Jongsung; Yun, Kyusik

    2017-01-01

    Since the last two decades, protein conjugated fluorescent gold nanoclusters (NCs) owe much attention in the field of medical and nanobiotechnology due to their excellent photo stability characteristics. In this paper, we reported stable, nontoxic and red fluorescent emission BSA-Au NCs for selective detection of L-dopamine (DA) in cerebrospinal fluid (CSF). The evolution was probed by various instrumental techniques such as UV-vis spectroscopy, High resolution transmission electron microscopy (HTEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), photoluminescence spectroscopy (PL). The synthesised BSA-Au NCs were showing 4–6 nm with high fluorescent ~8% Quantum yield (QY). The fluorescence intensity of BSA-Au NCs was quenched upon the addition of various concentrations of DA via an electron transfer mechanism. The decrease in BSA-Au NCs fluorescence intensity made it possible to determine DA in PBS buffer and the spiked DA in CSF in the linear range from 0 to 10 nM with the limit of detection (LOD) 0.622 and 0.830 nM respectively. Best of our knowledge, as-prepared BSA-Au NCs will gain possible strategy and good platform for biosensor, drug discovery, and rapid disease diagnosis such as Parkinson’s and Alzheimer diseases. PMID:28067307

  13. DNA abasic site-directed formation of fluorescent silver nanoclusters for selective nucleobase recognition

    Science.gov (United States)

    Ma, Kun; Cui, Qinghua; Liu, Guiying; Wu, Fei; Xu, Shujuan; Shao, Yong

    2011-07-01

    DNA single-nucleotide polymorphism (SNP) detection has attracted much attention due to mutation related diseases. Various methods for SNP detection have been proposed and many are already in use. Here, we find that the abasic site (AP site) in the DNA duplex can be developed as a capping scaffold for the generation of fluorescent silver nanoclusters (Ag NCs). As a proof of concept, the DNA sequences from fragments near codon 177 of cancer supression gene p53 were used as a model for SNP detection by in situ formed Ag NCs. The formation of fluorescent Ag NCs in the AP site-containing DNA duplex is highly selective for cytosine facing the AP site and guanines flanking the site and can be employed in situ as readout for SNP detection. The fluorescent signal-on sensing for SNP based on this inorganic fluorophore is substantially advantageous over the previously reported signal-off responses using low-molecular-weight organic ligands. The strong dependence of fluorescent Ag NC formation on the sequences surrounding the AP site was successfully used to identify mutations in codon 177 of cancer supression gene p53. We anticipate that this approach will be employed to develop a practical SNP detection method by locating an AP site toward the midway cytosine in a target strand containing more than three consecutive cytosines.

  14. Imaging C. elegans with thiolated tryptophan-based NIR fluorescent gold nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Barman, Apurba Kr. [Indian Institute of Technology Kanpur, Department of Chemistry (India); Chaturbedi, Amaresh; Subramaniam, K. [Indian Institute of Technology Kanpur, Department of Biological Sciences and Bioengineering (India); Verma, Sandeep, E-mail: sverma@iitk.ac.in [Indian Institute of Technology Kanpur, Department of Chemistry (India)

    2013-11-15

    Multidentate, thiolated, tryptophan-containing peptide conjugates were synthesized for the preparation of gold nanoclusters (AuNCs). Precursor Au{sub 11}(PPh{sub 3}){sub 8}Cl{sub 3} was prepared by the reduction of HAuCl{sub 4}, followed by the use of tryptophan-containing peptide conjugates in ligand displacement reactions, to afford near-infrared fluorescent AuNCs. The emission maxima for these newly synthesized AuNCs were ∼715 nm. AuNCs were characterized with the help of UV–Vis, FTIR, fluorescence and MALDI analysis. FTIR spectra showed that the ligands bind to Au atoms through Au–S bonds, while MALDI mass spectra revealed that the clusters consisted of 20–23 Au atoms. Introduction of hydrophilic –COOH groups engendered water solubility to these AuNCs, enabling bioimaging applications. We demonstrate fluorescence imaging of the nematode C. elegans and confirm distribution of these AuNCs in nematode gut with the help of green fluorescent protein co-localization experiments.

  15. One-step synthesis of boronic acid functionalized gold nanoclusters for photoluminescence sensing of dopamine

    Science.gov (United States)

    Chen, Huide; Liu, Chunxiu; Xia, Yunsheng

    2017-03-01

    This study is the first to report one-step synthesis of boronic acid functionalized gold nanoclusters (AuNCs) using mixed ligands of 4-mercaptophenylboronic acid (MPBA) and glutathione. Furthermore, the emission color of the products can be fancily tuned from green to near-infrared by simply changing the proportion of the two stabilizers. In basic media, dopamine (DA) molecules themselves polymerize each other and form polydopamine with large amounts of cis-diol groups, which then react with boronic acid groups on the AuNC’s surface based on the formation of boronate esters. As a result, the photoluminescence of the AuNCs is well quenched by the electron transfer effect. Accordingly, DA molecules are assayed from 0.5 to 9 μM, and the detection limit is as low as 0.1 μM. The as-prepared AuNCs exhibit high selectivity; the existing biomolecules including various amino acids, ascorbic acid, uric acid, glucose, etc, do not interfere with the assay. The proposed method is successfully applied to the assay of DA in human serum, indicating its practical potential.

  16. Facile Fabrication of a Gold Nanocluster-Based Membrane for the Detection of Hydrogen Peroxide

    Directory of Open Access Journals (Sweden)

    Pu Zhang

    2016-07-01

    Full Text Available In this work, we present a simple and rapid method to synthesize red luminescent gold nanoclusters (AuNCs with high quantum yield (QY, ~16%, excellent photostability and biocompatibility. Next, we fabricated a solid membrane by loading the as-prepared AuNCs in an agar matrix. Different from nanomaterials dispersed in solution, the AuNCs-based solid membrane has distinct advantages including convenience of transportation, while still maintaining strong red luminescence, and relatively long duration storage without aggregation. Taking hydrogen peroxide (H2O2 as a typical example, we then employed the AuNCs as a luminescent probe and investigated their sensing performance, either in solution phase or on a solid substrate. The detection of H2O2 could be achieved in wide concentration ranges over 805 nM–1.61 mM and 161 μM–19.32 mM in solution and on a solid membrane, respectively, with limits of detection (LOD of 80 nM and 20 μM. Moreover, the AuNCs-based membrane could also be used for visual detection of H2O2 in the range of 0–3.22 mM. In view of the convenient synthesis route and attractive luminescent properties, the AuNCs-based membrane presented in this work is quite promising for applications such as optical sensing, fluorescent imaging, and photovoltaics.

  17. Cytotoxicity of BSA-Stabilized Gold Nanoclusters: In Vitro and In Vivo Study.

    Science.gov (United States)

    Dong, Liyun; Li, Mulin; Zhang, Song; Li, Jun; Shen, Guanxin; Tu, Yating; Zhu, Jintao; Tao, Juan

    2015-06-01

    Gold nanoclusters (Au NCs) are one of the most promising fluorescent nanomaterials for bioimaging, targeting, and cancer therapy due to their tunable optical properties, yet their biocompatibility still remains unclear. Herein, the cytotoxicity of bovine serum albumin (BSA)-stabilized Au NCs is studied by using three tumor cell lines and two normal cell lines. The results indicate that Au NCs induce the decline of cell viabilities of different cell lines to varying degrees in a dose- and time-dependent manner, and umbilical vein endothelial cells which had a higher intake of Au NCs than melanoma cells show more toxicity. Addition of free BSA to BSA-Au NCs solutions can relieve the cytotoxicity, implying that BSA can prevent cell damage. Moreover, Au NCs increase intracellular reactive oxygen species (ROS) production, further causing cell apoptosis. Furthermore, N-acetylcysteine, a ROS scavenger, partially reverses Au NCs-induced cell apoptosis and cytotoxicity, indicating that ROS might be one of the primary reasons for the toxicity of BSA-Au NCs. Surprisingly, Au NCs with concentrations of 5 and 20 nM significantly inhibit tumor growth in the xenograft mice model of human liver cancer, which might provide a new avenue for the design of anti-cancer drug delivery vehicles.

