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Sample records for ag nanocluster nucleation

  1. 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.

  2. 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...

  3. Luminescent molecular Ag-S nanocluster [Ag(62)S(13)(SBu(t))(32)](BF(4))(4).

    Science.gov (United States)

    Li, Gen; Lei, Zhen; Wang, Quan-Ming

    2010-12-22

    The first observation of luminescence from a structurally well-defined Ag(2)S molecular nanocluster is reported. Reaction of AgSBu(t)/AgBF(4) with N(2)H(4) in methanol affords the tetracationic cluster [Ag(62)S(13)(SBu(t))(32)](BF(4))(4), which has a core-shell configuration. The 14 silver(I) centers of the [Ag(14)S(13)] core are in a face-centered cubic arrangement with each edge bridged by a S(2-) ligand; the core is further connected to the [Ag(48)(SBu(t))(32)] shell via both Ag-S bonds and Ag···Ag interactions. This novel cluster displays intense red emission in both the solid state and solution at room temperature.

  4. 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.

  5. 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.

  6. 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

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  8. 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.

  9. 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.

  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. 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.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. Ice nucleation efficiency of AgI: review and new insights

    Science.gov (United States)

    Marcolli, Claudia; Nagare, Baban; Welti, André; Lohmann, Ulrike

    2016-07-01

    AgI is one of the best-investigated ice-nucleating substances. It has relevance for the atmosphere since it is used for glaciogenic cloud seeding. Theoretical and experimental studies over the last 60 years provide a complex picture of silver iodide as an ice-nucleating agent with conflicting and inconsistent results. This review compares experimental ice nucleation studies in order to analyze the factors that influence the ice nucleation ability of AgI. The following picture emerges from this analysis: the ice nucleation ability of AgI seems to be enhanced when the AgI particle is on the surface of a droplet, which is indeed the position that a particle takes when it can freely move in a droplet. The ice nucleation by particles with surfaces exposed to air depends on water adsorption. AgI surfaces seem to be most efficient at nucleating ice when they are exposed to relative humidity at or even above water saturation. For AgI particles that are completely immersed in water, the freezing temperature increases with increasing AgI surface area. Higher threshold freezing temperatures seem to correlate with improved lattice matches as can be seen for AgI-AgCl solid solutions and 3AgI·NH4I·6H2O, which have slightly better lattice matches with ice than AgI and also higher threshold freezing temperatures. However, the effect of a good lattice match is annihilated when the surfaces have charges. Also, the ice nucleation ability seems to decrease during dissolution of AgI particles. This introduces an additional history and time dependence for ice nucleation in cloud chambers with short residence times.

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. Sb-enhanced nucleation in the homoepitaxial growth of Ag(111)

    NARCIS (Netherlands)

    van der Vegt, H.A.; Meijer, J.A.; Vrijmoeth, J; Behm, R.J.; Vlieg, E.

    1998-01-01

    The effect of Sb on the homoepitaxial growth mode of a Ag(111) surface has been studied by scanning tunneling microscopy. In a previous paper we reported on the effect of Sb on the interlayer diffusion barrier of Ag(111). Here we describe in more detail the effect of Sb on the island nucleation and

  6. DFT study of selective hydrogenation of acetylene to ethylene on Pd doping Ag nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Liu, D., E-mail: liud@ysu.edu.cn

    2016-11-15

    Graphical abstract: The co-adsorption of H{sub 2} and C{sub 2}H{sub 4} on a single Pd doping atom of Ag clusters is impossible. Display Omitted - Highlights: • H{sub 2} and C{sub 2}H{sub 2} can simultaneously bind with a single Pd doping atom on Ag clusters. • The co-adsorption of H{sub 2} and C{sub 2}H{sub 4} on a single Pd doping atom is impossible. • C{sub 2}H{sub 4} can be hydrogenated to form C{sub 2}H{sub 6} on two neighboring Pd doping atoms. - Abstract: 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, C{sub 2}H{sub 2} hydrogenation reactions on Pd doping Ag nanoclusters are studied using density functional theory simulations. The simulation results indicate that H{sub 2} and C{sub 2}H{sub 2} can simultaneously bind with a single Pd doping atom no matter it is on vertex and edge sites of Ag clusters. The following H{sub 2} dissociation and C{sub 2}H{sub 2} hydrogenation are not difficult since the corresponding reaction barrier values are no more than 0.58 eV. The generated C{sub 2}H{sub 4} molecule can not be further hydrogenated since it locates on the top of Pd doping atom, which is the only adsorption site for H{sub 2}. On two Pd doping atoms at contiguous sites of Ag clusters, C{sub 2}H{sub 4} hydrogenation reactions can be carried out since there are enough sites for co-adsorption of H{sub 2} and C{sub 2}H{sub 4}.

  7. Nucleation promotion of Sn-Ag-Cu lead-free solder alloys via micro alloying

    Science.gov (United States)

    Mao, Jie

    Sn-Ag-Cu (SAC) alloy system is widely accepted as a viable Pb-free alternative to Sn-Pb alloys for microelectronics packaging applications. Compared with its Pb-containing predecessor SAC alloys tend to have coarse grain structure, which is believed to be caused by high undercooling prior to nucleation. This work explores the possibility of modifying the nucleation process and reducing the undercooling of SAC alloys via introducing minor alloying elements. The mechanisms through which effective alloying elements influenced the nucleation process of SAC alloys are investigated with microstructural and chemical analyses. Minor alloying elements (Mn and Zn) are found promoting beta-Sn nucleation and reducing the undercooling of SAC. Manganese promotes beta-Sn primary phase nucleation through the formation of MnSn2 intermetallic compound. Experimental results in this work support the claim by previous researchers that zinc promotes beta-Sn primary phase nucleation through the formation of zinc oxide. In addition to nucleation, this work also assesses the microstructural impact of minor elements on Sn-Ag-Cu based alloys. Methods have been developed to quantify and compare microstructural impacts of minor elements and efficiently study their partitioning behaviors. LA-ICPMS was introduced to SAC alloy application to efficiently study partitioning behaviors of minor elements.

  8. From monomer to monolayer: a global optimisation study of (ZnO)n nanoclusters on the Ag surface.

    Science.gov (United States)

    Demiroglu, Ilker; Woodley, Scott M; Sokol, Alexey A; Bromley, Stefan T

    2014-12-21

    We employ global optimisation to investigate how oxide nanoclusters of increasing size can best adapt their structure to lower the system energy when interacting with a realistic extended metal support. Specifically, we focus on the (ZnO)@Ag(111) system where experiment has shown that the infinite Ag(111)-supported ZnO monolayer limit corresponds to an epitaxially 7 : 8 matched graphene-like (Zn(3)O(3))-based hexagonal sheet. Using a two-stage search method based on classical interatomic potentials and then on more accurate density functional theory, we report global minina candidate structures for Ag-supported (ZnO)n cluster with sizes ranging from n = 1-24. Comparison with the respective global minina structure of free space (ZnO)n clusters reveals that the surface interaction plays a decisive role in determining the lowest energy Ag-supported (ZnO)n cluster structures. Whereas free space (ZnO)n clusters tend to adopt cage-like bubble structures as they grow larger, Ag-supported (ZnO)n clusters of increasing size become progressively more like planar cuts from the infinite graphene-like ZnO single monolayer. This energetic favourability for planar hexagonal Ag-supported clusters over their 3D counterparts can be partly rationalised by the ZnO-Ag(111) epitaxial matching and the increased number of close interactions with the Ag surface. Detailed analysis shows that this tendency can also be attributed to the capacity of 2D clusters to distort to improve their interaction with the Ag surface relative to more rigid 3D bubble cluster isomers. For the larger sized clusters we find that the adsorption energies and most stable structural types appear to be rather converged confirming that our study makes a bridge between the Ag-supported ZnO monomer and the infinite Ag-supported ZnO monolayer.

  9. Monodispersed bimetallic PdAg nanoparticles with twinned structures: Formation and enhancement for the methanol oxidation

    OpenAIRE

    Zhen Yin; Yining Zhang; Kai Chen; Jing Li; Wenjing Li; Pei Tang; Huabo Zhao; Qingjun Zhu; Xinhe Bao; Ding Ma

    2014-01-01

    Monodispersed bimetallic PdAg nanoparticles can be fabricated through the emulsion-assisted ethylene glycol (EG) ternary system. Different compositions of bimetallic PdAg nanoparticles, Pd80Ag20, Pd65Ag35 and Pd46Ag54 can be obtained via adjusting the reaction parameters. For the formation process of the bimetallic PdAg nanoparticles, there have two-stage growth processes: firstly, nucleation and growth of the primary nanoclusters; secondly, formation of the secondary nanoparticles with the s...

  10. Effect of salts, solvents and buffer on miRNA detection using DNA silver nanocluster (DNA/AgNCs) probes

    Science.gov (United States)

    Shah, Pratik; Cho, Seok Keun; Waaben Thulstrup, Peter; Bhang, Yong-Joo; Ahn, Jong Cheol; Choi, Suk Won; Rørvig-Lund, Andreas; Yang, Seong Wook

    2014-01-01

    MicroRNAs (miRNAs) are small regulatory RNAs (size ˜21 nt to ˜25 nt) which regulate a variety of important cellular events in plants, animals and single cell eukaryotes. Especially because of their use in diagnostics of human diseases, efforts have been directed towards the invention of a rapid, simple and sequence selective detection method for miRNAs. Recently, we reported an innovative method for the determination of miRNA levels using the red fluorescent properties of DNA/silver nanoclusters (DNA/AgNCs). Our method is based on monitoring the emission drop of a DNA/AgNCs probe in the presence of its specific target miRNA. Accordingly, the accuracy and efficiency of the method relies on the sensitivity of hybridization between the probe and target. To gain specific and robust hybridization between probe and target, we investigated a range of diverse salts, organic solvents, and buffer to optimize target sensing conditions. Under the newly adjusted conditions, the target sensitivity and the formation of emissive DNA/AgNCs probes were significantly improved. Also, fortification of the Tris-acetate buffer with inorganic salts or organic solvents improved the sensitivity of the DNA/AgNC probes. On the basis of these optimizations, the versatility of the DNA/AgNCs-based miRNA detection method can be expanded.

  11. Crystal structure and optical properties of the [Ag62S12(SBu(t))32](2+) nanocluster with a complete face-centered cubic kernel.

    Science.gov (United States)

    Jin, Shan; Wang, Shuxin; Song, Yongbo; Zhou, Meng; Zhong, Juan; Zhang, Jun; Xia, Andong; Pei, Yong; Chen, Man; Li, Peng; Zhu, Manzhou

    2014-11-05

    The crystal structure of the [Ag62S12(SBu(t))32](2+) nanocluster (denoted as NC-I) has been successfully determined, and it shows a complete face-centered-cubic (FCC) Ag14 core structure with a Ag48(SBu(t))32 shell configuration interconnected by 12 sulfide ions, which is similar to the [Ag62S13(SBu(t))32](4+) structure (denoted as NC-II for short) reported by Wang. Interestingly, NC-I exhibits prominent differences in the optical properties in comparison with the case of the NC-II nanocluster. We employed femtosecond transient absorption spectroscopy to further identify the differences between the two nanoclusters. The results show that the quenching of photoluminescence in NC-I in comparison to that of NC-II is caused by the free valence electrons, which dramatically change the ligand to metal charge transfer (LMCT, S 3p → Ag 5s). To get further insight into these, we carried out time-dependent density functional theory (TDDFT) calculations on the electronic structure and optical absorption spectra of NC-I and NC-II. These findings offer a new insight into the structure and property evolution of silver cluster materials.

  12. A label-free fluorescent molecular beacon based on DNA-Ag nanoclusters for the construction of versatile Biosensors.

    Science.gov (United States)

    Cao, Qiao; Teng, Ye; Yang, Xuan; Wang, Jin; Wang, Erkang

    2015-12-15

    In this paper, we developed a simple, low-cost and sensitive DNA sequences detection biosensor based on a label-free molecular beacon (MB) whose DNA hairpin structure terminal has a guanine-rich sequence that can enhance fluorescence of silver nanoclusters (Ag NCs). Without hybridization between hairpin probe and target DNA, the Ag NCs presented bright fluorescence for the proximity of guanine-rich sequences (GRSs). After binding with target DNA, the hairpin shape was destroyed which results in a decrease of the Ag NCs fluorescence intensity. With this biosensor, we detected three disease-related genes that were the human immunodeficiency virus (HIV) gene, hepatitis B virus (HBV) gene and human T-lymphotropic virus type I (HTLV-I) gene. The detection limits based on S/N of 3 were 4.4 nM, 6.8 nM and 8.5 nM for HIV gene, HBV gene and HTLV-I gene, respectively. Our sensor was also of high selectivity and could distinguish even one nucleotide mismatched target.

  13. Irradiation induced dissolution of Cu and growth of Ag nanoclusters in Cu/Ag ion-exchanged soda-lime glass

    CERN Document Server

    Manikandan, D; Magudapathy, P; Nair, K G M

    2002-01-01

    Complex metal nanoclusters of Cu/Ag are formed in a soda-lime glass matrix by sequential copper and silver ion-exchange followed by ion irradiation. Optical absorption measurements showed signature of copper clusters alone in the Cu/Ag ion-exchanged sample. Irradiation of the ion-exchanged sample with He sup + ions of energy 100 keV of different fluences resulted in the growth of the silver clusters with, the optical absorption spectrum exhibiting two peaks corresponding to the surface plasmon resonance of copper and silver in the same matrix. It was found that with increase in fluence the silver clusters begin to grow while the already formed copper clusters segregate, which can be visualized from the absorption spectra, where the copper band disappears while the silver band grows with the increase in dose. Vacuum annealing of the Cu/Ag ion-exchanged samples resulted in complete disappearance of copper clusters while the silver clusters grew till they attained saturation. The glancing incidence X-ray diffrac...

  14. Locking-to-unlocking system is an efficient strategy to design DNA/silver nanoclusters (AgNCs) probe for human miRNAs

    DEFF Research Database (Denmark)

    Shah, Pratik; Choi, Suk Won; Kim, Ho-jin;

    2016-01-01

    MicroRNAs (miRNAs), small non-coding RNA molecules, are important biomarkers for research and medical purposes. Here, we describe the development of a fast and simple method using highly fluorescent oligonucleotide-silver nanocluster probes (DNA/AgNCs) to efficiently detect specific miRNAs. Due t...... detect a number of cancer related miRNAs in RNA extracts from human cancer cell lines....

  15. RETRACTED: Optical limiting performance of Ag nanoclusters synthesized by ion implantation

    Science.gov (United States)

    Wang, Y. H.; Wei, L.; Yuan, J.; Wang, R. W.; Lu, J. D.; Ji, L. L.

    2013-01-01

    Metal nanoparticles synthesized by 200 keV Ag ions into silica with dose of 2×1017 ions/cm2 has been studied. Third-order nonlinear optical properties of the nanoparticles were measured at 1064 nm excitations using the Z-scan technique. Results of the investigation of nonlinear refraction by the single beam Z-scan configuration are presented and the mechanisms responsible for the nonlinear response were discussed. Curve fitting analysis, based on MATLAB features for Ag nanoparticle optical limiting experiment, is used. The results show that Ag nanoparticles display a refractive optical limiting effect at 1064 nm.