  18. Comparison of photoluminescence properties of HSA-protected and BSA-protected Au25 nanoclusters

    Science.gov (United States)

    Tsukamoto, Masato; Kawasaki, Hideya; Saitoh, Tadashi; Inada, Mitsuru; Kansai Univ. Collaboration

    Gold nanoclusters (NCs) have attracted great interest for a wide range of applications. In particular, red light-emitting Au25 NCs have been prepared with various biological ligands. It has been shown that Au25 NCs have Au13-core/6Au2(SR)3-semiring structure. The red luminescence thought to be originated from both core (670 nm) and semiring (625 nm). It is important to reveal a structure of Au25 NCs to facilitate the progress of applications. However, the precise structure of Au25 NCs has not been clarified. There is a possibility of obtaining structural information about Au25 NCs to compare optical properties of the NCs that protected by slightly different molecules. Bovine and human serum albumin (BSA, HSA) are suitable one for this purpose. It has been suggested that rich tyrosine and cysteine residues in these molecules are important to produce the thiolate-protected Au NCs. If Au25 NCs have core/shell structure, only the luminescence of the semiring will be affected by the difference of the albumin molecules. We carefully compared PL characteristics of BSA- and HSA- protected Au25 NCs. As a result, there was no difference in the PL at 670 nm (core), while differences were observed in the PL at 625 nm (semiring). The results support that Au25 NCs have core/semiring structure.

  19. Ag nanocluster/DNA hybrids: functional modules for the detection of nitroaromatic and RDX explosives.

    Science.gov (United States)

    Enkin, Natalie; Sharon, Etery; Golub, Eyal; Willner, Itamar

    2014-08-13

    Luminescent Ag nanoclusters (NCs) stabilized by nucleic acids are implemented as optical labels for the detection of the explosives picric acid, trinitrotoluene (TNT), and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX). The sensing modules consist of two parts, a nucleic acid with the nucleic acid-stabilized Ag NCs and a nucleic acid functionalized with electron-donating units, including L-DOPA, L-tyrosine and 6-hydroxy-L-DOPA, self-assembled on a nucleic acid scaffold. The formation of donor-acceptor complexes between the nitro-substituted explosives, exhibiting electron-acceptor properties, and the electron-donating sites, associated with the sensing modules, concentrates the explosives in close proximity to the Ag NCs. This leads to the electron-transfer quenching of the luminescence of the Ag NCs by the explosive molecule. The quenching of the luminescence of the Ag NCs provides a readout signal for the sensing process. The sensitivities of the analytical platforms are controlled by the electron-donating properties of the donor substituents, and 6-hydroxy-L-DOPA was found to be the most sensitive donor. Picric acid, TNT, and RDX are analyzed with detection limits corresponding to 5.2 × 10(-12) M, 1.0 × 10(-12) M, and 3.0 × 10(-12) M, respectively, using the 6-hydroxy-L-DOPA-modified Ag NCs sensing module.

  20. Synthesis and Optical Properties of a Dithiolate/Phosphine-Protected Au28 Nanocluster

    KAUST Repository

    Aljuhani, Maha A.

    2016-12-17

    While monothiols and simple phosphines are commonly exploited for size-controlled synthesis of atomically precise gold nanoclusters (NCs), dithiols or dithiol-phosphine combinations are seldom applied. Herein, we used a dithiol (benzene-1,3-dithiol, BDT) and a phosphine (triphenylphosphine, TPP) together as ligands and synthesized an atomically precise gold NC with the formula [Au28(BDT)4(TPP)9]2+. This NC exhibited multiple absorption features and a charge of +2, which are distinctly different from the reported all-thiolated [Au28(SR)20]0 NC (SR: monothiolate). The composition of [Au28(BDT)4(TPP)9]2+ NC was deduced from high-resolution electrospray ionization mass spectrometry (ESI MS) and it was further corroborated by thermogravimetric analysis (TGA). Differential pulse voltammetry (DPV) revealed a HOMO–LUMO gap of 1.27 eV, which is in good agreement with the energy gap of 1.3 eV obtained from its UV–vis spectrum. The successful synthesis of atomically precise, dithiol-protected Au28 NC would stimulate theoretical and experimental research into bidentate ligands as a new path for expanding the library of different metal NCs, which have so far been dominated by monodentate thiols.

  1. Ultrasmall near-infrared gold nanoclusters for tumor fluorescence imaging in vivo

    Science.gov (United States)

    Wu, Xu; He, Xiaoxiao; Wang, Kemin; Xie, Can; Zhou, Bing; Qing, Zhihe

    2010-10-01

    In this paper, we explore the possibility of using ultrasmall near-infrared (NIR) gold nanoclusters (AuNCs) as novel contrast imaging agents for tumor fluorescence imaging in vivo. The fluorescence imaging signal of the tail vein administrated AuNCs in living organisms can spectrally be well distinguished from the background with maximum emission wavelength at about 710 nm, and the high photostability of AuNCs promises continuous imaging in vivo. The uptake of AuNCs by the reticuloendothelial system is relatively low in comparison with other nanoparticle-based contrast imaging agents due to their ultrasmall hydrodynamic size (~2.7 nm). Through the body weight change analysis, the results show that the body weight of the mice administrated with AuNCs has not been changed obviously in comparison with that of the control mice injected with PBS. Furthermore, using MDA-MB-45 and Hela tumor xenograft models, in vivo and ex vivo imaging studies show that the ultrasmall NIR AuNCs are able to be highly accumulated in the tumor areas, thanks to the enhanced permeability and retention (EPR) effects. And the tumor-to-background ratio is about 15 for 6 h postinjection. The results indicate that the ultrasmall NIR AuNCs appear as very promising contrast imaging agents for in vivo fluorescence tumor imaging.

  2. Nano-cluster stability following neutron irradiation in MA957 oxide dispersion strengthened material

    Energy Technology Data Exchange (ETDEWEB)

    Ribis, J., E-mail: joel.ribis@cea.fr [CEA, DEN, DMN, SRMA, F-91191 Gif sur Yvette (France); Lozano-Perez, S. [Department of Materials, University of Oxford, Parks Road, OX1 3PH Oxford (United Kingdom)

    2014-01-15

    ODS steels are promising materials for Sodium cooled Fast Reactors since their fine distribution of nano-clusters confers excellent mechanical properties. However, the nano-feature stability needs to be assessed under neutron irradiation. Before irradiation, the characterizations show that nano-particles are finely distributed within the ferritic matrix and are identified to have a pyrochlore type structure. After irradiation of the MA957 alloy in the Phenix French reactor at 412 °C up to 50 dpa and 430 °C up to 75 dpa, transmission electron microscopy characterization reveals a very slight density fall but no distinguishable difference in nano-features size before and after irradiation. In addition, after both irradiations, the nano-oxides are still (Y, Ti, O) compounds with orientation relationship with the matrix. A multislice simulation of high resolution images suggests that nano-particles still have a fcc pyrochlore type structure after irradiation. A possible change of lattice parameter seems to be highlighted, possibly due to disordering by cascade effect.

  3. Copper nano-clusters prepared by one-step electrodeposition and its application on nitrate sensing

    Directory of Open Access Journals (Sweden)

    Y. Li

    2015-04-01

    Full Text Available This paper describes the fabrication and characterization of copper nano-clusters prepared by a simple one-step electrodeposition process on platinum microelectrode, and the application for nitrate determination. The one-step electrodepostion process was performed by chronoamperometry scan in acidic copper sulphate electrolyte directly. The SEM and electrochemical examination showed that the morphologies and microstructures of deposited copper layers can be precisely controlled by using different deposition voltages. It was found that the copper layer is porous when the deposition voltage is higher than -500 mV, and this porous layer has a larger effective surface area compared with the corresponding smooth flat copper layer deposited under voltage less than -300 mV. Under the optimized deposition voltage, copper clusters constructed by uniform nanoparticles with an average diameter of about 100 nm can be obtained. The mechanism of electrodeposition process for this method was also speculated. The copper layers deposited under different voltages are used in a series of tests in order to evaluate their performance for nitrate sensing. The experimental results reveal that the microelectrode modified by fixed potential deposition under -700 mV had a higher sensitivity of 39.31 μA/mmolL−1 for nitrate detection within the concentration ranging from 0.1 mmolL−1 to 4.0 mmolL−1.

  4. A new approach to studying the luminescence spectra of free icosahedral and crystalline argon nanoclusters

    Science.gov (United States)

    Doronin, Yu. S.; Vakula, V. L.; Kamarchuk, G. V.; Tkachenko, A. A.; Samovarov, V. N.

    2016-02-01

    We propose a new approach to analyzing the cathodoluminescence spectra of free argon nanoclusters, forming in a supersonic jet flowing into vacuum. Based on this approach, we conduct an analysis of the intensities of the luminescence bands of neutral and charged excimer complexes (Ar2)* and (Ar+4)*, measured for clusters with an average size ranging from 500 to 8900 atoms per cluster, and a diameter of 32-87 Å. It is shown that the concentration of the substance condensed into clusters, which determines the integrated intensity of the bands, is proportional to the logarithm of the average size of the clusters in the jet. An analysis of the normalized intensities of the (Ar2)* and (Ar+4)* bands for crystalline clusters with an fcc structure allowed us to establish that the luminescence of neutral (Ar2)* molecules comes from within the volume of the cluster, while the charged complexes (Ar+4)* emit from the subsurface layer. We highlighted an area of cluster dimensions at which the jet is dominated by quasi-crystalline clusters with an icosahedral structure, and it is shown that the transition from icosahedral clusters to fcc structures occurs when the average size of the cluster in the jet is N ¯ = (1000-1800) atoms/cluster.

  5. Relative edge energy in the stability of transition metal nanoclusters of different motifs.

    Science.gov (United States)

    Zhao, X J; Xue, X L; Guo, Z X; Li, S F

    2016-07-07

    When a structure is reduced to a nanometer scale, the proportion of the edge atoms increases significantly, which can play a crucial role in determining both their geometric and electronic properties, as demonstrated by the recently established generalized Wulff construction principle [S. F. Li, et al., Phys. Rev. Lett., 2013, 111, 115501]. Consequently, it is of great interest to clarify quantitatively the role of the edge atoms that dominate the motifs of these nanostructures. In principle, establishing an effective method valid for determining the absolute value of the surface energy and particularly the edge energy for a given nanostructure is expected to resolve such a problem. However, hitherto, it is difficult to obtain the absolute edge energy of transition metal clusters, particularly when their sizes approach the nanometer regime. In this paper, taking Ru nanoclusters as a prototypical example, our first-principles calculations introduce the concept of relative edge energy (REE), reflecting the net edge atom effect over the surface (facet) atom effect, which is fairly powerful to quasi-quantitatively estimate the critical size at which the crossover occurs between different configurations of a given motif, such as from an icosahedron to an fcc nanocrystal. By contrast, the bulk effect should be re-considered to rationalize the power of the REE in predicting the relative stability of larger nanostructures between different motifs, such as fcc-like and hcp-like nanocrystals.

  6. Oligonucleotide-stabilized fluorescent silver nanoclusters for the specific and sensitive detection of biotin.

    Science.gov (United States)

    Xiong, Xiaoli; Tang, Yan; Zhao, Jingjin; Zhao, Shulin

    2016-02-21

    A novel biotin fluorescent probe based on oligonucleotide-stabilized silver nanoclusters (DNA-AgNCs) was synthesized by employing a biotinylated cytosine-rich sequence as a synthesized template. The fluorescence properties of the DNA-AgNCs are related to the modified position of the DNA. When biotin is linked to the middle thymine base of the DNA sequence, the DNA-AgNCs emit the strongest fluorescence. Moreover, the stability of the DNA-AgNCs was affected by avidin through biotin-avidin binding, quenching the fluorescence of the DNA-AgNCs. In contrast, if free biotin is further introduced into this system, the quenching is apparently weakened by competition, leading to the restoration of fluorescence. This phenomenon can be utilized for the detection of biotin. Under the optimal conditions, the fluorescence recovery is linearly proportional to the concentration of biotin in the range of 10 nM-1.0 μM with a detection limit of 6.0 nM. This DNA-AgNCs probe with excellent fluorescent properties is sensitive and selective for the detection of biotin and has been applied for the determination of biotin in wheat flour.

  7. Bio-NCs--the marriage of ultrasmall metal nanoclusters with biomolecules.

    Science.gov (United States)

    Goswami, Nirmal; Zheng, Kaiyuan; Xie, Jianping

    2014-11-21

    Ultrasmall metal nanoclusters (NCs) have attracted increasing attention due to their fascinating physicochemical properties. Today, functional metal NCs are finding growing acceptance in biomedical applications. To achieve a better performance in biomedical applications, metal NCs can be interfaced with biomolecules, such as proteins, peptides, and DNA, to form a new class of biomolecule-NC composites (or bio-NCs in short), which typically show synergistic or novel physicochemical and physiological properties. This feature article focuses on the recent studies emerging at the interface of metal NCs and biomolecules, where the interactions could impart unique physicochemical properties to the metal NCs, as well as mutually regulate biological functions of the bio-NCs. In this article, we first provide a broad overview of key concepts and developments in the novel biomolecule-directed synthesis of metal NCs. A special focus is placed on the key roles of biomolecules in metal NC synthesis. In the second part, we describe how the encapsulated metal NCs affect the structure and function of biomolecules. Followed by that, we discuss several unique synergistic effects observed in the bio-NCs, and illustrate them with examples highlighting their potential biomedical applications. Continued interdisciplinary efforts are required to build up in-depth knowledge about the interfacial chemistry and biology of bio-NCs, which could further pave their ways toward biomedical applications.

  8. Papain-templated Cu nanoclusters: assaying and exhibiting dramatic antibacterial activity cooperating with H₂O₂.

    Science.gov (United States)

    Miao, Hong; Zhong, Dan; Zhou, Zinan; Yang, Xiaoming

    2015-12-07

    Herein, papain-functionalized Cu nanoclusters (CuNCs@Papain) were originally synthesized in aqueous solution together with a quantum yield of 14.3%, and showed obviously red fluorescence at 620 nm. Meanwhile, their corresponding fluorescence mechanism was fully elucidated by fluorescence spectroscopy, HR-TEM, FTIR spectroscopy, and XPS. Subsequently, the as-prepared CuNCs were employed as probes for detecting H2O2. Using CuNCs as probes, H2O2 was determined in the range from 1 μM to 50 μM based on a linear decrease of fluorescence intensity as well as a detection limit of 0.2 μM with a signal-to-noise ratio of 3. More significantly, it has been proved that CuNCs could convert H2O2 to ˙OH, which exhibited dramatic antibacterial activity. Both in vitro and in vivo experiments were performed to validate their antibacterial activity against Gram-positive/negative bacteria and actual wound infection, suggesting their potential for serving as one type of promising antibacterial material.

  9. Charge-transfer optical absorption mechanism of DNA:Ag-nanocluster complexes

    Science.gov (United States)

    Longuinhos, R.; Lúcio, A. D.; Chacham, H.; Alexandre, S. S.

    2016-05-01

    Optical properties of DNA:Ag-nanoclusters complexes have been successfully applied experimentally in Chemistry, Physics, and Biology. Nevertheless, the mechanisms behind their optical activity remain unresolved. In this work, we present a time-dependent density functional study of optical absorption in DNA:Ag4. In all 23 different complexes investigated, we obtain new absorption peaks in the visible region that are not found in either the isolated Ag4 or isolated DNA base pairs. Absorption from red to green are predominantly of charge-transfer character, from the Ag4 to the DNA fragment, while absorption in the blue-violet range are mostly associated to electronic transitions of a mixed character, involving either DNA-Ag4 hybrid orbitals or intracluster orbitals. We also investigate the role of exchange-correlation functionals in the calculated optical spectra. Significant differences are observed between the calculations using the PBE functional (without exact exchange) and the CAM-B3LYP functional (which partly includes exact exchange). Specifically, we observe a tendency of charge-transfer excitations to involve purines bases, and the PBE spectra error is more pronounced in the complexes where the Ag cluster is bound to the purines. Finally, our results also highlight the importance of adding both the complementary base pair and the sugar-phosphate backbone in order to properly characterize the absorption spectrum of DNA:Ag complexes.