  16. [Ag67(SPhMe2)32(PPh3)8]3+: Synthesis, Total Structure, and Optical Properties of a Large Box-Shaped Silver Nanocluster

    KAUST Repository

    Alhilaly, Mohammad J.

    2016-10-13

    Engineering the surface ligands of metal nanoparticles is critical in designing unique arrangements of metal atoms. Here, we report the synthesis and total structure determination of a large box-shaped Ag-67 nanocluster (NC) protected by a mixed shell of thiolate (2,4-dimethylbenzenethiolate, SPhMe2) and phosphine (triphenylphosphine, PPh3) ligands. Single crystal X-ray diffraction (SCXRD) and electrospray ionization mass spectrometry (ESI-MS) revealed the cluster formula to be [Ag-67(SPhMe2)(32)(PPh3)(8)](3+). The crystal structure shows an Ag-23 metal core covered by a layer of Ag44S32P8 arranged in the shape of a box. The Ag-13, core was formed through an unprecedented centered cuboctahedron, i.e., Ag-13, unlike the common centered Ag-13 icosahedron geometry. Two types of ligand motifs, eight AgS3P and eight bridging thiols, were found to stabilize the whole cluster. The optical spectrum of this NC displayed highly structured multiple absorption peaks. The electronic structure and optical spectrum of Ag-67 were computed using time-dependent density functional theory (TDDFT) for both the full cluster [Ag-67(SPhMe2)(32)(PPh3)(8)](3+) and a reduced model [Ag-67(SH)(32)(PH3)(8)](3+). The lowest metal-to-metal transitions in the range 500-800 nm could be explained by considering the reduced model that shows almost identical electronic states to 32 free electrons in a jellium box. The successful synthesis of the large box-shaped Ag-67 NC facilitated by the combined use of phosphine and thiol paves the way for synthesizing other metal clusters with unprecedented shapes by judicious choice of thiols and phosphines.

  17. Doping-Induced Anisotropic Self-Assembly of Silver Icosahedra in [Pt2Ag23Cl7(PPh3)10] Nanoclusters

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa

    2017-01-09

    Atomically precise self-assembled architectures of noble metals with unique surface structures are necessary for prospective applications. However, the synthesis of such structures based on silver is challenging because of their instability. In this work, by developing a selective and controlled doping strategy, we synthesized and characterized a rod-shaped, charge-neutral, diplatinum-doped Ag nanocluster (NC) of [Pt2Ag23Cl7(PPh3)10]. Its crystal structure revealed the self-assembly of two Pt-centered Ag icosahedra through vertex sharing. Five bridging and two terminal chlorides and 10 PPh3 ligands were found to stabilize the cluster. Electronic structure simulations corroborated structural and optical characterization of the cluster and provided insights into the effect of the Pt dopants on the optical properties and stability of the cluster. Our study will open new avenues for designing novel self-assembled NCs using different elemental dopants.

  18. Integrated logic gate for fluorescence turn-on detection of histidine and cysteine based on Ag/Au bimetallic nanoclusters-Cu²⁺ ensemble.

    Science.gov (United States)

    Sun, Jian; Yang, Fan; Zhao, Dan; Chen, Chuanxia; Yang, Xiurong

    2015-04-01

    By means of employing 11-mercaptoundecanoic acid (11-MUA) as a reducing agent and protecting ligand, we present straightforward one-pot preparation of fluorescent Ag/Au bimetallic nanoclusters (namely AgAuNCs@11-MUA) from AgNO3 and HAuCl4 in alkaline aqueous solution at room temperature. It is found that the fluorescence of AgAuNCs@11-MUA has been selectively quenched by Cu(2+) ions, and the nonfluorescence off-state of the as-prepared AgAuNCs@11-MUA-Cu(2+) ensemble can be effectively switched on upon the addition of histidine and cysteine. By incorporating Ni(2+) ions and N-ethylmaleimide, this phenomenon is further exploited as an integrated logic gate and a specific fluorescence turn-on assay for selectively and sensitively sensing histidine and cysteine has been designed and established based on the original noncovalent AgAuNCs@11-MUA-Cu(2+) ensemble. Under the optimal conditions, histidine and cysteine can be detected in the concentration ranges of 0.25-9 and 0.25-7 μM; besides, the detection limits are found to be 87 and 111 nM (S/N = 3), respectively. Furthermore, we demonstrate that the proposed AgAuNCs@11-MUA-based fluorescent assay can be successfully utilized for biological fluids sample analysis.

  19. Synthesis, structure and gas-phase reactivity of the mixed silver hydride borohydride nanocluster [Ag3(μ3-H)(μ3-BH4)L(Ph)3]BF4 (L(Ph) = bis(diphenylphosphino)methane).

    Science.gov (United States)

    Zavras, Athanasios; Ariafard, Alireza; Khairallah, George N; White, Jonathan M; Mulder, Roger J; Canty, Allan J; O'Hair, Richard A J

    2015-11-21

    Borohydrides react with silver salts to give products that span multiple scales ranging from discrete mononuclear compounds through to silver nanoparticles and colloids. The cluster cations [Ag3(H)(BH4)L3](+) are observed upon electrospray ionization mass spectrometry of solutions containing sodium borohydride, silver(I) tetrafluoroborate and bis(dimethylphosphino)methane (L(Me)) or bis(diphenylphosphino)methane (L(Ph)). By adding NaBH4 to an acetonitrile solution of AgBF4 and L(Ph), cooled to ca. -10 °C, we have been able to isolate the first mixed silver hydride borohydride nanocluster, [Ag3(μ3-H)(μ3-BH4)L(Ph)3]BF4, and structurally characterise it via X-ray crystallography. Combined gas-phase experiments (L(Me) and L(Ph)) and DFT calculations (L(Me)) reveal how loss of a ligand from the cationic complexes [Ag3(H)(BH4)L3](+) provides a change in geometry that facilitates subsequent loss of BH3 to produce the dihydride clusters, [Ag3(H)2Ln](+) (n = 1 and 2). Together with the results of previous studies (Girod et al., Chem. - Eur. J., 2014, 20, 16626), this provides a direct link between mixed silver hydride/borohydride nanoclusters, silver hydride nanoclusters, and silver nanoclusters.

  20. Ag nanoclusters could efficiently quench the photoresponse of CdS quantum dots for novel energy transfer-based photoelectrochemical bioanalysis.

    Science.gov (United States)

    Zhang, Ling; Sun, Yue; Liang, Yan-Yu; He, Jian-Ping; Zhao, Wei-Wei; Xu, Jing-Juan; Chen, Hong-Yuan

    2016-11-15

    Herein the influence of ultrasmall Ag nanoclusters (Ag NCs) against CdS quantum dots (QDs) in a photoelectrochemical (PEC) nanosystem was exploited for the first time, based on which a novel PEC bioanalysis was successfully developed via the efficient quenching effect of Ag NCs against the CdS QDs. In a model system, DNA assay was achieved by using molecular beacon (MB) probes anchored on a CdS QDs modified electrode, and the MB probes contain two segments that can hybridize with both target DNA sequence and the label of DNA encapsulated Ag NCs. After the MB probe was unfolded by the target DNA sequence, the labels of oligonucleotide encapsulated Ag NCs would be brought in close proximity to the CdS QDs electrode surface, and efficient photocurrent quenching of QDs could be resulted from an energy transfer process that originated from NCs. Thus, by monitoring the attenuation in the photocurrent signal, an elegant and sensitive PEC DNA bioanalysis could be accomplished. The developed biosensor displayed a linear range from 1.0pM to 10nM and the detection limit was experimentally found to be of 0.3pM. This work presents a feasible signaling principle that could act as a common basis for general PEC bioanalysis development.

  1. Plasmon-exciton coupling at Ag nanocluster decorated TiO2(110) surface studied by time-resolved two-photon photoemission spectroscopy

    Science.gov (United States)

    Tan, Shijing; Argondizzo, Adam; Petek, Hrvoje

    We study the spectroscopy and electron dynamics at Ag nanocluster decorated TiO2(110) surface upon photoexcitation of plasmonic modes by two-photon photoemission spectroscopy (2PP). Depositing Ag onto a reduced rutile TiO2(110) surface at room temperature forms pancake-like Ag particles with an average diameter of 4 nm and height of 1.5 nm. Measurements of the 2PP yield from Ag/TiO2 surface with tunable femtosecond laser excitation show enhancement at plasmonic resonances. Exciting with s-polarization (S -->) the plasmonic resonance enhancement has a single peak at 3.1 eV, whereas with p-polarization (P -->) there is an additional more intense resonance at 3.8 eV. We attribute the 3.1 and 3.8 eV peaks to the in-plane and the surface-normal plasmon modes respectively. Crystal azimuth orientation dependent excitation with (S -->) shows an anisotropy in the 2PP spectra for the 3.1 eV in-plane plasmon mode when the laser electric field is aligned in the [001] vs. [ 1 1 0 ] directions. The existence of two plasmon modes and the in-plane plasmon anisotropy imply that the plasmon modes are perturbed by coherent coupling with excitons in the rutile TiO2 substrate. We speculate that plasmon-exciton resonant energy transfer could play an important role in the plasmonically enhanced photocatalysis at the Ag/TiO2 surface.

  2. Quantum sized Ag nanocluster assisted fluorescence enhancement in Tm{sup 3+}-Yb{sup 3+} doped optical fiber beyond plasmonics

    Energy Technology Data Exchange (ETDEWEB)

    Chattopadhyay, Rik; Haldar, Arindam; Paul, Mukul C.; Das, Shyamal; Bhadra, Shyamal 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)

    2015-12-07

    We report a process for enhancing fluorescence emission from conventional rare earth ions in optical fiber by metal nanocluster (MNC) in nonresonant indirect pumping. The process is completely different from formal metal enhanced fluorescence phenomenon as the MNCs are too small in size to support localized surface plasmon and the excitation wavelength is far from plasmon resonance frequency. We used an established theory of two coupled oscillators to explain the simultaneous enhancement of Ytterbium (Yb{sup 3+}) and Thulium (Tm{sup 3+}) emission by silver (Ag) NCs under nonresonant pumping in optical fiber. The fiber is pumped with a 980 nm fiber pigtailed laser diode with input power of 20–100 mW to excite the Yb{sup 3+}. Four times enhancement of Yb{sup 3+} emission of 900–1100 nm and Tm{sup 3+} upconversion emission around 474 nm, 650 nm, and 790 nm is observed in the fiber with Ag NCs.

  3. Synthesis of unidirectional structures of SiO{sub 2}-Ag using Au nanoparticles as nucleation centers; Sintesis de estructuras unidireccionales de SiO{sub 2}-Ag utilizando nanoparticulas de Au como centros de nucleacion

    Energy Technology Data Exchange (ETDEWEB)

    Villa S, G.; Mendoza A, D.; Gutierrez W, C.; Perez H, R. [ININ, Carretera Mexico-Toluca s/n, Ocoyoacac 52750, Estado de Mexico (Mexico)], e-mail: demetrio.mendoza@inin.gob.mx

    2008-07-01

    This paper reports a method to synthesize Ag unidirectional structures covered with SiO{sub 2} by sol-gel technique using Au nanoparticles as nucleation centers of the unidirectional structures. In the first phase unidirectional structures of SiO{sub 2}-Ag CI are obtained by sol-gel, using TEOS as a precursor of metallic structures (Ag) and the incorporation of Au nanoparticles as nucleation centers for growth of unidirectional structures. In the second stage, one-way systems are subjected to thermal treatment in H{sub 2} atmosphere for obtain AG{sup 0} particles through mechanisms that diffusion and coalescence of silver to form structures that have a thin cover of SiO{sub 2}. Analysis by scanning electron microscopy, transmission and atomic force microscopy allowed to determine the chemical composition and microstructural properties of unidirectional systems SiO{sub 2}-Ag. (Author)

  4. Nucleation, growth, and dissolution of Ag nanostructures formed in nanotubular J-aggregates of amphiphilic cyanine dyes

    CERN Document Server

    Polzer, Egon Steeg Frank; Qiao, Yan; Rabe, Jürgen P; Kirstein, Stefan

    2015-01-01

    The nucleation, growth, and dissolution of silver nanowires within tubular aggregates of the dye C8S3 are investigated. The tubular aggregates are formed in aqueous solution from amphiphilic dyes and the silver wires are grown from silver salt. Samples were investigated systematically and in detail using cryo-TEM and TEM at different time steps after addition of silver salt (AgNO3) and short illumination with blue light (420 nm) for production of nuclei. The enhanced concentration of silver ions in proximity of the aggregates surface leads to favoured growth of seeds at or within the aggregates. The early stage of the seed growth is observable by cryo-TEM and shows to be well separated and isolated. There are no indications that nuclei are formed at preferred defect sites at the aggregates which is interpreted as homogeneous nucleation. The spatial position of the majority of initially formed seeds discriminates between growth of particles at the outer surface of the aggregate or wires at the inner space. The...

  5. Enhanced magnetic properties of FePt nanoparticles codeposited on Ag nanoislands

    Science.gov (United States)

    Castaldi, L.; Giannakopoulos, K.; Travlos, A.; Boukos, N.; Niarchos, D.; Boukari, S.; Beaurepaire, E.

    2009-05-01

    Ag nanoislands have been used as nucleation sites for FePt nanoparticles when deposited on SiO2 surfaces by electron beam evaporation. We demonstrate that it is possible to nucleate FePt nanoparticles on predeposited Ag clusters and that this results in a significant improvement of the hard magnetic Ag/FePt nanoparticles' properties. We find that, besides the usual annealing treatments, a simple predeposition of Ag nanoclusters promotes the formation of the FePt L10 phase at larger FePt nominal thicknesses (fFePt). All the nanoparticles studied are ferromagnetic, except for those FePt samples deposited with lower nominal thicknesses (fFePt˜1.8 nm), which are superparamagnetic. The presence of Ag seeds promotes the A1/L10 transition, which results in a remarkable enhancement of the coercivity (Hc) for both the as-deposited and the annealed samples. Maximum Hc of 8.9 and 9.4 kOe are obtained for the Ag/FePt nanoparticles with fFePt˜1.8 and 3.5 nm, respectively. Our results are a strong indication that the nucleation of the FePt nanoparticles on Ag nanoclusters can promote significant magnetic hardening of the FePt nanoparticles by easing the transition from the disordered to the ordered phase.

  6. Gas-phase VUV photoionisation and photofragmentation of the silver deuteride nanocluster [Ag10D8L6](2+) (L = bis(diphenylphosphino)methane). A joint experimental and theoretical study.