  10. Zwitterion functionalized gold nanoclusters for multimodal near infrared fluorescence and photoacoustic imaging

    Directory of Open Access Journals (Sweden)

    Danjin Shen

    2017-05-01

    Full Text Available Gold nanoclusters (Au NCs are an emerging type of theranostic agents combining therapeutic and imaging features with reduced toxicity. Au NCs stabilized by a zwitterion ligand with a fine control of the metal core size and the ligand coverage were synthesized by wet chemistry. Intense fluorescence signal is reported for the highest ligand coverage, whereas photoacoustic signal is stronger for the largest metal core. The best Au NC candidate with an average molecular weight of 17 kDa could be detected with high sensitivity on a 2D-near-infrared imaging instrument (limit of detection (LOD = 2.3 μM and by photoacoustic imaging. In vitro and in vivo experiments demonstrate an efficient cell uptake in U87 cell lines, a fast renal clearance (t1/2α = 6.5 ± 1.3 min, and a good correlation between near infrared fluorescence and photoacoustic measurements to follow the early uptake of Au NCs in liver.

  11. Boron carbide nanoclusters as H2 and N2 gases nanosensors: theoretical investigation

    Science.gov (United States)

    Fallahpour, F.; Gorgani, S. Soleimani; Nouraliei, M.

    2016-08-01

    Interactions between boron carbide nanoclusters (B16C16 and B24C24) and H2 and N2 molecules have been investigated using the structural and electronic properties of the adsorbate/cluster complexes derived from density functional theory. The adsorption energies of the most stable configurations have been calculated to be about -0.13, -0.66 eV for H2 and N2 adsorbed on the B16C16 surface and -1.05, -3.80 eV for H2 and N2 adsorbed on the B24C24 surface, respectively. Moreover, the interaction between H2 and the B16C16 has induced dramatic changes to the cluster electronic properties, so that the HOMO/LUMO gap of the cluster decreases to its original value. It has been shown that this phenomenon has led to an increment in the electrical conductivity of the cluster at a definite temperature. Thus, this work suggests that the B16C16 and B24C24 nano-cages function selectively as a gas sensor device for H2 and N2 molecules.

  12. Tuning luminescent properties of CdSe nanoclusters by phosphine surface passivation

    Science.gov (United States)

    Lysova, Iryna; Anton, Halina; Dmitruk, Igor; Mely, Yves

    2016-12-01

    Appropriate surface ligands are required for tuning the physicochemical and photophysical properties of nanoclusters (NCs). These surface ligands are especially critical for passivating the small (CdSe)33,34 NCs where the majority of atoms are at the NC surface. In this study, triphenylphosphine (TPP), trioctylphosphine (TOP) and tris(pentafluorophenyl)phosphine (TPFP) have been tested as capping agents for alkylamine-coated CdSe NCs. TPP and TOP compounds are found to increase the quantum yield of photoluminescence (PL) from 0.15% to 0.6% and 0.53%, respectively, and to preserve this increased PL with time, probably by preventing charge leakage as a result of their binding to Se atoms. Since no dramatic change in the shape of NCs’ PL spectrum occurs after surface treatment, both the exciton band and the low-energy broad band in magic NCs are thought to describe the intrinsic luminescence properties of the NCs. As a result, the PL increase due to Se passivation is thought to be mainly caused by a decrease in the efficiency of the NC nonradiative pathways.

  13. Probing the Absorption and Emission Transition Dipole Moment of DNA Stabilized Silver Nanoclusters.

    Science.gov (United States)

    Hooley, Emma N; Carro-Temboury, Miguel R; Vosch, Tom

    2017-02-09

    Using single molecule polarization measurements, we investigate the excitation and emission polarization characteristics of DNA stabilized silver nanoclusters (C24-AgNCs). Although small changes in the polarization generally accompany changes to the emission spectrum, the emission and excitation transition dipoles tend to be steady over time and aligned in a similar direction, when immobilized in PVA. The emission transition dipole patterns, observed for C24-AgNCs in defocused wide field imaging, match that of a single emitter. The small changes to the polarization and spectral shifting that were observed could be due to changes to the conformation of the AgNC or the DNA scaffold. Although less likely, an alternative explanation could be that several well aligned spectrally similar emitters are present within the DNA scaffold which, due to Förster resonance energy transfer (FRET) processes such as energy hopping, energy transfer, and singlet-singlet annihilation, behave as a single emitter. The reported results can provide more insight in the structural and photophysical properties of DNA-stabilized AgNCs.

  14. Storage of Gold Nanoclusters in Muscle Leads to their Biphasic in Vivo Clearance

    CERN Document Server

    Zhang, Xiao-Dong; Chen, Jie; Wang, Hao; Song, Sha Sha; Shen, Xiu; Long, Wei; Sun, Yuan-Ming; Fan, Saijun; Zheng, Kaiyuan; Leong, David Tai; Xie, Jianping

    2014-01-01

    Ultrasmall gold nanoclusters show great potential in biomedical applications. Long term biodistribution, retention, toxicity, and pharmacokinetics profiles are prerequisites in their potential clinical applications. Here we systematically investigated the biodistribution, clearance, and toxicity of one widely used Au NC species glutathione protected Au NCs or GSH Au NCs, over a relatively long period of 90 days in mice. We observed that most of the Au NCs were cleared at 30 days post injection with a major accumulation in liver and kidney. However, it is surprising that an abnormal increase of Au amount in the heart, liver, spleen, lung, and testis was observed at 60 and 90 days, indicating that the injected Au NCs formed a V shaped time dependent distribution profile in various organs. Further investigations revealed that Au NCs were steadily accumulating in the muscle in the first 30 days p.i., and the as stored Au NCs gradually released into blood in 30 to 90 days, which induced a redistribution and reaccu...

  15. Morphology and atomic-scale structure of single-layer WS2 nanoclusters.

    Science.gov (United States)

    Füchtbauer, Henrik G; Tuxen, Anders K; Moses, Poul G; Topsøe, Henrik; Besenbacher, Flemming; Lauritsen, Jeppe V

    2013-10-14

    Two-dimensional sheets of transition metal (Mo and W) sulfides are attracting strong attention due to the unique electronic and optical properties associated with the material in its single-layer form. The single-layer MoS2 and WS2 are already in widespread commercial use in catalytic applications as both hydrotreating and hydrocracking catalysts. Consequently, characterization of the morphology and atomic structure of such particles is of utmost importance for the understanding of the catalytic active phase. However, in comparison with the related MoS2 system only little is known about the fundamental properties of single-layer WS2 (tungstenite). Here, we use an interplay of atom-resolved Scanning Tunneling Microscopy (STM) studies of Au(111)-supported WS2 nanoparticles and calculated edge structures using Density Functional Theory (DFT) to reveal the equilibrium morphology and prevalent edge structures of single-layer WS2. The STM results reveal that the single layer S-W-S sheets adopt a triangular equilibrium shape under the sulfiding conditions of the synthesis, with fully sulfided edges. The predominant edge structures are determined to be the (101[combining macron]0) W-edge, but for the smallest nanoclusters also the (1[combining macron]010) S-edges become important. DFT calculations are used to construct phase diagrams of the WS2 edges, and describe their sulfur and hydrogen coordination under different conditions, and in this way shed light on the catalytic role of WS2 edges.

  16. Engineering ultrasmall water-soluble gold and silver nanoclusters for biomedical applications.

    Science.gov (United States)

    Luo, Zhentao; Zheng, Kaiyuan; Xie, Jianping

    2014-05-25

    Gold and silver nanoclusters or Au/Ag NCs with core sizes smaller than 2 nm have been an attractive frontier of nanoparticle research because of their unique physicochemical properties such as well-defined molecular structure, discrete electronic transitions, quantized charging, and strong luminescence. As a result of these unique properties, ultrasmall size, and good biocompatibility, Au/Ag NCs have great potential for a variety of biomedical applications, such as bioimaging, biosensing, antimicrobial agents, and cancer therapy. In this feature article, we will first discuss some critical biological considerations, such as biocompatibility and renal clearance, of Au/Ag NCs that are applied for biomedical applications, leading to some design criteria for functional Au/Ag NCs in the biological settings. According to these biological considerations, we will then survey some efficient synthetic strategies for the preparation of protein- and peptide-protected Au/Ag NCs with an emphasis on our recent contributions in this fast-growing field. In the last part, we will highlight some potential biomedical applications of these protein- and peptide-protected Au/Ag NCs. It is believed that with continued efforts to understand the interactions of biomolecule-protected Au/Ag NCs with the biological systems, scientists can largely realize the great potential of Au/Ag NCs for biomedical applications, which could finally pave their way towards clinical use.

  17. Rational Design of Biomolecular Templates for Synthesizing Multifunctional Noble Metal Nanoclusters toward Personalized Theranostic Applications.

    Science.gov (United States)

    Yu, Yong; Mok, Beverly Y L; Loh, Xian Jun; Tan, Yen Nee

    2016-08-01

    Biomolecule-templated or biotemplated metal nanoclusters (NCs) are ultrasmall (<2 nm) metal (Au, Ag) particles stabilized by a certain type of biomolecular template (e.g., peptides, proteins, and DNA). Due to their unique physiochemical properties, biotemplated metal NCs have been widely used in sensing, imaging, delivery and therapy. The overwhelming applications in these individual areas imply the great promise of harnessing biotemplated metal NCs in more advanced biomedical aspects such as theranostics. Although applications of biotemplated metal NCs as theranostic agents are trending, the rational design of biomolecular templates suitable for the synthesis of multifunctional metal NCs for theranostics is comparatively underexplored. This progress report first identifies the essential attributes of biotemplated metal NCs for theranostics by reviewing the state-of-art applications in each of the four modalities of theranostics, namely sensing, imaging, delivery and therapy. To achieve high efficacy in these modalities, we elucidate the design principles underlying the use of biomolecules (proteins, peptides and nucleic acids) to control the NC size, emission color and surface chemistries for post-functionalization of therapeutic moieties. We then propose a unified strategy to engineer biomolecular templates that combine all these modalities to produce multifunctional biotemplated metal NCs that can serve as the next-generation personalized theranostic agents.

  18. Nano-cluster stability following neutron irradiation in MA957 oxide dispersion strengthened material

    Science.gov (United States)

    Ribis, J.; Lozano-Perez, S.

    2014-01-01

    ODS steels are promising materials for Sodium cooled Fast Reactors since their fine distribution of nano-clusters confers excellent mechanical properties. However, the nano-feature stability needs to be assessed under neutron irradiation. Before irradiation, the characterizations show that nano-particles are finely distributed within the ferritic matrix and are identified to have a pyrochlore type structure. After irradiation of the MA957 alloy in the Phenix French reactor at 412 °C up to 50 dpa and 430 °C up to 75 dpa, transmission electron microscopy characterization reveals a very slight density fall but no distinguishable difference in nano-features size before and after irradiation. In addition, after both irradiations, the nano-oxides are still (Y, Ti, O) compounds with orientation relationship with the matrix. A multislice simulation of high resolution images suggests that nano-particles still have a fcc pyrochlore type structure after irradiation. A possible change of lattice parameter seems to be highlighted, possibly due to disordering by cascade effect.

  19. High selectivity of colorimetric detection of p-nitrophenol based on Ag nanoclusters

    Science.gov (United States)

    Qu, Fei; Chen, Ping; Zhu, Shuyun; You, Jinmao

    2017-01-01

    Ag nanoclusters (Ag NCs) templated by hyperbranched polyethyleneimine (PEI) with different terminal groups and molecular weights had been developed as a special optical sensor for detecting p-nitrophenol (p-NP). When adding p-NP into Ag NCs, an obvious color change from pale yellow to deep yellow could be observed by naked eyes, accompanying with an apparent red-shift of absorption peak, and the reason was attributed to the formation of oxygen anion of p-NP based on the transfer of H+ from p-NP to amine groups of PEI. The molecular weights of template would greatly affect the sensitivity of p-NP. Ag NCs capped by PEI terminated ethylenediamine (EDA) possessed better sensitivity than other Ag NCs, showing good linear range from 5 to 140 μM with the limit of detection as low as 1.28 μM. Most importantly, this present system displayed high selectivity toward p-NP even in the presence of other nitrophenols and nitrotoluenes. This reliable method had been successfully applied for the detection of p-NP in real water and soil samples.

  20. DNA abasic site-directed formation of fluorescent silver nanoclusters for selective nucleobase recognition

    Energy Technology Data Exchange (ETDEWEB)

    Ma Kun; Cui Qinghua; Liu Guiying; Wu Fei; Xu Shujuan; Shao Yong, E-mail: yshao@zjnu.cn [Institute of Physical Chemistry, Zhejiang Normal University, Jinhua 321004, Zhejiang (China)

    2011-07-29

    DNA single-nucleotide polymorphism (SNP) detection has attracted much attention due to mutation related diseases. Various methods for SNP detection have been proposed and many are already in use. Here, we find that the abasic site (AP site) in the DNA duplex can be developed as a capping scaffold for the generation of fluorescent silver nanoclusters (Ag NCs). As a proof of concept, the DNA sequences from fragments near codon 177 of cancer supression gene p53 were used as a model for SNP detection by in situ formed Ag NCs. The formation of fluorescent Ag NCs in the AP site-containing DNA duplex is highly selective for cytosine facing the AP site and guanines flanking the site and can be employed in situ as readout for SNP detection. The fluorescent signal-on sensing for SNP based on this inorganic fluorophore is substantially advantageous over the previously reported signal-off responses using low-molecular-weight organic ligands. The strong dependence of fluorescent Ag NC formation on the sequences surrounding the AP site was successfully used to identify mutations in codon 177 of cancer supression gene p53. We anticipate that this approach will be employed to develop a practical SNP detection method by locating an AP site toward the midway cytosine in a target strand containing more than three consecutive cytosines.

  1. Continuous and rapid synthesis of nanoclusters and nanocrystals using scalable microstructured reactors

    Science.gov (United States)

    Jin, Hyung Dae

    Recent advances in nanocrystalline materials production are expected to impact the development of next generation low-cost and/or high efficiency solar cells. For example, semiconductor nanocrystal inks are used to lower the fabrication cost of the absorber layers of the solar cells. In addition, some quantum confined nanocrystals display electron-hole pair generation phenomena with greater than 100% quantum yield, called multiple exciton generation (MEG). These quantum dots could potentially be used to fabricate solar cells that exceed the Schockley-Queisser limit. At present, continuous syntheses of nanoparticles using microreactors have been reported by several groups. Microreactors have several advantages over conventional batch synthesis. One advantage is their efficient heat transfer and mass transport. Another advantage is the drastic reduction in the reaction time, in many cases, down to minutes from hours. Shorter reaction time not only provides higher throughput but also provide better particle size control by avoiding aggregation and by reducing probability of oxidizing precursors. In this work, room temperature synthesis of Au11 nanoclusters and high temperature synthesis of chalcogenide nanocrystals were demonstrated using continuous flow microreactors with high throughputs. A high rate production of phosphine-stabilized Au11 nanoclusters was achieved using a layer-up strategy which involves the use of microlamination architectures; the patterning and bonding of thin layers of material (laminae) to create a multilayered micromixer in the range of 25-250 mum thick was used to step up the production of phosphine-stabilized Au11 nanoclusters. Continuous production of highly monodispersed phosphine-stabilized Au 11 nanoclusters at a rate of about 11.8 [mg/s] was achieved using a microreactor with a size of 1.687cm3. This result is about 30,000 times over conventional batch synthesis according to production rate/per reactor volume. We have elucidated the

  2. DFT study of selective hydrogenation of acetylene to ethylene on Pd doping Ag nanoclusters

    Science.gov (United States)

    Liu, D.

    2016-11-01

    Recently, it has been reported that the reaction selectivity of catalytic hydrogenation of acetylene to ethylene can be significantly enhanced via the approach of Pd mono-atomic catalysis [Pei et al. ACS Catal. 5 (2015) 3717-3725]. To explain the catalytic mechanism of this binary alloy catalyst, C2H2 hydrogenation reactions on Pd doping Ag nanoclusters are studied using density functional theory simulations. The simulation results indicate that H2 and C2H2 can simultaneously bind with a single Pd doping atom no matter it is on vertex and edge sites of Ag clusters. The following H2 dissociation and C2H2 hydrogenation are not difficult since the corresponding reaction barrier values are no more than 0.58 eV. The generated C2H4 molecule can not be further hydrogenated since it locates on the top of Pd doping atom, which is the only adsorption site for H2. On two Pd doping atoms at contiguous sites of Ag clusters, C2H4 hydrogenation reactions can be carried out since there are enough sites for co-adsorption of H2 and C2H4.