    Science.gov (United States)

    Daly, Steven; Krstić, Marjan; Giuliani, Alexandre; Antoine, Rodolphe; Nahon, Laurent; Zavras, Athanasios; Khairallah, George N; Bonačić-Koutecký, Vlasta; Dugourd, Philippe; O'Hair, Richard A J

    2015-10-21

    The bis(diphenylphosphino)methane (L = Ph2PCH2PPh2) ligated silver deuteride nanocluster dication, [Ag10D8L6](2+), has been synthesised in the condensed phase via the reaction of bis(diphenylphosphino)methane, silver nitrate and sodium borodeuteride in the methanol : chloroform (1 : 1) mixed solvent system. The photoionisation and photofragmentation of this mass-selected cluster were studied using a linear ion trap coupled to the DESIRS VUV beamline of the SOLEIL Synchrotron. At 15.5 eV the main ionic products observed are [Ag10D8L5](2+), [Ag10D8L4](2+), [Ag10D8L6](3+)˙, [Ag9D8L4](2+)˙, and [AgL2](+). The later two products arise from fragmentation of [Ag10D8L6](3+)˙. An analysis of the yields of these product ions as a function of the photon energy reveals the onset for the formation of [AgL2](+) and [Ag9D8L4](2+)˙ is around 2 eV higher than that for ionisation to produce [Ag10D8L5](3+)˙. The onset of ionisation energy of [Ag10D8L6](2+) was determined to be 9.3 ± 0.3 eV from a fit of the yield of the product ion, [Ag10D8L6](3+)˙, as a function of the VUV photon energy. DFT calculations at the RI-PBE/RECP-def2-SVP level of theory were carried out to search for a possible structure of the cluster and to estimate its vertical and adiabatic ionisation energies. The calculated lowest energy structure of the [Ag10D8L6](2+) nanocluster contains a symmetrical bicapped square antiprism as a silver core in which hydrides are located as a mix of triangular faces and edges. Four of the bisphosphines bind to the edges of the cluster core as bidentate ligands, the remaining two bisphosphines bind via a single phosphorus donor atom to each of the apical silver atoms. The DFT calculated adiabatic ionisation energy for this structure is 8.54 eV, in satisfactory agreement with experiment.

  7. Advanced surface characterization of silver nanocluster segregation in Ag-TiCN bioactive coatings by RBS, GDOES, and ARXPS.

    Science.gov (United States)

    Escobar Galindo, R; Manninen, N K; Palacio, C; Carvalho, S

    2013-07-01

    Surface modification by means of wear protective and antibacterial coatings represents, nowadays, a crucial challenge in the biomaterials field in order to enhance the lifetime of bio-devices. It is possible to tailor the properties of the material by using an appropriate combination of high wear resistance (e.g., nitride or carbide coatings) and biocide agents (e.g., noble metals as silver) to fulfill its final application. This behavior is controlled at last by the outmost surface of the coating. Therefore, the analytical characterization of these new materials requires high-resolution analytical techniques able to provide information about surface and depth composition down to the nanometric level. Among these techniques are Rutherford backscattering spectrometry (RBS), glow discharge optical emission spectroscopy (GDOES), and angle resolved X-ray photoelectron spectroscopy (ARXPS). In this work, we present a comparative RBS-GDOES-ARXPS study of the surface characterization of Ag-TiCN coatings with Ag/Ti atomic ratios varying from 0 to 1.49, deposited at room temperature and 200 °C. RBS analysis allowed a precise quantification of the silver content along the coating with a non-uniform Ag depth distribution for the samples with higher Ag content. GDOES surface profiling revealed that the samples with higher Ag content as well as the samples deposited at 200 °C showed an ultrathin (1-10 nm) Ag-rich layer on the coating surface followed by a silver depletion zone (20-30 nm), being the thickness of both layers enhanced with Ag content and deposition temperature. ARXPS analysis confirmed these observations after applying general algorithm involving regularization in addition to singular value decomposition techniques to obtain the concentration depth profiles. Finally, ARXPS measurements were used to provide further information on the surface morphology of the samples obtaining an excellent agreement with SEM observations when a growth model of silver islands with

  8. A sensitive spectrofluorometric method for detection of berberine hydrochloride using Ag nanoclusters directed by natural fish sperm DNA.

    Science.gov (United States)

    Liang, Sheng; Kuang, Yangfang; Ma, Fangfang; Chen, Shu; Long, Yunfei

    2016-11-15

    A novel DNA-directed AgNCs (DNA-AgNCs) was synthesized with economical raw material (natural fish sperm DNA) through a simple and rapid approach, and it first showed high and stable fluorescence emission as a AgNCs stabilized by natural DNA at about 635nm. Moreover, its emission intensity could be enhanced tremendously in acetic acid (HAc) medium. Whereas, when berberine hydrochloride (BRH) entered the solution system, it would interact and combine efficiently with DNA on the surface of AgNCs, which could lead to subtle change of charge distribution on its surface, and make it more lyophobic, inducing aggregation of DNA-AgNCs. As a result, fluorescence of the system was quenched visually; the process represented a color variance from yellow to hot pink under HAc medium, then back to yellowish-brown when BRH worked. Based on above phenomenon, a selective and accurate spectrofluorometric method for BRH detection was established. It can be applied to detect trace amounts of BRH in aqueous solution in the linear range from 1.0nM to 2000.0nM; and the detection limit (3σ/k) was 0.3nM, which is pretty lower compared to most reported spectral methods. Simultaneously, a semi-quantitative determination by visual evaluation from 5.0nM to 2000.0nM was also achieved. This method provided excellent selectivity for the detection of BRH in the presence of ten kinds of common natural amino acids and nine kinds of common mental ions. Furthermore, the BRH content in compound berberine tablets from drugstore was successfully investigated by this method and the results showed high accuracy.

  9. Two-component spin-coated Ag/CNT composite films based on a silver heterogeneous nucleation mechanism adhesion-enhanced by mechanical interlocking and chemical grafting

    Science.gov (United States)

    Zhang, Yang; Kang, Zhixin; Bessho, Takeshi

    2017-03-01

    In this paper, a new method for the synthesis of silver carbon nanotube (Ag/CNT) composite films as conductive connection units for flexible electronic devices is presented. This method is about a two-component solution process by spin coating with an after-treatment annealing process. In this method, multi-walled carbon nanotubes (MWCNTs) act as the core of silver heterogeneous nucleation, which can be observed and analyzed by a field-emission scanning electron microscope. With the effects of mechanical interlocking, chemical grafting, and annealing, the interfacial adhesive strength between films and PET sheets was enhanced to 12 N cm‑1. The tensile strength of the Ag/CNT composite films was observed to increase by 38% by adding 5 g l‑1 MWCNTs. In the four-probe method, the resistivity of Ag/CNT-5 declined by 78.2% compared with pristine Ag films. The anti-fatigue performance of the Ag/CNT composite films was monitored by cyclic bending deformation and the results revealed that the growth rate of electrical resistance during the deformation was obviously retarded. As for industrial application, this method provides an efficient low-cost way to prepare Ag/CNT composite films and can be further applied to other coating systems.

  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. A new signal-on method for the detection of protein based on binding-induced strategy and photoinduced electron transfer between Ag nanoclusters and split G-quadruplex-hemin complexes

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Kai, E-mail: zhangkai@jsinm.org; Wang, Ke; Zhu, Xue; Xie, Minhao

    2015-08-05

    Proteins play important roles in biological and cellular processes. The levels of proteins can be useful biomarkers for cellular events or disease diagnosis, thus the method for sensitive and selective detection of proteins is imperative to proteins express, study, and clinical diagnosis. Herein, we report a “signal-on” platform for the assay of protein based on binding-induced strategy and photoinduced electron transfer between Ag nanoclusters and split G-quadruplex-hemin complexes. By using biotin as the affinity ligand, this simple protocol could sensitively detect streptavidin with a detection limit down to 10 pM. With the use of an antibody as the affinity ligand, a method for homogeneous fluorescence detection of Prostate Specific Antigen (PSA) was also proposed with a detection limit of 10 pM. The one-step and wash-free assay showed good selectivity. Its high sensitivity, acceptable accuracy, and satisfactory versatility of analytes led to various applications in bioanalysis. - Highlights: • AgNCs have great potential for application in biomedicine. • Binding of two affinity ligands can result in binding-induced DNA assemblies. • PET can be happened between DNA/AgNCs and G-quadruplex/hemin complexes. • A platform for the detection of proteins was proposed by using PET and binding-induced strategy.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  16. RHEED studies of the nucleation, growth, and mobility of Ag atoms on the Si(111)7 x 7 surface

    Energy Technology Data Exchange (ETDEWEB)

    Roos, K.R.

    1993-07-01

    The low temperature and flux dependent growth of ultrathin Ag films on the Si(111)7x7 surface is studied with Reflection High-Energy Electron Diffraction (RHEED). The grazing incidence geometry of RHEED allows for an incident molecular beam normal to the surface, and makes it an ideal surface probe for studying ultrathin film growth in real time. Short-lived oscillations in the diffracted intensity are observed during Ag deposition at 150 K, indicating quasi-layer-by-layer growth mediated by adatom mobility. When the 150 K growth is performed over a wide range of deposition rates F, the peak intensity is observed to scale, i.e. I(Ft) depends only on the total amount deposited, which implies thermally activated diffusion is absent at 150 K. Scaling is not obeyed at higher temperatures (T{ge}473 K) for the growth of the {radical}3{times}{radical}3 R30{degrees} ({radical}3) superstructure. Testing for scaling of the diffracted intensity constitutes a new experimental method which can be applied generally to determine if thermal diffusion is active at a particular temperature. Scaling is consistent with a constant diffusion length R{sub 0}, independent of substrate temperature and deposition rate. The presence of a non-thermal diffusion mechanism (responsible for the constant diffusion length R{sub 0}) is confirmed by monitoring the flux dependence of the {radical}3 superstructure growth during deposition at T{ge}473 K. At these temperatures the total diffusion length R is given by R=R{sub 0}+(4Dt){sup 1/2}, where (4Dt){sup 1/2} is the thermal component. A non-zero intercept R{sub 0} is found by plotting the peak intensity I{sub p}{sup 1/2} (a measure of the average domain size) vs. deposition rate F{sup {minus}1/2} (F{sup {minus}1} is proportional to the available diffusion time.) From the FWHM of a low coverage (0.2 ML) {radical}3 spot, an estimation of 50 {angstrom} is made for a lower bound of the magnitude of R{sub 0}.

  17. 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

  18. Localized surface plasmon resonance light-scattering detection of Hg(II) with 3-aminopropyltriethoxysilane-assisted synthesis of highly stabilized Ag nanoclusters.

    Science.gov (United States)

    Zhu, Jingjing; Mao, Qinli; Gao, Lang; He, Yu; Song, Gongwu

    2013-03-21

    We employed 3-aminopropyltriethoxysilane to assist the synthesis of Ag NCs using polyethyleneimine as the template for detecting Hg(2+) by localized surface plasmon resonance light-scattering technology. The developed selective and sensitive method presaged more opportunities for application in environmental systems.

  19. Nucleation and Growth of Cu-Al Intermetallics in Al-Modified Sn-Cu and Sn-Ag-Cu Lead-Free Solder Alloys

    Science.gov (United States)

    Reeve, Kathlene N.; Anderson, Iver E.; Handwerker, Carol A.

    2015-03-01

    Lead-free solder alloys Sn-Cu (SC) and Sn-Ag-Cu (SAC) are widely used by the microelectronics industry, but enhanced control of the microstructure is needed to improve solder performance. For such control, nucleation and stability of Cu-Al intermetallic compound (IMC) solidification catalysts were investigated by variation of the Cu (0.7-3.0 wt.%) and Al (0.0-0.4 wt.%) content of SC + Al and SAC + Al alloys, and of SAC + Al ball-grid array (BGA) solder joints. All of the Al-modified alloys produced Cu-Al IMC particles with different morphologies and phases (occasionally non-equilibrium phases). A trend of increasing Cu-Al IMC volume fraction with increasing Al content was established. Because of solidification of non-equilibrium phases in wire alloy structures, differential scanning calorimetry (DSC) experiments revealed delayed, non-equilibrium melting at high temperatures related to quenched-in Cu-Al phases; a final liquidus of 960-1200°C was recorded. During cooling from 1200°C, the DSC samples had the solidification behavior expected from thermodynamic equilibrium calculations. Solidification of the ternary alloys commenced with formation of ternary β and Cu-Al δ phases at 450-550°C; this was followed by β-Sn, and, finally, Cu6Sn5 and Cu-Al γ1. Because of the presence of the retained, high-temperature phases in the alloys, particle size and volume fraction of the room temperature Cu-Al IMC phases were observed to increase when the alloy casting temperature was reduced from 1200°C to 800°C, even though both temperatures are above the calculated liquidus temperature of the alloys. Preliminary electron backscatter diffraction results seemed to show Sn grain refinement in the SAC + Al BGA alloy.

  20. 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.

  1. 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〉

  2. 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.

  3. 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.

  4. Comparison of optical transients during the picosecond laser pulse-induced crystallization of GeSbTe and AgInSbTe phase-change thin films: Nucleation-driven versus growth-driven processes

    Science.gov (United States)

    Liang, Guangfei; Li, Simian; Huang, Huan; Wang, Yang; Lai, Tianshu; Wu, Yiqun

    2013-09-01

    Direct comparison of the real-time in-situ crystallization behavior of as-deposited amorphous Ge2Sb2Te5 (GeSbTe) and Ag8In14Sb55Te23 (AgInSbTe) phase-change thin films driven by picosecond laser pulses was performed by a time-resolved optical pump-probe technique with nanosecond resolution. Different optical transients showed various crystallization processes because of the dissimilar nucleation- and growth-dominated mechanisms of the two materials. The effects of laser pulse fluence, thermal conductive structure, and successive pulse irradiation on their crystallization dynamics were also discussed. A schematic was then established to describe the different crystallization processes beginning from the as-deposited amorphous state. The results may provide further insight into the phase-change mechanism under extra-non-equilibrium conditions and aid the development of ultrafast phase-change memory materials.

  5. 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).

  6. 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.

  7. 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.

  8. 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.

  9. Microwave-assisted hydrothermal synthesis of Ag₂(W(1-x)Mox)O₄ heterostructures: Nucleation of Ag, morphology, and photoluminescence properties.

    Science.gov (United States)

    Silva, M D P; Gonçalves, R F; Nogueira, I C; Longo, V M; Mondoni, L; Moron, M G; Santana, Y V; Longo, E

    2016-01-15

    Ag2W(1-x)MoxO4 (x=0.0 and 0.50) powders were synthesized by the co-precipitation (drop-by-drop) method and processed using a microwave-assisted hydrothermal method. We report the real-time in situ formation and growth of Ag filaments on the Ag2W(1-x)MoxO4 crystals using an accelerated electron beam under high vacuum. Various techniques were used to evaluate the influence of the network-former substitution on the structural and optical properties, including photoluminescence (PL) emission, of these materials. X-ray diffraction results confirmed the phases obtained by the synthesis methods. Raman spectroscopy revealed significant changes in local order-disorder as a function of the network-former substitution. Field-emission scanning electron microscopy was used to determine the shape as well as dimensions of the Ag2W(1-x)MoxO4 heterostructures. The PL spectra showed that the PL-emission intensities of Ag2W(1-x)MoxO4 were greater than those of pure Ag2WO4, probably because of the increase of intermediary energy levels within the band gap of the Ag2W(1-x)MoxO4 heterostructures, as evidenced by the decrease in the band-gap values measured by ultraviolet-visible spectroscopy.

  10. 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.