  3. Blue and red shifts of interband transition energy in supported Au nanoclusters on SiO2 and HOPG investigated by reflection electron energy-loss spectroscopy.

    Science.gov (United States)

    Borisyuk, P V; Troyan, V I; Pushkin, M A; Borman, V D; Tronin, V N

    2012-11-01

    Gold nanoclusters supported on SiO2 and HOPG are experimentally investigated by the reflection electron energy-loss spectroscopy. Two different trends in the size-dependence of the position of the energy-loss peak corresponding to the interband Au 5d --> 6s6p transition is observed: a blue shift for Au clusters on SiO2 and a red shift for Au clusters on HOPG. The different behaviors are qualitatively explained by the influence of the substrate on the spectrum of electronic states in Au nanoclusters.

  4. Target-controlled formation of silver nanoclusters in abasic site-incorporated duplex DNA for label-free fluorescence detection of theophylline

    Science.gov (United States)

    Park, Ki Soo; Oh, Seung Soo; Soh, H. Tom; Park, Hyun Gyu

    2014-08-01

    A novel, label-free, fluorescence based sensor for theophylline has been developed. In the new sensor system, an abasic site-incorporated duplex DNA probe serves as both a pocket for recognition of theophylline and a template for the preparation of fluorescent silver nanoclusters. The strategy relies on theophylline-controlled formation of fluorescent silver nanoclusters from abasic site-incorporated duplex DNA. When theophylline is not present, silver ions interact with the cytosine groups opposite to the abasic site in duplex DNA. This interaction leads to efficient formation of intensely red fluorescent silver nanoclusters. In contrast, when theophylline is bound at the abasic site through pseudo base-pairing with appropriately positioned cytosines, silver ion binding to the cytosine nucleobase is prevented. Consequently, fluorescent silver nanoclusters are not formed causing a significant reduction of the fluorescence signal. By employing this new sensor, theophylline can be highly selectively detected at a concentration as low as 1.8 μM. Finally, the diagnostic capability and practical application of this sensor were demonstrated by its use in detecting theophylline in human blood serum.A novel, label-free, fluorescence based sensor for theophylline has been developed. In the new sensor system, an abasic site-incorporated duplex DNA probe serves as both a pocket for recognition of theophylline and a template for the preparation of fluorescent silver nanoclusters. The strategy relies on theophylline-controlled formation of fluorescent silver nanoclusters from abasic site-incorporated duplex DNA. When theophylline is not present, silver ions interact with the cytosine groups opposite to the abasic site in duplex DNA. This interaction leads to efficient formation of intensely red fluorescent silver nanoclusters. In contrast, when theophylline is bound at the abasic site through pseudo base-pairing with appropriately positioned cytosines, silver ion binding to

  5. Magnetic response of dilute cobalt nanoparticles in an organic matrix : the effects of aging and interface chemistry.

    Energy Technology Data Exchange (ETDEWEB)

    Provencio, Paula Polyak; Wilcoxon, Jess Patrick; Venturini, Eugene Leo

    2003-06-01

    We report studies of the magnetic response of dilute frozen solutions of nanocrystalline Co particles grown in inverse micelles. Crystalline nanoclusters which initially exhibit only a small fraction of the bulk saturation moment restructure in solution without any change in cluster size or blocking temperature over a period of {approx}30-60 days, finally yielding a moment/atom which exceeds that of bulk Co. The saturation magnetism maintains its enhanced value for temperatures up to the melting point of the solvent matrix, but is strongly dependent on surface active additives and molecular oxygen.

  6. The impact of Au doping on the charge carrier dynamics at the interfaces between cationic porphyrin and silver nanoclusters

    KAUST Repository

    Almansaf, Abdulkhaleq A.

    2017-02-04

    We explore the impact of Au doping on the charge transfer dynamics between the positively charged porphyrin (TMPyP) and negatively charged silver nanoclusters (Ag29 NCs). Our transient absorption (TA) spectroscopic results demonstrate that the interfacial charge transfer, the intersystem crossing and the triplet state lifetime of porphyrin can be tuned by the doping of Au atoms in Ag29 NCs. Additionally, we found that the electrostatic interaction between the negative charge of the cluster and the positive charge on the TMPyP is the driving force that brings them close to each other for complex formation and subsequently facilitates the transfer process.

  7. pH-Induced Surface Modification of Atomically Precise Silver Nanoclusters: An Approach for Tunable Optical and Electronic Properties

    KAUST Repository

    AbdulHalim, Lina G.

    2016-10-24

    Noble metal nanoclusters (NCs) play a pivotal role in bridging the gap between molecules and quantum dots. Fundamental understanding of the evolution of the structural, optical, and electronic properties of these materials in various environments is of paramount importance for many applications. Using state-of-the-art spectroscopy, we provide the first decisive experimental evidence that the structural, electronic, and optical properties of Ag-44(MNBA)(30) NCs can now be tailored by controlling the chemical environment. Infrared and photoelectron spectroscopies clearly indicate that there is a dimerization between two adjacent ligands capping the NCs that takes place upon lowering the pH from 13 to 7.

  8. Chiral structure of thiolate-protected 28-gold-atom nanocluster determined by X-ray crystallography.

    Science.gov (United States)

    Zeng, Chenjie; Li, Tao; Das, Anindita; Rosi, Nathaniel L; Jin, Rongchao

    2013-07-10

    We report the crystal structure of a new nanocluster formulated as Au28(TBBT)20, where TBBT = 4-tert-butylbenzenethiolate. It exhibits a rod-like Au20 kernel consisting of two interpenetrating cuboctahedra. The kernel is protected by four dimeric "staples" (-SR-Au-SR-Au-SR-) and eight bridging thiolates (-SR-). The unit cell of Au28(TBBT)20 single crystals contains a pair of enantiomers. The origin of chirality is primarily rooted in the rotating arrangement of the four dimeric staples as well as the arrangement of the bridging thiolates (quasi-D2 symmetry). The enantiomers were separated by chiral HPLC and characterized by circular dichroism spectroscopy.

  9. In situ synthesis of lead sulfide nanoclusters on eggshell membrane fibers by an ambient bio-inspired technique

    Science.gov (United States)

    Su, Huilan; Han, Jie; Wang, Na; Dong, Qun; Zhang, Di; Zhang, Chunfu

    2008-02-01

    An ambient aqueous soakage technique is successfully developed to prepare PbS nanoclusters on eggshell membrane (ESM) fibers containing some active functional groups (hydroxyl, amine, imine, etc). Based on the biomaterial ESM serving as the reactive substrate and some ESM biomacromolecules acting as the surfactant, PbS nanocrystallites are in situ formed and further assembled into well-distributed nanoparticle aggregations. This moderate bio-inspired strategy would be of great value in preparing novel functional nanomaterials. The as-prepared hybrid PbS/ESM nanocomposites could have great potential for applications in semiconductor industries, optoelectronic fields, and nanostructured devices.

  10. Use of an Ethanol-Driven Pressure Cell to Measure Hydrostatic Pressure Response of Protein-Stabilized Gold Nanoclusters

    Science.gov (United States)

    2016-01-01

    and properties of metal nanoclusters. Chem Soc Rev. 2006;35(11):1162–1194. 2. Deheer WA. The physics of simple metal - clusters - experimental aspects...and simple-models. Rev Mod Phys. 1993;65(3):611–676. 3. Brack M. The physics of simple metal - clusters - self-consistent jellium model and...6. Zheng J, Nicovich PR, Dickson RM. Highly fluorescent noble- metal quantum dots. Annu Rev Phys Chem. 2007;58:409–431. 7. Chevrier DM, Chatt A

  11. Mo polyoxometalate nanoclusters capable of inhibiting the aggregation of Aβ-peptide associated with Alzheimer's disease

    Science.gov (United States)

    Chen, Qingchang; Yang, Licong; Zheng, Chuping; Zheng, Wenjing; Zhang, Jingnan; Zhou, Yunshan; Liu, Jie

    2014-05-01

    A neuropathological hallmark of Alzheimer's disease (AD) is aggregation of a forty-residue peptide known as amyloid beta forty (Aβ40). While past work has indicated that blocking Aβ40 aggregation could be an effective strategy for the treatment of AD, developing therapies with this goal has been met with limited success. Polyoxometalates (POMs) have been previously investigated for their anti-viral and anti-tumoral properties and we report here that three representative POM nanoclusters have been synthesized for use against Aβ40 aggregation. Through the use of thioflavin T fluorescence, turbidity, circular dichroism spectroscopy, and transmission electron microscopy (TEM), we found that all three POM complexes can significantly inhibit both natural Aβ40 self-aggregation and metal-ion induced Aβ40 aggregation. We also evaluated the protective effect of POM complexes on Aβ40-induced neurotoxicity in cultured PC12 cells and found that treatment with POM complexes can elevate cell viability, decrease levels of intracellular reactive oxygen species, and stabilize mitochondrial membrane potential. These findings indicate that all three representative POM complexes are capable of inhibiting Aβ40 aggregation and subsequent neurotoxicity. While a complete mechanistic understanding remains to be elucidated, the synthesized POM complexes may work through a synergistic interaction with metal ions and Aβ40. These data indicate that POM complexes have high therapeutic potential for use against one of the primary neuropathological features of AD.A neuropathological hallmark of Alzheimer's disease (AD) is aggregation of a forty-residue peptide known as amyloid beta forty (Aβ40). While past work has indicated that blocking Aβ40 aggregation could be an effective strategy for the treatment of AD, developing therapies with this goal has been met with limited success. Polyoxometalates (POMs) have been previously investigated for their anti-viral and anti-tumoral properties

  12. Atomically monodisperse nickel nanoclusters as highly active electrocatalysts for water oxidation

    Science.gov (United States)

    Joya, Khurram S.; Sinatra, Lutfan; Abdulhalim, Lina G.; Joshi, Chakra P.; Hedhili, M. N.; Bakr, Osman M.; Hussain, Irshad

    2016-05-01

    Achieving water splitting at low overpotential with high oxygen evolution efficiency and stability is important for realizing solar to chemical energy conversion devices. Herein we report the synthesis, characterization and electrochemical evaluation of highly active nickel nanoclusters (Ni NCs) for water oxidation at low overpotential. These atomically precise and monodisperse Ni NCs are characterized by using UV-visible absorption spectroscopy, single crystal X-ray diffraction and mass spectrometry. The molecular formulae of these Ni NCs are found to be Ni4(PET)8 and Ni6(PET)12 and are highly active electrocatalysts for oxygen evolution without any pre-conditioning. Ni4(PET)8 are slightly better catalysts than Ni6(PET)12 which initiate oxygen evolution at an amazingly low overpotential of ~1.51 V (vs. RHE; η ~ 280 mV). The peak oxygen evolution current density (J) of ~150 mA cm-2 at 2.0 V (vs. RHE) with a Tafel slope of 38 mV dec-1 is observed using Ni4(PET)8. These results are comparable to the state-of-the-art RuO2 electrocatalyst, which is highly expensive and rare compared to Ni-based materials. Sustained oxygen generation for several hours with an applied current density of 20 mA cm-2 demonstrates the long-term stability and activity of these Ni NCs towards electrocatalytic water oxidation. This unique approach provides a facile method to prepare cost-effective, nanoscale and highly efficient electrocatalysts for water oxidation.Achieving water splitting at low overpotential with high oxygen evolution efficiency and stability is important for realizing solar to chemical energy conversion devices. Herein we report the synthesis, characterization and electrochemical evaluation of highly active nickel nanoclusters (Ni NCs) for water oxidation at low overpotential. These atomically precise and monodisperse Ni NCs are characterized by using UV-visible absorption spectroscopy, single crystal X-ray diffraction and mass spectrometry. The molecular formulae of these

  13. Relative edge energy in the stability of transition metal nanoclusters of different motifs

    Science.gov (United States)

    Zhao, X. J.; Xue, X. L.; Guo, Z. X.; Li, S. F.

    2016-06-01

    When a structure is reduced to a nanometer scale, the proportion of the lowly-coordinated edge atoms increases significantly, which can play a crucial role in determining both their geometric and electronic properties, as demonstrated by the recently established generalized Wulff construction principle [S. F. Li, et al., Phys. Rev. Lett., 2013, 111, 115501]. Consequently, it is of great interest to clarify quantitatively the role of the edge atoms that dominate the motifs of these nanostructures. In principle, establishing an effective method valid for determining the absolute value of the surface energy and particularly the edge energy for a given nanostructure is expected to resolve such a problem. However, hitherto, it is difficult to obtain the absolute edge energy of transition metal clusters, particularly when their sizes approach the nanometer regime. In this paper, taking Ru nanoclusters as a prototypical example, our first-principles calculations introduce the concept of relative edge energy (REE), reflecting the net edge atom effect over the surface (facet) atom effect, which is fairly powerful to quasi-quantitatively estimate the critical size at which the crossover occurs between different configurations of a given motif, such as from an icosahedron to an fcc nanocrystal. By contrast, the bulk effect should be re-considered to rationalize the power of the REE in predicting the relative stability of larger nanostructures between different motifs, such as fcc-like and hcp-like nanocrystals.When a structure is reduced to a nanometer scale, the proportion of the lowly-coordinated edge atoms increases significantly, which can play a crucial role in determining both their geometric and electronic properties, as demonstrated by the recently established generalized Wulff construction principle [S. F. Li, et al., Phys. Rev. Lett., 2013, 111, 115501]. Consequently, it is of great interest to clarify quantitatively the role of the edge atoms that dominate the

  14. Protein-Assisted Assembly of Modular 3D Plasmonic Raspberry-like Core/Satellite Nanoclusters: Correlation of Structure and Optical Properties.

    Science.gov (United States)

    Höller, Roland P M; Dulle, Martin; Thomä, Sabrina; Mayer, Martin; Steiner, Anja Maria; Förster, Stephan; Fery, Andreas; Kuttner, Christian; Chanana, Munish

    2016-06-28

    We present a bottom-up assembly route for a large-scale organization of plasmonic nanoparticles (NPs) into three-dimensional (3D) modular assemblies with core/satellite structure. The protein-assisted assembly of small spherical gold or silver NPs with a hydrophilic protein shell (as satellites) onto larger metal NPs (as cores) offers high modularity in sizes and composition at high satellite coverage (close to the jamming limit). The resulting dispersions of metal/metal nanoclusters exhibit high colloidal stability and therefore allow for high concentrations and a precise characterization of the nanocluster architecture in dispersion by small-angle X-ray scattering (SAXS). Strong near-field coupling between the building blocks results in distinct regimes of dominant satellite-to-satellite and core-to-satellite coupling. High robustness against satellite disorder was proved by UV/vis diffuse reflectance (integrating sphere) measurements. Generalized multiparticle Mie theory (GMMT) simulations were employed to describe the electromagnetic coupling within the nanoclusters. The close correlation of structure and optical property allows for the rational design of core/satellite nanoclusters with tailored plasmonics and well-defined near-field enhancement, with perspectives for applications such as surface-enhanced spectroscopies.

  15. Water-gas shift reaction on metal nanoclusters encapsulated in mesoporous ceria studied with ambient-pressure X-ray photoelectron spectroscopy.

    Science.gov (United States)

    Wen, Cun; Zhu, Yuan; Ye, Yingchun; Zhang, Shiran; Cheng, Fang; Liu, Yi; Wang, Paul; Tao, Franklin Feng

    2012-10-23

    Metal nanoclusters (Au, Pt, Pd, Cu) encapsulated in channels of mesoporous ceria (mp-CeO(2)) were synthesized. The activation energies of water-gas shift (WGS) reaction performed at oxide-metal interfaces of metal nanoclusters encapsulated in mp-CeO(2) (M@mp-CeO(2)) are lower than those of metal nanoclusters impregnated on ceria nanorods (M/rod-CeO(2)). In situ studies using ambient-pressure XPS (AP-XPS) suggested that the surface chemistry of the internal concave surface of CeO(2) pores of M@mp-CeO(2) is different from that of external surfaces of CeO(2) of M/rod-CeO(2) under reaction conditions. AP-XPS identified the metallic state of the metal nanoclusters of these WGS catalysts (M@mp-CeO(2) and M/rod-CeO(2)) under a WGS reaction condition. The lower activation energy of M@mp-CeO(2) in contrast to M/rod-CeO(2) is related to the different surface chemistry of the two types of CeO(2) under the same reaction condition.