  11. Nonclassical nucleation and growth of inorganic nanoparticles

    Science.gov (United States)

    Lee, Jisoo; Yang, Jiwoong; Kwon, Soon Gu; Hyeon, Taeghwan

    2016-08-01

    The synthesis of nanoparticles with particular compositions and structures can lead to nanoparticles with notable physicochemical properties, thus promoting their use in various applications. In this area of nanoscience, the focus is shifting from size- and shape-uniform single-component nanoparticles to multicomponent nanoparticles with enhanced performance and/or multifunctionality. With the increasing complexity of synthetic reactions, an understanding of the formation mechanisms of the nanoparticles is needed to enable a systematic synthetic approach. This Review highlights mechanistic studies underlying the synthesis of nanoparticles, with an emphasis on nucleation and growth behaviours that are not expected from classical theories. We discuss the structural properties of nanoclusters that are of a size that bridges molecules and solids. We then describe the role of nanoclusters in the prenucleation process as well as in nonclassical nucleation models. The growth of nanoparticles via the assembly and merging of primary particles is also overviewed. Finally, we present the heterogeneous nucleation mechanisms behind the synthesis of multicomponent nanoparticles.

  12. 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.

  13. Comparison of optical transients during the picosecond laser pulse-induced crystallization of GeSbTe and AgInSbTe phase-change thin films: Nucleation-driven versus growth-driven processes

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Guangfei [Key Laboratory of High Power Laser Materials, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800 (China); Li, Simian [State Key Laboratory of Optoelectronic Materials and Technology, Department of Physics, Sun Yat-Sen University, Guangzhou 510275 (China); Huang, Huan [Key Laboratory of High Power Laser Materials, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800 (China); Wang, Yang, E-mail: ywang@siom.ac.cn [Key Laboratory of High Power Laser Materials, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800 (China); Lai, Tianshu, E-mail: stslts@mail.sysu.edu.cn [State Key Laboratory of Optoelectronic Materials and Technology, Department of Physics, Sun Yat-Sen University, Guangzhou 510275 (China); Wu, Yiqun [Key Laboratory of High Power Laser Materials, Shanghai Institute of Optics and Fine Mechanics, Chinese Academy of Sciences, Shanghai 201800 (China)

    2013-09-01

    Direct comparison of the real-time in-situ crystallization behavior of as-deposited amorphous Ge{sub 2}Sb{sub 2}Te{sub 5} (GeSbTe) and Ag{sub 8}In{sub 14}Sb{sub 55}Te{sub 23} (AgInSbTe) phase-change thin films driven by picosecond laser pulses was performed by a time-resolved optical pump-probe technique with nanosecond resolution. Different optical transients showed various crystallization processes because of the dissimilar nucleation- and growth-dominated mechanisms of the two materials. The effects of laser pulse fluence, thermal conductive structure, and successive pulse irradiation on their crystallization dynamics were also discussed. A schematic was then established to describe the different crystallization processes beginning from the as-deposited amorphous state. The results may provide further insight into the phase-change mechanism under extra-non-equilibrium conditions and aid the development of ultrafast phase-change memory materials.

  14. 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).

  15. Nucleation Mechanism for Bainite

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    Based on the experimental results that solute-depleted zone was observed in Cu-28Zn-4Al (mass fraction) at 523 K,△G is calculated as a positive according to the thermodynamic criteria for the spinodal decomposition of a ternarysystems. So, the solute-depleted zone cannot be formed by spinodal decomposition. Dislocation density requiredby the formation of solute-depleted zone is estimated greater than 7.89×109 cm-2 according to the segregationof solute atoms around dislocations, which is not consistent with the practical situation for the alloy at 523 K.Associated with the internal friction experimental fact that internal friction peaks appear within the incubation forbainitic transformation in Cu-Zn-Al alloy, the equilibrium temperature, T0, is evaluated as 433 K for solute-depletedCu-25Zn-3.4Al, which is lower than the experimental temperature 523 K. Thus, nucleation by shear mechanism isimpossible in this circumstance. Therefore, it is concluded that , like bainite in steels and Ag-Cd, bainite in Cu-Zn-Alalloys nucleates by diffusional mechanism, just implied by the experimental existence of solute-depleted zone.

  16. 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.

  17. Multistep nucleation of nanocrystals in aqueous solution

    Science.gov (United States)

    Loh, N. Duane; Sen, Soumyo; Bosman, Michel; Tan, Shu Fen; Zhong, Jun; Nijhuis, Christian A.; Král, Petr; Matsudaira, Paul; Mirsaidov, Utkur

    2017-01-01

    The nucleation and growth of solids from solutions impacts many natural processes and is fundamental to applications in materials engineering and medicine. For a crystalline solid, the nucleus is a nanoscale cluster of ordered atoms that forms through mechanisms still poorly understood. In particular, it is unclear whether a nucleus forms spontaneously from solution via a single- or multiple-step process. Here, using in situ electron microscopy, we show how gold and silver nanocrystals nucleate from supersaturated aqueous solutions in three distinct steps: spinodal decomposition into solute-rich and solute-poor liquid phases, nucleation of amorphous nanoclusters within the metal-rich liquid phase, followed by crystallization of these amorphous clusters. Our ab initio calculations on gold nucleation suggest that these steps might be associated with strong gold-gold atom coupling and water-mediated metastable gold complexes. The understanding of intermediate steps in nuclei formation has important implications for the formation and growth of both crystalline and amorphous materials.

  18. Dynamics of homogeneous nucleation

    DEFF Research Database (Denmark)

    Toxværd, Søren

    2015-01-01

    The classical nucleation theory for homogeneous nucleation is formulated as a theory for a density fluctuation in a supersaturated gas at a given temperature. But molecular dynamics simulations reveal that it is small cold clusters which initiates the nucleation. The temperature in the nucleating...

  19. 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.

  20. 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.

  1. 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.

  2. 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.)

  3. Site Preference in Multimetallic Nanoclusters: Incorporation of Alkali Metal Ions or Copper Atoms into the Alkynyl-Protected Body-Centered Cubic Cluster [Au7 Ag8 (C≡C(t) Bu)12 ]().

    Science.gov (United States)

    Wang, Yu; Su, Haifeng; Ren, Liting; Malola, Sami; Lin, Shuichao; Teo, Boon K; Häkkinen, Hannu; Zheng, Nanfeng

    2016-11-21

    The synthesis, structure, substitution chemistry, and optical properties of the gold-centered cubic monocationic cluster [Au@Ag8 @Au6 (C≡C(t) Bu)12 ](+) are reported. The metal framework of this cluster can be described as a fragment of a body-centered cubic (bcc) lattice with the silver and gold atoms occupying the vertices and the body center of the cube, respectively. The incorporation of alkali metal atoms gave rise to [Mn Ag8-n Au7 (C≡C(t) Bu)12 ](+) clusters (n=1 for M=Na, K, Rb, Cs and n=2 for M=K, Rb), with the alkali metal ion(s) presumably occupying the vertex site(s), whereas the incorporation of copper atoms produced [Cun Ag8 Au7-n (C≡C(t) Bu)12 ](+) clusters (n=1-6), with the Cu atom(s) presumably occupying the capping site(s). The parent cluster exhibited strong emission in the near-IR region (λmax =818 nm) with a quantum yield of 2 % upon excitation at λ=482 nm. Its photoluminescence was quenched upon substitution with a Na(+) ion. DFT calculations confirmed the superatom characteristics of the title compound and the sodium-substituted derivatives.

  4. 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.

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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

  11. 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$_{...

  12. 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.

  13. Effect of strain on surface diffusion and nucleation

    DEFF Research Database (Denmark)

    Brune, Harald; Bromann, Karsten; Röder, Holger;

    1995-01-01

    The influence of strain on diffusion and nucleation has been studied by means of scanning tunneling microscopy and effective-medium theory for Ag self-diffusion on strained and unstrained (111) surfaces. Experimentally, the diffusion barrier is observed to be substantially lower on a pseudomorphic...... Ag monolayer on Pt(111), 60 meV, compared to that on Ag(111), 97 meV. The calculations show that this strong effect is due to the 4.2% compressive strain of the Ag monolayer on Pt. It is shown that in general isotropic two-dimensional strain as well as its relief via dislocations have a drastic...

  14. 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

  15. 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

  16. 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.

  17. Nonequilibrium thermodynamics of nucleation

    Energy Technology Data Exchange (ETDEWEB)

    Schweizer, M., E-mail: marco.schweizer@math.ethz.ch [ETH Zurich, Department of Materials, Polymer Physics, Vladimir-Prelog-Weg 2, 8093 Zurich (Switzerland); Sagis, L. M. C., E-mail: leonard.sagis@wur.nl [ETH Zurich, Department of Materials, Polymer Physics, Vladimir-Prelog-Weg 2, 8093 Zurich (Switzerland); Food Physics Group, Wageningen University, Bornse Weilanden, 6708 WG Wageningen (Netherlands)

    2014-12-14

    We present a novel approach to nucleation processes based on the GENERIC framework (general equation for the nonequilibrium reversible-irreversible coupling). Solely based on the GENERIC structure of time-evolution equations and thermodynamic consistency arguments of exchange processes between a metastable phase and a nucleating phase, we derive the fundamental dynamics for this phenomenon, based on continuous Fokker-Planck equations. We are readily able to treat non-isothermal nucleation even when the nucleating cores cannot be attributed intensive thermodynamic properties. In addition, we capture the dynamics of the time-dependent metastable phase being continuously expelled from the nucleating phase, and keep rigorous track of the volume corrections to the dynamics. Within our framework the definition of a thermodynamic nuclei temperature is manifest. For the special case of nucleation of a gas phase towards its vapor-liquid coexistence, we illustrate that our approach is capable of reproducing recent literature results obtained by more microscopic considerations for the suppression of the nucleation rate due to nonisothermal effects.

  18. Nucleation in food colloids

    Science.gov (United States)

    Povey, Malcolm J. W.

    2016-12-01

    Nucleation in food colloids has been studied in detail using ultrasound spectroscopy. Our data show that classical nucleation theory (CNT) remains a sound basis from which to understand nucleation in food colloids and analogous model systems using n-alkanes. Various interpretations and modifications of CNT are discussed with regard to their relevance to food colloids. Much of the evidence presented is based on the ultrasound velocity spectrometry measurements which has many advantages for the study of nucleating systems compared to light scattering and NMR due to its sensitivity at low solid contents and its ability to measure true solid contents in the nucleation and early crystal growth stages. Ultrasound attenuation spectroscopy also responds to critical fluctuations in the induction region. We show, however, that a periodic pressure fluctuation such as a quasi-continuous (as opposed to a pulse comprising only a few pressure cycles) ultrasound field can alter the nucleation process, even at very low acoustic intensity. Thus care must be taken when using ultrasound techniques that the measurements do not alter the studied processes. Quasi-continuous ultrasound fields may enhance or suppress nucleation and the criteria to determine such effects are derived. The conclusions of this paper are relevant to colloidal systems in foods, pharmaceuticals, agro-chemicals, cosmetics, and personal products.

  19. 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.

  20. Surface effects in nucleation

    CERN Document Server

    Alekseechkin, Nikolay V

    2016-01-01

    The classical nucleation theory (CNT) concept of a nucleus as a fragment of the bulk new phase fails for nanosized nuclei. An extension of CNT taking into account the properties of the transition region between coexisting bulk phases is proposed. For this purpose, the finite-thickness layer method which is an alternative to the Gibbs one is used; the transition region is considered as a separate (surface) phase. An equation for the nucleation work is derived which is basic for the multivariable theory of nucleation.

  1. Ice nucleation terminology

    Directory of Open Access Journals (Sweden)

    G. Vali

    2014-08-01

    Full Text Available Progress in the understanding of ice nucleation is being hampered by the lack of uniformity in how some terms are used in the literature. This even extends to some ambiguity of meanings attached to some terms. Suggestions are put forward here for common use of terms. Some are already well established and clear of ambiguities. Others are less engrained and will need a conscious effort in adoption. Evolution in the range of systems where ice nucleation is being studied enhances the need for a clear nomenclature. The ultimate limit in the clarity of definitions is, of course, the limited degree to which ice nucleation processes are understood.

  2. Interface controlled growth of nanostructures in discontinuous Ag and Au thin films fabricated by ion beam sputter deposition for plasmonic applications

    Indian Academy of Sciences (India)

    R Brahma; M Ghanashyam Krishna

    2012-08-01

    The growth of discontinuous thin films of Ag and Au by low energy ion beam sputter deposition is reported. The study focuses on the role of the film–substrate in determining the shape and size of nanostructures achieved in such films. Ag films were deposited using Ar ion energy of 150 eV while the Au films were deposited with Ar ion energies of 250–450 eV. Three types of interfaces were investigated in this study. The first set of film–substrate interfaces consisted of Ag and Au films grown on borosilicate glass and carbon coated Cu grids used as substrates. The second set of films was metallic bilayers in which one of the metals (Ag or Au) was grown on a continuous film of the other metal (Au or Ag). The third set of interfaces comprised of discontinuous Ag and Au films deposited on different dielectrics such as SiO2, TiO2 and ZrO2. In each case, a rich variety of nanostructures including self organized arrays of nanoparticles, nanoclusters and nanoneedles have been achieved. The role of the film–substrate interface is discussed within the framework of existing theories of thin film nucleation and growth. Interfacial nanostructuring of thin films is demonstrated to be a viable technique to realize a variety of nanostructures. The use of interfacial nanostructuring for plasmonic applications is demonstrated. It is shown that the surface Plasmon resonance of the metal nanostructures can be tuned over a wide range of wavelengths from 400 to 700 nm by controlling the film–substrate interface.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. Functionalized Carbon Molecular Sieve membranes containing Ag-nanoclusters

    NARCIS (Netherlands)

    Barsema, J.N.; Balster, J.; Jordan, V.; Vegt, van der N.F.A.; Wessling, M.

    2003-01-01

    In Carbon Molecular Sieve (CMS) membranes, the separation of O2 and N2 is primarily based on the difference in size between the gas molecules. To enhance the separation properties of these CMS membranes it is necessary to functionalize the carbon matrix with materials that show a high affinity to on

  13. Non-covalent attachment of silver nanoclusters onto single-walled carbon nanotubes with human serum albumin as linking molecule

    Energy Technology Data Exchange (ETDEWEB)

    Rodríguez-Galván, Andrés, E-mail: andres.rodriguez@nucleares.unam.mx [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior C.U., 04510 México D.F. (Mexico); Instituto de Física, Dpto. Física Experimental, Universidad Nacional Autónoma de México, Coyoacán, México, DF 04510 (Mexico); Unidad de Investigación Biomédica en Cáncer INCan-UNAM, Instituto Nacional de Cancerología, México, DF 14080 (Mexico); Heredia, Alejandro [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior C.U., 04510 México D.F. (Mexico); Amelines-Sarria, Oscar; Rivera, Margarita [Instituto de Física, Dpto. Materia Condensada, Universidad Nacional Autónoma de México, Coyoacán, 04510 México D.F. (Mexico); and others

    2015-03-15

    The attachment of silver nanoclusters (AgNCs) onto single-walled carbon nanotubes (SWNTs) for the formation of integrated fluorescence sites has attracted much attention due their potential applications as biological probes and nanovectors in theragnosis. Here, we report the preparation through assembly of fluorescent quasi 1-D nanomaterial based on SWNTs and silver nanoclusters (AgNCs) non-covalently attached to human serum albumin as biological linker. The fluorescent SWNT–AgNCs–HSA conjugates were characterized by atomic force microscopy, high-resolution transmission electron microscopy (HRTEM), high angle annular dark field scanning TEM (HAADF-STEM), fluorescent and UV–vis spectroscopy. The above techniques confirmed that AgNCs were non-covalently attached onto the external surface of SWNTs. In addition, it was observed that the modification did not affect the optical properties of the synthesized AgNCs since the absorption spectra and fluorescence under UV irradiation (λ = 365 nm) remain the same. The effect of the functionalized systems was tested on mammal red blood cells (RBCs) and it was found that their structural integrity was compromised by the conjugates, limiting their biological and medical applications.