  16. The Size of Activating and Inhibitory Killer Ig-like Receptor Nanoclusters Is Controlled by the Transmembrane Sequence and Affects Signaling

    Directory of Open Access Journals (Sweden)

    Anna Oszmiana

    2016-05-01

    Full Text Available Super-resolution microscopy has revealed that immune cell receptors are organized in nanoscale clusters at cell surfaces and immune synapses. However, mechanisms and functions for this nanoscale organization remain unclear. Here, we used super-resolution microscopy to compare the surface organization of paired killer Ig-like receptors (KIR, KIR2DL1 and KIR2DS1, on human primary natural killer cells and cell lines. Activating KIR2DS1 assembled in clusters two-fold larger than its inhibitory counterpart KIR2DL1. Site-directed mutagenesis established that the size of nanoclusters is controlled by transmembrane amino acid 233, a lysine in KIR2DS1. Super-resolution microscopy also revealed two ways in which the nanoscale clustering of KIR affects signaling. First, KIR2DS1 and DAP12 nanoclusters are juxtaposed in the resting cell state but coalesce upon receptor ligation. Second, quantitative super-resolution microscopy revealed that phosphorylation of the kinase ZAP-70 or phosphatase SHP-1 is favored in larger KIR nanoclusters. Thus, the size of KIR nanoclusters depends on the transmembrane sequence and affects downstream signaling.

  17. Inter-cluster distance dependence of electrical conduction in nanocluster assembled films of silver: a new paradigm for design of nanostructures.

    Science.gov (United States)

    Bansal, Chandrahas; Praveen, S G; Kumaran, J T T; Chatterjee, Ashok

    2015-01-08

    The transport properties of films assembled from metal nanoclusters can be significantly different from the metals in their bulk or thin film forms due to quantum confinement effects and several competing energy and length scales. For a film composed of metal nanoclusters as its building blocks, the cluster size and the inter-cluster separation are parameters that can be varied experimentally. Here we show that the electrical conductivity of a film composed of silver nanoclusters can be changed by 9 orders of magnitude as a function of the average inter-cluster separation while keeping the average cluster size same. For inter-cluster separations of 9 nanometres or more the conductivity is insulating type whereas for lesser inter-cluster separations the conductivity behaviour is metallic type with a positive temperature coefficient of resistance. In the intermediate range between the two regions, a very interesting temperature-independent conductivity is seen. Our work provides a new paradigm for design of artificial solid structures composed of nanoclusters. The properties of these nanostructures could be tuned by varying the inter-cluster distances to get the desired properties in the same material.

  18. Enhancing 4-propylheptane dissociation with nickel nanocluster based on molecular dynamics simulations.

    Science.gov (United States)

    Ilyina, Margarita G; Khamitov, Edward M; Galiakhmetov, Rail N; Mustafin, Ildar A; Mustafin, Akhat G

    2017-03-01

    In the present work, a 0.4nm nickel cluster has been theoretically studied. Its equilibrium structural parameters have been calculated by the DFT method based on the PBEH1PBE hybrid functional and split-valence basis set Lanl2DZ including effective core potentials. We have systematically considered diverse spin states of this cluster and find out its ground state. The relative stability of these states depends on the HOMO-LUMO gap. The interaction of the Ni6 with 4-propylheptane С10Н22 has been studied to simulate the process of catalytic cracking of hydrocarbons. The optimization of this structure has been performed by the ωPBE/Lanl2DZ_ecp method (the TeraChem V.1.9 program package) with no symmetry restrictions; the electron shells of the metal were described by effective core pseudopotentials. For visualization and quantitative estimation of the bonding bonds between the nickel nanocluster and 4-propylheptane, the analysis of weak interactions based on RGD has been performed. To confirm the proposition about the formation of Ni-H bonds, we have scrutinized critical points of electronic density. Values of laplasian of electronic density and Bader atomic charge distribution in the global minimum of the total energy have been estimated by the AIMAll 15.05.18 program suite. Finally, we have simulated interaction of Ni6 with 4-propylheptane in terms of the Born-Oppenheimer ab initio molecular dynamics. The results of the molecular dynamics simulation provide pair radial distribution function CH at 1500°C and a detailed picture of the processes occurring in the system.

  19. Shape-Controlled Synthesis of Trimetallic Nanoclusters: Structure Elucidation and Properties Investigation.

    Science.gov (United States)

    Kang, Xi; Xiong, Lin; Wang, Shuxin; Yu, Haizhu; Jin, Shan; Song, Yongbo; Chen, Tao; Zheng, Liwei; Pan, Chensong; Pei, Yong; Zhu, Manzhou

    2016-11-21

    The shape-controlled synthesis of metal nanoclusters (NCs) with precise atomic arrangement is crucial for tailoring the properties. In this work, we successfully control the shape of alloy NCs by altering the dopants in the alloying processes. The shape of the spherical [Pt1 Ag24 (SPhMe2 )18 ] NC is maintained when [Au(I) SR] is used as dopant. By contrast, the shape of Pt1 Ag24 is changed to be rodlike by alloying with [Au(I) (PPh3 )Br]. The structures of the trimetallic NCs were determined by X-ray crystallography and further confirmed by both DFT and far-IR measurements. The shape-preserved [Pt1 Au6.4 Ag17.6 (SPhMe2 )18 ] NC is in a tristratified arrangement-[Pt(center)@Au/Ag(shell)@Ag(exterior)]-and is indeed the first X-ray crystal structure of thiolated trimetallic NCs. On the other hand, the resulting rodlike NC ([Pt2 Au10 Ag13 (PPh3 )10 Br7 ]) exhibits a high quantum yield (QY=14.7 %), which is in striking contrast to the weakly luminescent Pt1 Ag24 (QY=0.1 %, about 150-fold enhancement). In addition, the thermal stabilities of both trimetallic products are remarkably improved. This study presents a controllable strategy for synthesis of alloy NCs with different shapes (by alloying heteroatom complexes coordinated by different ligands), and may stimulate future work for a deeper understanding of the morphology (shape)-property correlation in NCs.

  20. The aptamer DNA-templated fluorescence silver nanoclusters: ATP detection and preliminary mechanism investigation.

    Science.gov (United States)

    Xu, Jiaona; Wei, Chunying

    2017-01-15

    Two general and reliable fluorescence sensors were proposed in this work utilizing aptamer DNA-templated silver nanoclusters (Ag NCs). Both DNA-AgNCs could be used for label-free detecting of ATP with the limits of detection of 0.44 and 0.65mM. One of them was further applied to monitor the activity of adenosine deaminase (ADA). In our effort to elucidate the light-up mechanism, we studied a total of six Ag NCs prepared by different DNA sequences, and found that they showed different sensitivity to ATP. Both BT3T3- and BT3T3(R)-templated Ag NCs were chose to make particular studies by UV-vis, TEM, fluorescence, and TCSPC methods. The results showed that when DNA-Ag NCs was kept for 1.5h and presented a strong fluorescence, the addition of ATP failed to cause a large change of fluorescence intensity; on the contrary, after Ag NCs was kept for 24h and emitted a weak fluorescence, adding ATP was able to result in the large fluorescence enhanced of 43 and 33 times for BT3T3- and BT3T3(R)-templated Ag NCs, respectively. The possible mechanism was also suggested that ATP binding to aptamer segment of template induced the change of the DNA secondary structure, which made the aggregated Ag nanoparticles disperse into Ag NCs with an average diameter of about 2nm that were responsible for the large fluorescence increase. Moreover, ATP could protect the fluorescence intensity of BT3T3(R)-templated Ag NCs from quenching for at least 9h.