  14. 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.

  15. 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.

  16. 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.

  17. 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...

  18. Relationship of heterogeneous nucleation and condensational growth on aerosol nanoparticles

    Science.gov (United States)

    Smorodin, Vladimir Y.; Hopke, Philip K.

    2006-12-01

    Heterogeneous nucleation and condensation of dibutylphthalate, octadecane, octadecanol, and octadecanoic acid vapors at various pressures on insoluble AgCl and Ag nanoparticles in a turbulent mixing condensation nuclei counter (TMCNC) have been studied theoretically. A method to interpret the particle size distributions measured with a DMA and estimate the parameters for nucleation on single particles is proposed. Based on this semi-empirical method, the Gibbs free energy is calculated and a rate of heterogeneous nucleation on single particles is estimated directly from the experimental "condensation spectra" of inactive and active CN using the DMA data. In some cases, the dependence of the Gibbs nucleation energy on the vapor supersaturation had two maximums and one minimum, instead of one maximum as described by Gibbs' classical thermodynamics of phase transitions. This phenomenon, called "double barrier nucleation" (DBN) is caused by the surface heterogeneity of nano-CN; this is first experimental verification of DBN that had been previously predicted theoretically. Two types of heterogeneity may be present: topographic or energetic. Focusing on energetic heterogeneity, a theoretical model of DBN for spherical geometry is developed. The surface heterogeneity for insoluble nano-sized CN is shown to be critical to explaining the unusual transformation of a monomodal size distribution of inactive CN into a bimodal distribution of activated CN when coagulation is excluded. Future studies will be directed toward more data for further refining the theory and developing a model that simultaneously accounts for both types of surface heterogeneity of nano-CN.

  19. 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 different emitters, which can influence the reproducibility of the optical response and the evolution over time of the populations of these emitters. We have developed a simple method to characterize the spectral heterogeneity and time evolution of these emissive species at any given point in time after...... the spectral heterogeneity of other fluorophores, such as luminescent colloidal nanoparticles, and to assess the reproducibility of a synthetic procedure containing an unknown distribution of emissive species....

  20. 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.

  1. 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.

  2. Martensitic nucleation mechanism

    Institute of Scientific and Technical Information of China (English)

    陈奇志; 桑灿; 吴杏芳; 柯俊

    1997-01-01

    A sort of special dislocation configuration was deformation-induced in an Fe-Ni-V-C alloy by in-situ elongation tests of TEM. The cooling in-situ observations, as well as the SADPs from the region of the special dislocation configurations, proved that they are martensitic nuclei. In martensitic transformation, a nucleus changed into a small martensitic sub-plate, and a group of parallel sub-plates that formed from a group of parallel nuclei made up a big martensitic plate Martensitic transformation involved opposite shear between adjacent martensitic nuclei. By using the reduced-cell method, the crystallographic structure of observed martensitic nuclei was indexed as a face-centered orthogonal (FCO) lattice, which was explained by the nucleation mechanism proposed by the present authors. The crystallographic analysis confirmed that the defect faulting involved in martensitic nucleation took place among three close pakked planes, instead of between two adjacent planes as an ordinary stacking fault.

  3. Overview: Nucleation of clathrate hydrates

    Science.gov (United States)

    Warrier, Pramod; Khan, M. Naveed; Srivastava, Vishal; Maupin, C. Mark; Koh, Carolyn A.

    2016-12-01

    Molecular level knowledge of nucleation and growth of clathrate hydrates is of importance for advancing fundamental understanding on the nature of water and hydrophobic hydrate formers, and their interactions that result in the formation of ice-like solids at temperatures higher than the ice-point. The stochastic nature and the inability to probe the small length and time scales associated with the nucleation process make it very difficult to experimentally determine the molecular level changes that lead to the nucleation event. Conversely, for this reason, there have been increasing efforts to obtain this information using molecular simulations. Accurate knowledge of how and when hydrate structures nucleate will be tremendously beneficial for the development of sustainable hydrate management strategies in oil and gas flowlines, as well as for their application in energy storage and recovery, gas separation, carbon sequestration, seawater desalination, and refrigeration. This article reviews various aspects of hydrate nucleation. First, properties of supercooled water and ice nucleation are reviewed briefly due to their apparent similarity to hydrates. Hydrate nucleation is then reviewed starting from macroscopic observations as obtained from experiments in laboratories and operations in industries, followed by various hydrate nucleation hypotheses and hydrate nucleation driving force calculations based on the classical nucleation theory. Finally, molecular simulations on hydrate nucleation are discussed in detail followed by potential future research directions.

  4. Morphology, Orientation Relationship and Stability Analysis of Cu2O nanoclusters on SrTiO3 (100)

    Energy Technology Data Exchange (ETDEWEB)

    Kuchibhatla, Satyanarayana V N T; Hu, Shenyang Y.; Yu, Zhongqing; Shutthanandan, V.; Li, Ye; Nachimuthu, Ponnusamy; Jiang, Weilin; Thevuthasan, Suntharampillai; Henager, Charles H.; Sundaram, S. K.

    2009-08-03

    Reflection high energy electron diffraction (RHEED), atomic force microscopy (AFM) and theoretical studies based on classical nucleation theory have been used to understand the morphology, orientation relationship and stability of Cu2O nanoclusters on SrTiO3 (100) (STO). We propose that the competing interfacial and elastic energies facilitate an in-plane rotation of the Cu2O clusters by 45o with respect to the STO substrate and stabilize Cu2O clusters on STO(100) with an orientation relationship of (001) Cu 2o //(001) SrTiO3 and <100> Cu 2o //<110> SrTiO3. Preliminary theoretical analysis also suggests that this particular orientation results in smaller critical nucleus sizes and lower nucleation barriers. The study also indicates a chemical potential (growth rate) dependence of the orientation relationship.

  5. Bleb Nucleation through Membrane Peeling

    CERN Document Server

    Alert, Ricard

    2016-01-01

    We study the nucleation of blebs, i.e., protrusions arising from a local detachment of the membrane from the cortex of a cell. Based on a simple model of elastic linkers with force-dependent kinetics, we show that bleb nucleation is governed by membrane peeling. By this mechanism, the growth or shrinkage of a detached membrane patch is completely determined by the linker kinetics, regardless of the energetic cost of the detachment. We predict the critical nucleation radius for membrane peeling and the corresponding effective energy barrier. These may be typically smaller than those predicted by classical nucleation theory, implying a much faster nucleation. We also perform simulations of a continuum stochastic model of membrane-cortex adhesion to obtain the statistics of bleb nucleation times as a function of the stress on the membrane. The determinant role of membrane peeling changes our understanding of bleb nucleation and opens new directions in the study of blebs.

  6. 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.

  7. 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.

  8. 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...

  9. Kinetics of Ag-rich precipitates formation in Cu-Al-Ag alloys

    Energy Technology Data Exchange (ETDEWEB)

    Adorno, A.T.; Guerreiro, M.R.; Silva, R.A.G

    2004-06-15

    The kinetics of Ag-rich precipitates formation in the Cu-2 wt.% Al alloy with additions of 2, 4, 6, 8, 10 and 12 wt.% Ag was studied using microhardness changes with temperature and time, differential scanning calorimetry (DSC), differential thermal analysis (DTA), scanning electron microscopy (SEM), optical microscopy (OM), energy dispersive X-ray analysis (EDX) and X-ray diffractometry (XRD). The results indicated that an increase in the Ag content decreases the activation energy for Ag-rich precipitates formation, and that it is possible to estimate the values of the diffusion and nucleation activation energies for the Ag precipitates.

  10. 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.

  11. Primary nucleation of lithium carbonate

    Institute of Scientific and Technical Information of China (English)

    Yuzhu SUN; Xingfu SONG; Jin WANG; Yan LUO; Jianguo YU

    2009-01-01

    A set of laser apparatus was used to explore the induction period and the primary nucleation of lithium carbonate. Results show that the induction period increases with the decrease of supersaturation, temperature and stirring speed. Through the classical theory of primary nucleation, many important properties involved in primary nucleation under different conditions were obtained quantitatively, including the interfacial tension between solid and liquid, contact angle, critical nucleus size, critical nuleation free energy etc.

  12. 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.

  13. Nucleate boiling heat transfer

    Energy Technology Data Exchange (ETDEWEB)

    Saiz Jabardo, J.M. [Universidade da Coruna (Spain). Escola Politecnica Superior], e-mail: mjabardo@cdf.udc.es

    2009-07-01

    Nucleate boiling heat transfer has been intensely studied during the last 70 years. However boiling remains a science to be understood and equated. In other words, using the definition given by Boulding, it is an 'insecure science'. It would be pretentious of the part of the author to explore all the nuances that the title of the paper suggests in a single conference paper. Instead the paper will focus on one interesting aspect such as the effect of the surface microstructure on nucleate boiling heat transfer. A summary of a chronological literature survey is done followed by an analysis of the results of an experimental investigation of boiling on tubes of different materials and surface roughness. The effect of the surface roughness is performed through data from the boiling of refrigerants R-134a and R-123, medium and low pressure refrigerants, respectively. In order to investigate the extent to which the surface roughness affects boiling heat transfer, very rough surfaces (4.6 {mu}m and 10.5 {mu}m ) have been tested. Though most of the data confirm previous literature trends, the very rough surfaces present a peculiar behaviour with respect to that of the smoother surfaces (Ra<3.0 {mu}m). (author)

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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...

  20. 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

  1. Nucleation of Crystals in Solution

    Science.gov (United States)

    Vekilov, Peter G.

    2010-07-01

    Solution crystallization is an essential part of processes in the chemical and pharmaceutical industries and a major step in physiological and pathological phenomena. Crystallization starts with nucleation and control of nucleation is crucial for the control of the number, size, perfection, polymorphism and other characteristics of the crystalline materials. Recently, there have been significant advances in the understanding of the mechanism of nucleation of crystals in solution. The most significant of these is the two-step mechanism of nucleation, according to which the crystalline nucleus appears inside pre-existing metastable clusters of size several hundred nanometers, which consist of dense liquid and are suspended in the solution. While initially proposed for protein crystals, the applicability of this mechanism has been demonstrated for small molecule organic materials, colloids, and biominerals. This mechanism helps to explain several long-standing puzzles of crystal nucleation in solution: nucleation rates which are many orders of magnitude lower than theoretical predictions, nucleation kinetic dependencies with steady or receding parts at increasing supersaturation, the role of heterogeneous substrates for polymorph selection, the significance of the dense protein liquid, and others. More importantly, this mechanism provides powerful tools for control of the nucleation process by varying the solution thermodynamic parameters so that the volume occupied by the dense liquid shrinks or expands.

  2. 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.

  3. 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.

  4. Label-Free Fluorescent Detection of Trypsin Activity Based on DNA-Stabilized Silver Nanocluster-Peptide Conjugates

    Directory of Open Access Journals (Sweden)

    Cai-Xia Zhuo

    2016-11-01

    Full Text Available Trypsin is important during the regulation of pancreatic exocrine function. The detection of trypsin activity is currently limited because of the need for the substrate to be labeled with a fluorescent tag. A label-free fluorescent method has been developed to monitor trypsin activity. The designed peptide probe consists of six arginine molecules and a cysteine terminus and can be conjugated to DNA-stabilized silver nanoclusters (DNA-AgNCs by Ag-S bonding to enhance fluorescence. The peptide probe can also be adsorbed to the surface of graphene oxide (GO, thus resulting in the fluorescence quenching of DNA-AgNCs-peptide conjugate because of Förster resonance energy transfer. Once trypsin had degraded the peptide probe into amino acid residues, the DNA-AgNCs were released from the surface of GO, and the enhanced fluorescence of DNA-AgNCs was restored. Trypsin can be determined with a linear range of 0.0–50.0 ng/mL with a concentration as low as 1 ng/mL. This label-free method is simple and sensitive and has been successfully used for the determination of trypsin in serum. The method can also be modified to detect other proteases.

  5. Highly selective detection of bacterial alarmone ppGpp with an off-on fluorescent probe of copper-mediated silver nanoclusters.

    Science.gov (United States)

    Zhang, Pu; Wang, Yi; Chang, Yong; Xiong, Zu Hong; Huang, Cheng Zhi

    2013-11-15

    In this study, a facile strategy for highly selective and sensitive detection of bacterial alarmone, ppGpp, which is generated when bacteria face stress circumstances such as nutritional deprivation, has been established by developing an off-on fluorescent probe of Cu(2+)-mediated silver nanoclusters (Ag NCs). This work not only achieves highly selective detection of ppGpp in a broad range concentration of 2-200 μM, but also improves our understanding of the specific recognitions among DNA-Ag NCs, Cu(2+), and ppGpp. The present strategy, together with other reports on the Ag NCs-related analytical methods, has also identified that Ag NCs functionalized with different molecules on their surfaces can be engineered fluorescent probes for a wide range of applications such as biosensing and bioimaging.

  6. Surface-supported Ag islands stabilized by a quantum size effect: Their interaction with small molecules relevant to ethylene epoxidation

    Energy Technology Data Exchange (ETDEWEB)

    Shao, Dahai [Iowa State Univ., Ames, IA (United States)

    2013-05-15

    This dissertation focuses on how QSE-stabilized, surface-supported Ag nanoclusters will interact with ethylene or oxygen. Experiments are performed to determine whether the QSE-mediated Ag islands react differently toward adsorption of ethylene or oxygen, or whether the adsorption of these small molecules will affect the QSE-mediated stability of Ag islands. Studies of the interaction of oxygen with Ag/Si(111)-7×7 were previously reported, but these studies were performed at a low Ag coverage where 3D Ag islands were not formed. So the study of such a system at a higher Ag coverage will be a subject of this work. The interaction of ethylene with Ag/Si(111)-7×7, as well as the interaction of oxygen with Ag/NiAl(110) are also important parts of this study.

  7. Effect of compartmentalization of donor and acceptor on the ultrafast resonance energy transfer from DAPI to silver nanoclusters

    Science.gov (United States)

    Prajapati, Roopali; Chatterjee, Surajit; Kannaujiya, Krishna K.; Mukherjee, Tushar Kanti

    2016-06-01

    The mechanism and dynamics of excitation energy transfer (EET) from photo-excited 4',6-diamidino-2-phenylindole (DAPI) to silver nanoclusters (Ag NCs) and its subsequent modulation in the presence of cationic polymer poly(diallyldimethylammonium chloride) (PDADMAC) and Calf Thymus DNA (CT-DNA) have been demonstrated using steady-state fluorescence and femtosecond fluorescence upconversion techniques. The synthesized Ag NCs were characterized using FTIR, mass spectrometry, XPS, HRTEM, DLS, UV-Vis and PL spectroscopy. Mass spectrometric analysis reveals the formation of ultrasmall Ag4 NCs with a small amount of Ag5 NCs. UV-Vis and PL spectra reveal distinct molecular-like optoelectronic behaviour of these ultrasmall Ag NCs. The dihydrolipoic acid-capped Ag NCs strongly quench the fluorescence of DAPI with concomitant increase in its photoluminescence (PL) intensity at 675 nm. This steady-state fluorescence quenching proceeds with a significant shortening of the fluorescence lifetime of DAPI in the presence of Ag NCs, signifying the nonradiative Förster resonance energy transfer (FRET) from DAPI to Ag NCs. Various energy transfer parameters have been estimated from FRET theory. The present FRET pair shows a characteristic Förster distance of 2.45 nm and can be utilized as a reporter of short-range distances in various FRET based applications. Moreover, this nonradiative FRET is completely suppressed in the presence of both 0.2 wt% PDADMAC and CT-DNA. Our results reveal selective compartmentalization of Ag NCs and DAPI in the presence of 0.2 wt% PDADMAC and CT-DNA, respectively. This selective compartmentalization of donor and acceptor and the subsequent modification of the FRET process may find application in various sensing, photovoltaic, and light harvesting applications.The mechanism and dynamics of excitation energy transfer (EET) from photo-excited 4',6-diamidino-2-phenylindole (DAPI) to silver nanoclusters (Ag NCs) and its subsequent modulation in the presence

  8. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  10. Tailoring the magnetic properties of cobalt-ferrite nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    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.

  11. Binary nucleation beyond capillarity approximation

    NARCIS (Netherlands)

    Kalikmanov, V.I.

    2010-01-01

    Large discrepancies between binary classical nucleation theory (BCNT) and experiments result from adsorption effects and inability of BCNT, based on the phenomenological capillarity approximation, to treat small clusters. We propose a model aimed at eliminating both of these deficiencies. Adsorption

  12. Short review on Controlled Nucleation

    Directory of Open Access Journals (Sweden)

    Gupta Anuj

    2012-09-01

    Full Text Available Freeze-drying (also known as lyophilization or cryodesiccation is a dehydration process mainly used to preserve for perishable material and this method make the material more convenient for transport. Freezedrying works by freezing the material and then reducing the surrounding pressure and giving sufficient heat to allow the frozen water into the material to sublime directly from the solid phase to gas phase. Sublimation is the transition of a substance from the solid to the vapor state, without first passing through an intermediate liquid phase. A method to achieve controlled ice nucleation during the freeze-drying process using an ice fog, vial treatment, ultrasound, additives and electro freezing technique was demonstrated in an earlier report. And by the potential of a high electric field was utilized to induce ice nucleus formation in aqueous solutions. Using this technique it was possible to reduce the primary drying time during lyophilization. [1] Many technical issues surrounding the freeze-drying process have been addressed over the past several decades. Better understanding of critical formulation characteristics and cycle conditions. There are two types of technique for nucleation 1 Uncontrolled Nucleation, 2 Controlled Nucleation. The objectives of the present study simply introduce controlled Nucleation is the rapid ice nucleation in freeze drying technique. [2

  13. 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 ...

  14. 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.

  15. 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...

  16. Microwave-assisted synthesis of photoluminescent glutathione-capped Au/Ag nanoclusters: A unique sensor-on-a-nanoparticle for metal ions, anions, and small molecules

    Institute of Scientific and Technical Information of China (English)

    Jia Zhang[1; Yue Yuan[1; Yu Wang[2; Fanfei Sun[2; Gaolin Liang[1; Zheng Jiang[2; Shu-Hong Yu[1,3

    2015-01-01

    Even though great advances have been achieved in the synthesis of luminescent metal nanoclusters, it is still challenging to develop metal nanoclusters with high quantum efficiency as well as multiple sensing functionalities. Here, we demonstrate the rapid preparation of glutathione-capped Au/Ag nanoclusters (GS-Au/Ag NCs) using microwave irradiation and their unique sensing capacities. Compared to bare GS-Au NCs, the doped Au/Ag NCs possess an enhanced quantum yield (7.8% compared to 2.2% for GS-Au NCs). Several characterization techniques were used to elucidate the atomic composition, particulate character, and electronic structure of the fabricated NCs. According to the X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) spectra, a significant amount of Au exists in the oxidized state as Au(I), and the Ag atoms are positively charged. In contrast to those nanoclusters that detect only one analyte, the GS-Au/Ag NCs can be used as a versatile sensor for metal ions, anions, and small molecules. In this manner, the NCs can be regarded as a unique sensor-on-a-nanoparticle.

  17. Hairpin DNA probe with 5'-TCC/CCC-3' overhangs for the creation of silver nanoclusters and miRNA assay.

    Science.gov (United States)

    Xia, Xiaodong; Hao, Yuanqiang; Hu, Shengqiang; Wang, Jianxiu

    2014-01-15

    A facile strategy for the assay of target miRNA using fluorescent silver nanoclusters (AgNCs) has been described. Due to the preferable interaction between cytosine residues and Ag(+), a short cytosine-rich oligonucleotide (ODN) with only six bases 5'-TCCCCC-3' served as an efficient scaffold for the creation of the AgNCs. The AgNCs displayed a bright red emission when excited at 545nm. Such ODN base-stabilized AgNCs have been exploited for miRNA sensing. Overhangs of TCC at the 5' end (5'-TCC) and CCC at the 3' end (CCC-3') (denoted as 5'-TCC/CCC-3') appended to the hairpin ODN probe which also contains recognition sequences for target miRNA were included. Interestingly, the AgNCs/hairpin ODN probe showed similar spectral properties as that templated by 5'-TCCCCC-3'. The formation of the hairpin ODN probe/miRNA duplex separated the 5'-TCC/CCC-3' overhangs, thus disturbing the optical property or structure of the AgNCs. As a result, fluorescence quenching of the AgNCs/hairpin ODN probe was obtained, which allows for facile determination of target miRNA. The proposed method is simple and cost-effective, holding great promise for clinical applications.

  18. Improvement in the photocurrent collection due to enhanced absorption of light by synthesizing staggered layers of silver nanoclusters in silicon

    Energy Technology Data Exchange (ETDEWEB)

    Dhoubhadel, Mangal S.; Lakshantha, Wickramaarachchige J.; Rout, Bibhudutta; McDaniel, Floyd D., E-mail: mcdaniel@unt.edu [Ion Beam Modification and Analysis Laboratory, Department of Physics, University of North Texas, Denton, Texas 76203 (United States); Lightbourne, Sherard; D’Souza, Francis [Department of Chemistry, University of North Texas, Denton, Texas 76203 (United States)

    2015-07-23

    The quest for increased efficiency of solar cells has driven the research in synthesizing photovoltaic cells involving Si based materials. The efficiency of solar cells involving crystalline Si is stalled around 25% for the last decade. Recently Shi et al. had shown that light trapping can be enhanced by fabricating double layers of Ag nanoparticles in silicon based materials. The light trapping is critically important in a photo devices such as solar cells in order to increase light absorption and efficiency. In the present work, we report enhancement in the absorption of light in Ag ion implanted Si substrates. Multiple low energies Ag ions, ranging from ∼80 keV to ∼30 keV, with different fluences ranging from ∼1 × 10{sup 16} to ∼1 × 10{sup 17} atoms/cm{sup 2} were sequentially implanted into commercially available Si (100) substrates followed by post-thermal annealing to create different sizes of Ag nanoclusters (NC) at different depths in the top 100 nm of the Si. The absorbance of light is increased in Ag implanted Si with a significant increase in the current collection in I-V (current-voltage) photo switching measurements. The experimental photovoltaic cells fabricated with the Ag-implanted Si samples were optically characterized under AM (air mass) 1.5 solar radiation conditions (∼1.0 kW/m{sup 2}). An enhancement in the charge collection were measured in the annealed samples, where prominent Ag NCs were formed in the Si matrix compared to the as-implanted samples with amorphous layers. We believe the enhancement of the photo-current density from the samples with Ag NC is due to the improvement of efficiency of charge collection of e{sup −}-h{sup +} pairs produced by the incident light.

  19. 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

  20. 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.

  1. Nucleation and growth during recrystallization

    Directory of Open Access Journals (Sweden)

    Paulo Rangel Rios

    2005-09-01

    Full Text Available The evolution in the understanding of the recrystallization phenomena is summarized in this paper. Initially the main developments concerning recrystallization are presented from a historical perspective. Definitions and concepts involving recrystallization are presented regarding it as a solid-state reaction that occurs by nucleation and growth. The recrystallization nucleation mechanisms are subsequently discussed. Finally, the growth step is highlighted, emphasizing boundary and sub-boundary mobilities and the forces acting on the high angle grain boundaries that sweep the microstructure during recrystallization.

  2. 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.

  3. 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

  4. 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.

  5. Sodium cholate-templated blue light-emitting Ag subnanoclusters: in vivo toxicity and imaging in zebrafish embryos.

    Science.gov (United States)

    Chandirasekar, Shanmugam; Chandrasekaran, Chandramouli; Muthukumarasamyvel, Thangavel; Sudhandiran, Ganapasam; Rajendiran, Nagappan

    2015-01-28

    We report a novel green chemical approach for the synthesis of blue light-emitting and water-soluble Ag subnanoclusters, using sodium cholate (NaC) as a template at a concentration higher than the critical micelle concentration (CMC) at room temperature. However, under photochemical irradiation, small anisotropic and spherically shaped Ag nanoparticles (3-11 nm) were obtained upon changing the concentration of NaC from below to above the CMC. The matrix-assisted laser desorption ionization time-of-flight and electrospray ionization mass spectra showed that the cluster sample was composed of Ag4 and Ag6. The optical properties of the clusters were studied by UV-visible and luminescence spectroscopy. The lifetime of the synthesized fluorescent Ag nanoclusters (AgNCs) was measured using a time-correlated single-photon counting technique. High-resolution transmission electron microscopy was used to assess the size of clusters and nanoparticles. A protocol for transferring nanoclusters to organic solvents is also described. Toxicity and bioimaging studies of NaC templated AgNCs were conducted using developmental stage zebrafish embryos. From the survival and hatching experiment, no significant toxic effect was observed at AgNC concentrations of up to 200 μL/mL, and the NC-stained embryos exhibited blue fluorescence with high intensity for a long period of time, which shows that AgNCs are more stable in living system.

  6. 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.

  7. A selective and label-free strategy for rapid screening of telomere-binding Ligands via fluorescence regulation of DNA/silver nanocluster

    Science.gov (United States)

    Cheng, Rui; Xu, Jing; Zhang, Xiafei; Shi, Zhilu; Zhang, Qi; Jin, Yan

    2017-03-01

    Herein, the conformational switch of G-rich oligonucleotide (GDNA) demonstrated the obvious functional switch of GDNA which was found to significantly affect the fluorescence of the in-situ synthesized DNA/silver nanocluster (DNA-AgNC) in homogeneous solution. We envisioned that the allosteric interaction between GDNA and DNA-AgNC would be possible to be used for screening telomere-binding ligands. A unimolecular probe (12C5TG) is ingeniously designed consisting of three contiguous DNA elements: G-rich telomeric DNA (GDNA) as molecular recognition sequence, T-rich DNA as linker and C-rich DNA as template of DNA-AgNC. The quantum yield and stability of 12C5TG-AgNC is greatly improved because the nearby deoxyguanosines tended to protect DNA/AgNC against oxidation. However, in the presence of ligands, the formation of G-quadruplex obviously quenched the fluorescence of DNA-AgNC. By taking full advantage of intramolecular allosteric effect, telomere-binding ligands were selectively and label-free screened by using deoxyguanines and G-quadruplex as natural fluorescence enhancer and quencher of DNA-AgNC respectively. Therefore, the functional switching of G-rich structure offers a cost-effective, facile and reliable way to screen drugs, which holds a great potential in bioanalysis as well.

  8. A selective and label-free strategy for rapid screening of telomere-binding Ligands via fluorescence regulation of DNA/silver nanocluster

    Science.gov (United States)

    Cheng, Rui; Xu, Jing; Zhang, Xiafei; Shi, Zhilu; Zhang, Qi; Jin, Yan

    2017-01-01

    Herein, the conformational switch of G-rich oligonucleotide (GDNA) demonstrated the obvious functional switch of GDNA which was found to significantly affect the fluorescence of the in-situ synthesized DNA/silver nanocluster (DNA-AgNC) in homogeneous solution. We envisioned that the allosteric interaction between GDNA and DNA-AgNC would be possible to be used for screening telomere-binding ligands. A unimolecular probe (12C5TG) is ingeniously designed consisting of three contiguous DNA elements: G-rich telomeric DNA (GDNA) as molecular recognition sequence, T-rich DNA as linker and C-rich DNA as template of DNA-AgNC. The quantum yield and stability of 12C5TG-AgNC is greatly improved because the nearby deoxyguanosines tended to protect DNA/AgNC against oxidation. However, in the presence of ligands, the formation of G-quadruplex obviously quenched the fluorescence of DNA-AgNC. By taking full advantage of intramolecular allosteric effect, telomere-binding ligands were selectively and label-free screened by using deoxyguanines and G-quadruplex as natural fluorescence enhancer and quencher of DNA-AgNC respectively. Therefore, the functional switching of G-rich structure offers a cost-effective, facile and reliable way to screen drugs, which holds a great potential in bioanalysis as well. PMID:28262705

  9. 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.

  10. 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.

  11. 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.

  12. Magnetic properties of colloidal cobalt nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    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).

  13. 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.

  14. 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.

  15. Summary of in situ epitaxial nucleation and growth measurements. [for semiconducting single crystal PbSe films

    Science.gov (United States)

    Poppa, H.; Moorhead, R. D.; Heinemann, K.

    1974-01-01

    In situ nucleation and growth measurements of Ag and Au on single-crystal PbSe thin films were made using a transmission electron microscope. Properties studied were polymorphism, crystalline perfection, and the stoichiometric composition of the initial and the autoepitaxially thickened PbSe substrates. The quantitative nucleation and cluster growth measurements were limited to low-saturation conditions. The epitaxial orientations are discussed, and evidence is presented as to the stage of deposition at which the epitaxial order for Ag is introduced. Strong substrate/overgrowth interaction manifested itself by alloying and interdiffusion.

  16. 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.

  17. 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

  18. In-vitro Synthesis of Gold Nanoclusters in Neurons

    Science.gov (United States)

    2016-04-01

    and account for 80% of all head injuries.6 mTBIs are rarely accompanied with neuroanatomical abnormalities detectable by conventional imaging...Liu T-Y, Li H-W, Wu Y, Li Q, Wang K, Zou BJ. Pressure-induced fluorescence enhancement of the BSA-protected gold nanoclusters and the corresponding

  19. 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

  20. Electrochemical nucleation and growth of copper and copper alloys

    Science.gov (United States)

    Shao, Wenbo

    This dissertation aims to contribute to a fundamental understanding of the physicochemical processes occurring in electrochemical nucleation and growth. To this end, the effects of various anions (chloride (Cl-), sulfate (SO42-) and sulfamate (NH2SO 3-)) on the electrochemical kinetics and the mechanism of copper reduction, as well as on the microstructure of the resulting films, were studied. On the basis of this work, the deposition of copper alloys (Cu-Ag with positive heat of mixing, Cu-Au with negative heat of mixing) was investigated with the main objective to achieve an insight on the role of solid state thermodynamics on the electrocrystallization process. Chloride ions cause two competing effects: at low chloride concentration the formation of an adsorbed chloride layer introduces an additional reaction pathway, resulting in an overall depolarization of the reduction process with no significant change of the Tafel slope. At high chloride concentration, complexation phenomena induce a cathodic polarization of the deposition process and a decrease in the Tafel slope. Chlorides cause a decrease in the density and an increased size of copper nuclei. Sulfamate depolarizes copper reduction the most and results in the largest nucleus density. Chloride promotes the faceting, and dendritic growth of copper deposits along direction by introducing interfacial anisotropy. Addition of Ag in the solution or in the electrode substrate enhances copper deposition and results in an additional reduction peak. Codeposition of Cu-Ag increases nucleus density and decreases nucleus size. Such enhancement of copper deposition, the increase in nucleus density and the decrease in nucleus size by Ag could be due to the continued formation of a surface alloy of Cu-Ag and the fast interface dynamics of Ag deposition. Cu can be underpotentially codeposited in the Cu-Au alloy. Homogeneous solid solutions are grown under conditions of underpotential deposition of Cu, while precipitation

  1. Ice nucleation activity of polysaccharides

    Science.gov (United States)

    Bichler, Magdalena; Felgitsch, Laura; Haeusler, Thomas; Seidl-Seiboth, Verena; Grothe, Hinrich

    2015-04-01

    Heterogeneous ice nucleation is an important process in the atmosphere. It shows direct impact on our climate by triggering ice cloud formation and therefore it has much influence on the radiation balance of our planet (Lohmann et al. 2002; Mishchenko et al. 1996). The process itself is not completely understood so far and many questions remain open. Different substances have been found to exhibit ice nucleation activity (INA). Due to their vast differences in chemistry and morphology it is difficult to predict what substance will make good ice nuclei and which will not. Hence simple model substances must be found and be tested regarding INA. Our work aims at gaining to a deeper understanding of heterogeneous ice nucleation. We intend to find some reference standards with defined chemistry, which may explain the mechanisms of heterogeneous ice nucleation. A particular focus lies on biological carbohydrates in regards to their INA. Biological carbohydrates are widely distributed in all kingdoms of life. Mostly they are specific for certain organisms and have well defined purposes, e.g. structural polysaccharides like chitin (in fungi and insects) and pectin (in plants), which has also water-binding properties. Since they are widely distributed throughout our biosphere and mostly safe to use for nutrition purposes, they are well studied and easily accessible, rendering them ideal candidates as proxies. In our experiments we examined various carbohydrates, like the already mentioned chitin and pectin, as well as their chemical modifications. Lohmann U.; A Glaciation Indirect Aerosol Effect Caused by Soot Aerosols; J. Geoph. Res.; Vol. 24 No.4; pp 11-1 - 11-4; 2002 Mishchenko M.I., Rossow W.B., Macke A., Lacis A. A.; Sensitivity of Cirrus Cloud Albedo, Bidirectional Reflectance and Optical Thickness Retrieval Accuracy to Ice Particle Shape, J. Geoph. Res.; Vol. 101, No D12; pp. 16,973 - 16,985; 1996

  2. Ice nucleation properties of agricultural soil dusts

    Science.gov (United States)

    Steinke, Isabelle; Funk, Roger; Busse, Jacqueline; Iturri, Antonela; Kirchen, Silke; Leue, Martin; Möhler, Ottmar; Schwartz, Thomas; Sierau, Berko; Toprak, Emre; Ulrich, Andreas; Hoose, Corinna; Leisner, Thomas

    2015-04-01

    Soil dust particles emitted from agricultural areas contain large amounts of organic material such as fungi, bacteria and plant debris. Being carrier for potentially highly ice-active biological particles, agricultural soil dusts are candidates for being very ice-active as well. In this work, we present ice nucleation experiments conducted in the AIDA cloud chamber. We investigated the ice nucleation efficiency of four types of soil dust from different regions of the world. Results are presented for the immersion freezing and the deposition nucleation mode: all soil dusts show higher ice nucleation efficiencies than desert dusts, especially at temperatures above 254 K. For one soil dust sample, the effect of heat treatments was investigated. Heat treatments did not affect the ice nucleation efficiency which presumably excludes primary biological particles as the only source of the increased ice nucleation efficiency. Therefore, organo-mineral complexes or organic compounds may contribute substantially to the high ice nucleation activity of agricultural soil dusts.

  3. Synthesis and photoactivity of the highly efficient Ag species/TiO{sub 2} nanoflakes photocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Liu Yong [Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission and Ministry of Education, South-Central University for Nationalities, Wuhan 430074 (China); Hu Juncheng, E-mail: junchenghuhu@hotmail.com [Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission and Ministry of Education, South-Central University for Nationalities, Wuhan 430074 (China); Li Jinlin [Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission and Ministry of Education, South-Central University for Nationalities, Wuhan 430074 (China)

    2011-04-21

    Research highlights: > Highly efficient Ag species-TiO{sub 2} nanoflakes catalyst was prepared. > The variety and relative amount of Ag species in TiO{sub 2} can be well tuned. > The enhanced photocatalytic activity can be attributed to the Ag species. - Abstract: Ag species/TiO{sub 2} nanoflakes photocatalysts with different relative contents (Ag{sup +}, Ag{sup 2+}, Ag{sup 0}) have been successfully synthesized by a simple template-free synthetic strategy. X-ray photoelectron spectroscopy, X-ray diffraction, and UV-vis diffuse reflectance spectra indicated that the dopant ions (Ag{sup +} or Ag{sup 2+}) were partly incorporated into the titanium dioxide nanoflakes. Meanwhile, part of the silver ions migrated to the surface after the subsequent calcination and aggregated into ultra-small metallic Ag nanoclusters (NCs) (1-2 nm), which are well dispersed on the surface of TiO{sub 2} nanoflakes. The photocatalytic activities of the Ag species/TiO{sub 2} materials obtained were evaluated by testing the photodegradation of the azo dye reactive brilliant X-3B (X-3B) under near UV irradiation. Interestingly, it was found that the maximum photocatalytic efficiency was observed when Ag species coexisted in three valence states (Ag{sup +}, Ag{sup 2+}, Ag{sup 0} NCs), which was higher than that of Degussa P25. The high photocatalytic activity of the Ag species/TiO{sub 2} can be attributed to the synergy effect of the three Ag species.

  4. Flourescent Peptide-Stabilized Silver-Nanoclusters

    DEFF Research Database (Denmark)

    Gregersen, Simon

    to their physical and optoelectronic properties. These include great photostability, low toxicity, small size, and tunable spectral properties. Chemical stability of noble metal NCs is, however, very low, and they only exist transiently without a stabilizing scaffold. This has to date been done in solution using......, and better chemical stability than seen for many Ag-NCs published to date. By physical and optical characterization, we investigate the composition as well as the mechanism for formation of peptide-stabilized fluorescent Ag-NCs, which indicates that the process includes a dynamic folding....../reorganization of the peptide to facilitate NC formation. Following an initial chelation involving the thiol-functionality of cysteine side-chains, the coordination of silver into a defined NC is expected to be the driving force of the folding process. This work also illustrates the shortcomings of MALDI-TOF mass spectrometry...

  5. All-thiol-stabilized Ag44 and Au12Ag32 nanoparticles with single-crystal structures.

    Science.gov (United States)

    Yang, Huayan; Wang, Yu; Huang, Huaqi; Gell, Lars; Lehtovaara, Lauri; Malola, Sami; Häkkinen, Hannu; Zheng, Nanfeng

    2013-01-01

    Noble metal nanoparticles stabilized by organic ligands are important for applications in assembly, site-specific bioconjugate labelling and sensing, drug delivery and medical therapy, molecular recognition and molecular electronics, and catalysis. Here we report crystal structures and theoretical analysis of three Ag44(SR)30 and three Au12Ag32(SR)30 intermetallic nanoclusters stabilized with fluorinated arylthiols (SR=SPhF, SPhF2 or SPhCF3). The nanocluster forms a Keplerate solid of concentric icosahedral and dodecahedral atom shells, protected by six Ag2(SR)5 units. Positive counterions in the crystal indicate a high negative charge of 4(-) per nanoparticle, and density functional theory calculations explain the stability as an 18-electron superatom shell closure in the metal core. Highly featured optical absorption spectra in the ultraviolet-visible region are analysed using time-dependent density functional perturbation theory. This work forms a basis for further understanding, engineering and controlling of stability as well as electronic and optical properties of these novel nanomaterials.

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  7. Communication: Kinetics of scavenging of small, nucleating clusters: First nucleation theorem and sum rules

    Science.gov (United States)

    Malila, Jussi; McGraw, Robert; Laaksonen, Ari; Lehtinen, Kari E. J.

    2015-01-01

    Despite recent advances in monitoring nucleation from a vapor at close-to-molecular resolution, the identity of the critical cluster, forming the bottleneck for the nucleation process, remains elusive. During past twenty years, the first nucleation theorem has been often used to extract the size of the critical cluster from nucleation rate measurements. However, derivations of the first nucleation theorem invoke certain questionable assumptions that may fail, e.g., in the case of atmospheric new particle formation, including absence of sub-critical cluster losses and heterogeneous nucleation on pre-existing nanoparticles. Here, we extend the kinetic derivation of the first nucleation theorem to give a general framework to include such processes, yielding sum rules connecting the size dependent particle formation and loss rates to the corresponding loss-free nucleation rate and the apparent critical size from a naïve application of the first nucleation theorem that neglects them.

  8. 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.

  9. 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.

  10. 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.

  11. The IP6 micelle-stabilized small Ag cluster for synthesizing Ag-Au alloy nanoparticles and the tunable surface plasmon resonance effect

    Science.gov (United States)

    Wang, Na; Wen, Ying; Wang, Yao; Zhang, Rui; Chen, Xiyao; Ling, Bo; Huan, Shuangyan; Yang, Haifeng

    2012-04-01

    The stable small Ag seeds (size in diameter inositol hexakisphosphoric (IP6) micelles. Then Ag-Au bimetallic nanoparticles were synthesized through a replacement reaction with the rapid interdiffusion process between such small Ag seeds in nanoclusters and HAuCl4. Adjusting the dosage of HAuCl4 resulted in different products, which possessed unique surface plasmon resonances (SPR). The morphologies of the as-made nanoparticles were observed using transmission electron microscopy and field emission scanning electron microscopy and their compositions were determined by energy-dispersive x-ray spectroscopy. Among them, the Ag-Au alloy nanoparticles with the cauliflower-like structure had a suitable SPR for highly sensitive Raman detection application as a surface-enhanced Raman scattering (SERS) substrate with a long-term stability of six months.

  12. 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

  13. Stochastic analysis of nucleation rates

    Science.gov (United States)

    Johansson, Jonas

    2016-02-01

    We show that approximating the Becker-Döring equations with a Langevin equation results in multiplicative noise, which in turn leads to a family of possible Fokker-Planck equations according to the Ito-Stratonovich dilemma. Using a simple and general model for the attachment and detachment rates, we find that the Ito choice approximates the nucleation rate best and also coincides with the Fokker-Planck equation resulting from the common way to Taylor expand the original set of rate equations.

  14. Simple improvements to classical bubble nucleation models

    CERN Document Server

    Tanaka, Kyoko K; Angélil, Raymond; Diemand, Jürg

    2015-01-01

    We revisit classical nucleation theory (CNT) for the homogeneous bubble nucleation rate and improve the classical formula using a new prefactor in the nucleation rate. Most of the previous theoretical studies have used the constant prefactor determined by the bubble growth due to the evaporation process from the bubble surface. However, the growth of bubbles is also regulated by the thermal conduction, the viscosity, and the inertia of liquid motion. These effects can decrease the prefactor significantly, especially when the liquid pressure is much smaller than the equilibrium one. The deviation in the nucleation rate between the improved formula and the CNT can be as large as several orders of magnitude. Our improved, accurate prefactor and recent advances in molecular dynamics simulations and laboratory experiments for argon bubble nucleation enable us to precisely constrain the free energy barrier for bubble nucleation. Assuming the correction to the CNT free energy is of the functional form suggested by T...

  15. Human serum albumin-stabilized gold nanoclusters act as an electron transfer bridge supporting specific electrocatalysis of bilirubin useful for biosensing applications.

    Science.gov (United States)

    Santhosh, Mallesh; Chinnadayyala, Somasekhar R; Singh, Naveen K; Goswami, Pranab

    2016-10-01

    Human serum albumin (HSA)-stabilized Au18 nanoclusters (AuNCs) were synthesized and chemically immobilized on an Indium tin oxide (ITO) plate. The assembly process was characterized by advanced electrochemical and spectroscopic techniques. The bare ITO electrode generated three irreversible oxidation peaks, whereas the HSA-AuNC-modified electrode produced a pair of redox peaks for bilirubin at a formal potential of 0.27V (vs. Ag/AgCl). However, the native HSA protein immobilized on the ITO electrode failed to produce any redox peak for bilirubin. The results indicate that the AuNCs present in HSA act as electron transfer bridge between bilirubin and the ITO plate. Docking studies of AuNC with HSA revealed that the best docked structure of the nanocluster is located around the vicinity of the bilirubin binding site, with an orientation that allows specific oxidation. When the HSA-AuNC-modified electrode was employed for the detection of bilirubin using chronoamperometry at 0.3V (vs. Ag/AgCl), a steady-state current response against bilirubin in the range of 0.2μM to 7μM, with a sensitivity of 0.34μAμM(-1) and limit of detection of 86.32nM at S/N 3, was obtained. The bioelectrode was successfully applied to measure the bilirubin content in spiked serum samples. The results indicate the feasibility of using HSA-AuNC as a biorecognition element for the detection of serum bilirubin levels using an electrochemical technique.

  16. Nucleation kinetics of SrTiO3 3D islands and nanorings on Si substrates.

    Science.gov (United States)

    Tejedor, Paloma; Benedicto, Marcos; Vázquez, Luis; Galiana, Beatriz

    2014-11-07

    The nucleation of SrTiO3 three-dimensional (3D) islands and nanorings on Si substrates via a novel metalorganic decomposition (MOD) process has been investigated as a function of temperature and solution concentration of the SrTi(OC3H7)6 precursor. Quantitative analysis of island density and size distribution by atomic force microscopy (AFM) has revealed the existence of a nucleation regime at solution concentrations below 5 × 10(-3) M, in which the critical nucleus is a trimer and a coalescence regime at higher concentrations, dominated by growth of immobile clusters. Nanorings form preferentially under high supersaturation conditions and their size distribution is consistent with a dynamic coalescence. On the basis of recent theoretical models (Gill, 2012), we have proposed that the island-to-nanoring transition in the SrTiO3/Si system occurs above a critical size as a result of a competition between energetic and kinetic factors. The combination of high-resolution transmission electron microscopy (HRTEM) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) has shown that the monocrystalline SrTiO3 nanoclusters grow pseudomorphically on the Si substrate and exhibit a strain-induced tetragonal lattice distortion.

  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. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Surface poisoning in the nucleation and growth of palladium atomic layer deposition with Pd(hfac){sub 2} and formalin

    Energy Technology Data Exchange (ETDEWEB)

    Goldstein, D.N. [Department of Chemistry and Biochemistry, University of Colorado, 215 UCB, Boulder, CO 80309 (United States); George, S.M., E-mail: Steven.George@Colorado.Edu [Department of Chemistry and Biochemistry, University of Colorado, 215 UCB, Boulder, CO 80309 (United States); Department of Chemical and Biological Engineering, University of Colorado, 424 UCB, Boulder, CO (United States)

    2011-06-01

    Palladium (Pd) atomic layer deposition (ALD) can be performed with Pd(hfac){sub 2} (hfac = hexafluoroacetyl-acetone) and formalin as the reactants. For Pd ALD on oxide surfaces, the nucleation of Pd ALD has been observed to require between 20 and 100 ALD cycles. To understand the long nucleation periods, this study explored the surface reactions occurring during Pd ALD nucleation and growth on hydroxylated Al{sub 2}O{sub 3} substrates. In situ Fourier transform infrared (FTIR) spectroscopy on high surface area nanopowders was used to observe the surface species. The adsorption of Pd(hfac){sub 2} on hydroxylated Al{sub 2}O{sub 3} substrates was found to yield both Pd(hfac)* and Al(hfac)* surface species. The identity of the Al(hfac)* species was confirmed by separate FTIR studies of hfacH adsorption on the hydroxylated Al{sub 2}O{sub 3} substrates. Isothermal loss of the Al(hfac)* species revealed second-order kinetics at 448-523 K with an activation barrier of E{sub d} = 39.4 kcal/mol. The lack of correlation between Al(hfac)* and AlOH* species during the loss of Al(hfac)* species suggested that the Al(hfac)* species may desorb as Al(hfac){sub 3}. After Pd(hfac){sub 2} exposure and the subsequent formalin exposure on hydroxylated Al{sub 2}O{sub 3} substrates, only hfac ligands from Pd(hfac)* species were removed from the surface. In addition, the formalin exposure added formate species. The Al(hfac)* species was identified as the cause of the long nucleation period because Al(hfac)* behaves as a site blocker. The surface poisoning by Al(hfac)* species was corroborated by adsorbing hfacH prior to the Pd(hfac){sub 2} exposures. The amount of Pd(hfac)* species after Pd(hfac){sub 2} exposures decreased progressively versus the previous hfacH exposure. Pd ALD occurred gradually during the subsequent Pd ALD cycles as the Al(hfac)* species were slowly removed from the Al{sub 2}O{sub 3} surface. Ex situ transmission electron microscopy analysis revealed Pd nanoclusters

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Nucleation and mobility model of Agn clusters adsorbed on perfect and oxygen vacancy MgO surfaces.

    Science.gov (United States)

    Liu, Yongfei; Wang, Yan; Chen, Guangju

    2011-05-01

    The structures and energy properties for Ag(n) (n = 1-8) metal clusters adsorbed on the perfect and oxygen vacancy MgO surfaces have been studied by using the DFT/UB3LYP method with an embedded cluster model. The nucleation and mobility model for the Ag(n) (n = 1-8) clusters on the perfect and oxygen vacancy MgO(100) surfaces was investigated. The results show that the Ag atoms locate initially at the surface oxygen vacancy sites; then, with the growth of Ag cluster sizes, the large Ag clusters move possibly out of the vacancy sites by a rolling model, and diffuse on the MgO surface under a certain temperature condition. The relative energies needed for moving out of the oxygen vacancy region for the adsorbed Ag(n) clusters with the rolling model have been predicted. The even-odd oscillation behaviors for the cohesive energies, nucleation energies, first ionization potentials and HOMO-LUMO gaps of the adsorbed Ag(n) clusters with the variation of cluster sizes have also been discussed.

  9. 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.

  10. Rapid Detection of miRNA Using Nucleic Acids-templated AgNCs

    DEFF Research Database (Denmark)

    Shah, Pratik

    such as cancer, diabetes, cardiovascular disease and Alzheimer’s disease. MiRNAs, thus, can be useful markers for disease diagnosis, prognosis, and treatment. Because of its attractive optical properties such as brightness, tuneable emission wavelengths and photo-stability, DNA stabilized silver nano......-clusters (AgNCs) has increasingly been used to create nanoscale bio-sensing systems for selective and specific detection of bio-molecules. During the course of my Ph.D., I have focused on developing a novel diagnostic tool for miRNA detection using the fluorescent properties of DNA encapsulated AgNCs (DNA/Ag......NCs). I have showed that rapid, simple, sensitive and specific miRNA detection is possible. Two aspects of my research are 1) the implication of DNA secondary structure on the photoluminescence properties of DNA/AgNCs, 2) the development of a novel tool for miRNA detection in complex biological samples...

  11. 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

  12. Tuning Ice Nucleation with Supercharged Polypeptides

    NARCIS (Netherlands)

    Yang, Huige; Ma, Chao; Li, Kaiyong; Liu, Kai; Loznik, Mark; Teeuwen, Rosalie; van Hest, Jan C M; Zhou, Xin; Herrmann, Andreas; Wang, Jianjun

    2016-01-01

    Supercharged unfolded polypeptides (SUPs) are exploited for controlling ice nucleation via tuning the nature of charge and charge density of SUPs. The results show that positively charged SUPs facilitate ice nucleation, while negatively charged ones suppress it. Moreover, the charge density of the S

  13. Effects of clustered nucleation on recrystallization

    DEFF Research Database (Denmark)

    Storm, Søren; Juul Jensen, Dorte

    2009-01-01

    Computer simulations are used to study effects of an experimentally determined 3D distribution of nucleation sites on the recrystallization kinetics and on the evolution of the recrystallized microstructure as compared to simulations with random nucleation. It is found that although...

  14. Simple improvements to classical bubble nucleation models

    Science.gov (United States)

    Tanaka, Kyoko K.; Tanaka, Hidekazu; Angélil, Raymond; Diemand, Jürg

    2015-08-01

    We revisit classical nucleation theory (CNT) for the homogeneous bubble nucleation rate and improve the classical formula using a correct prefactor in the nucleation rate. Most of the previous theoretical studies have used the constant prefactor determined by the bubble growth due to the evaporation process from the bubble surface. However, the growth of bubbles is also regulated by the thermal conduction, the viscosity, and the inertia of liquid motion. These effects can decrease the prefactor significantly, especially when the liquid pressure is much smaller than the equilibrium one. The deviation in the nucleation rate between the improved formula and the CNT can be as large as several orders of magnitude. Our improved, accurate prefactor and recent advances in molecular dynamics simulations and laboratory experiments for argon bubble nucleation enable us to precisely constrain the free energy barrier for bubble nucleation. Assuming the correction to the CNT free energy is of the functional form suggested by Tolman, the precise evaluations of the free energy barriers suggest the Tolman length is ≃0.3 σ independently of the temperature for argon bubble nucleation, where σ is the unit length of the Lennard-Jones potential. With this Tolman correction and our prefactor one gets accurate bubble nucleation rate predictions in the parameter range probed by current experiments and molecular dynamics simulations.

  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. 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.

  17. A Brownian Model for Crystal Nucleation

    CERN Document Server

    Durán-Olivencia, Miguel A

    2013-01-01

    In this work a phenomenological Stochastic Differential Equation (SDE) is proposed for modelling the time-evolution of the radius of a pre-critical molecular cluster during nucleation (the classical order parameter). Such a SDE constitutes the basis for the calculation of the (nucleation) induction time under the Kramers' theory of thermally activated escape processes. Considering the nucleation stage as a Poisson's rare-event, analytical expressions for the induction time statistics are deduced for both steady and unsteady conditions, the latter assuming the semiadiabatic limit. These expressions can be used to identify the underlying mechanism of molecular cluster formation (distinguishing between homogeneous or heterogeneous nucleation from the nucleation statistics is possible) as well as to predict induction times and induction time distributions. The predictions of this model are in good agreement with experimentally measured induction times at constant temperature but agreement is not so good for induc...

  18. Nucleation in an Ultra Low Ionization Environment

    Science.gov (United States)

    Pedersen, J. O.; Enghoff, M. B.; Paling, S.; Svensmark, H.

    2010-12-01

    Atmospheric ions can enhance the nucleation of aerosols, as has been established by experiments, observation, and theory. In the clean marine atmosphere ionization is mainly caused by cosmic rays which in turn are controlled by the activity of the Sun, thus providing a potential link between solar activity and climate. In order to understand the effect ions may have on the production of cloud condensation nuclei the overall contribution of ion induced nucleation to the global production of secondary aerosols must be determined. One issue with determining this contribution is that several mechanisms for nucleation exist and it can be difficult to determine the relative importance of the various mechanisms in a given nucleation event when both ion induced and electrically neutral nucleation mechanisms are at work at the same time. We have carried out nucleation experiments in the Boulby Underground Laboratory, located 1100 meters below ground, thus reducing the flux of ionizing cosmic radiation by six orders of magnitude. Similarly we have reduced the gamma background by shielding the experiment in lead and copper. Finally we have used air stored for several weeks and passed through an active charcoal filter in order to reduce the Radon concentration. In this way we have been able to make nucleation experiments with very low ionizing background, meaning that we can rule out ion induced nucleation as a contributing mechanism. Our experimental setup is a 50 L electropolished stainless steel reactor at near atmospheric conditions. The chamber contains clean air with the addition of water vapor, ozone, and SO2. Using UV lights at 254 nm ozone is photolyzed, leading to the production of sulfuric acid and thus aerosols. An 18 MBq Caesium-137 gamma ray source with various amounts of lead in front allows us to alter the ionization in our chamber. By making series of nucleation bursts with varying amounts of ionizing radiation we then gauge the relative importance of ion

  19. Nucleation and growth in alkaline zinc electrodeposition An Experimental and Theoretical study

    Science.gov (United States)

    Desai, Divyaraj

    The current work seeks to investigate the nucleation and growth of zinc electrodeposition in alkaline electrolyte, which is of commercial interest to alkaline zinc batteries for energy storage. The morphology of zinc growth places a severe limitation on the typical cycle life of such batteries. The formation of mossy zinc leads to a progressive deterioration of battery performance while zinc dendrites are responsible for sudden catastrophic battery failure. The problems are identified as the nucleation-controlled formation of mossy zinc and the transport-limited formation of dendritic zinc. Consequently, this thesis work seeks to investigate and accurately simulate the conditions under which such morphologies are formed. The nucleation and early-stage growth of Zn electrodeposits is studied on carbon-coated TEM grids. At low overpotentials, the morphology develops by aggregation at two distinct length scales: ~5 nm diameter monocrystalline nanoclusters form ~50nm diameter polycrystalline aggregates, and second, the aggregates form a branched network. Epitaxial (0002) growth above a critical overpotential leads to the formation of hexagonal single-crystals. A kinetic model is provided using the rate equations of vapor solidification to simulate the evolution of the different morphologies. On solving these equations, we show that aggregation is attributed to cluster impingement and cluster diffusion while single-crystal formation is attributed to direct attachment. The formation of dendritic zinc is investigated using in-operando transmission X-ray microscopy which is a unique technique for imaging metal electrodeposits. The nucleation density of zinc nuclei is lowered using polyaniline films to cover the active nucleation sites. The effect of overpotential is investigated and the morphology shows beautiful in-operando formation of symmetric zinc crystals. A linear perturbation model was developed to predict the growth and formation of these crystals to first

  20. DNA-templated silver nanoclusters based label-free fluorescent molecular beacon for the detection of adenosine deaminase.

    Science.gov (United States)

    Zhang, Kai; Wang, Ke; Xie, Minhao; Zhu, Xue; Xu, Lan; Yang, Runlin; Huang, Biao; Zhu, Xiaoli

    2014-02-15

    A general and reliable fluorescent molecular beacon is proposed in this work utilizing DNA-templated silver nanoclusters (AgNCs). The fluorescent molecular beacon has been employed for sensitive determination of the concentration of adenosine deaminase (ADA) and its inhibition. A well-designed oligonucleotide containing three functional regions (an aptamer region for adenosine assembly, a sequence complementary to the region of the adenosine aptamer, and an inserted six bases cytosine-loop) is adopted as the core element in the strategy. The enzymatic reaction of adenosine catalyzed by ADA plays a key role as well in the regulation of the synthesis of the DNA-templated AgNCs, i.e. the signal indicator. The intensity of the fluorescence signal may thereby determine the concentration of the enzyme and its inhibitor. The detection limit of the ADA can be lowered to 0.05 UL(-1). Also, 100 fM of a known inhibitor erythro-9-(2-hydroxy-3-nonyl) adenine hydrochloride (EHNA) is enough to present distinguishable fluorescence emission. Moreover, since the fluorescent signal indicator is not required to be bound with the oligonucleotide, this fluorescent molecular beacon may integrate the advantages of both the label-free and signal-on strategies.

  1. Cu(2+) modulated silver nanoclusters as an on-off-on fluorescence probe for the selective detection of L-histidine.

    Science.gov (United States)

    Zheng, Xuyue; Yao, Tianming; Zhu, Ying; Shi, Shuo

    2015-04-15

    In the present study, a new strategy based on Cu(2+) mediated DNA-templated silver nanoclusters (DNA-Ag NCs) was developed, as a label-free, on-off-on fluorescent probe for the detection of l-histidine. Eight synthesized DNA oligonucleotides (D1-D8) were experimentally tested, and D5-Ag NCs was finally selected for l-histidine detection due to its best fluorescent properties. The fluorescence emission of D5-Ag NCs could be quenched by Cu(2+) via electron or energy transfer. Upon addition of l-histidine, the chelation between Cu(2+) and the imidazole group of l-histidine leads to Cu(2+) liberation from D5-Ag NCs, and subsequently results in a dramatic fluorescence enhancement of the probe. The method displayed a good selectivity toward l-histidine over all the other amino acids, with a linear relationship in the range of 0.20-80μM, and a limit of detection (LOD) of 4.3nM. The strategy was also successfully applied to detect l-histidine in diluted human urine, exhibiting great opportunities for practical application in biological system.

  2. Dynamic density functional theory for nucleation: Non-classical predictions of mesoscopic nucleation theory

    Science.gov (United States)

    Duran-Olivencia, Miguel A.; Yatsyshin, Peter; Lutsko, James F.; Kalliadasis, Serafim

    2016-11-01

    Classical density functional theory (DFT) for fluids and its dynamic extension (DDFT) provide an appealing mean-field framework for describing equilibrium and dynamics of complex soft matter systems. For a long time, homogeneous nucleation was considered to be outside the limits of applicability of DDFT. However, our recently developed mesoscopic nucleation theory (MeNT) based on fluctuating hydrodynamics, reconciles the inherent randomness of the nucleation process with the deterministic nature of DDFT. It turns out that in the weak-noise limit, the most likely path (MLP) for nucleation to occur is determined by the DDFT equations. We present computations of MLPs for homogeneous and heterogeneous nucleation in colloidal suspensions. For homogeneous nucleation, the MLP obtained is in excellent agreement with the reduced order-parameter description of MeNT, which predicts a multistage nucleation pathway. For heterogeneous nucleation, the presence of impurities in the fluid affects the MLP, but remarkably, the overall qualitative picture of homogeneous nucleation persists. Finally, we highlight the use of DDFT as a simulation tool, which is especially appealing as there are no known applications of MeNT to heterogeneous nucleation. We acknowledge financial support from the European Research Council via Advanced Grant No. 247031 and from EPSRC via Grants No. EP/L020564 and EP/L025159.

  3. Nanowires and nanoneedles nucleation on vicinal substrate

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xu, E-mail: zhangxubetter@gmail.com [Henan Key Laboratory of Laser and Opto-electric Information Technology, School of Information Engineering, Zhengzhou University, Zhengzhou 450052 (China); Xie, Dan; Huang, Genling [Zhengzhou Railway Vocational and Technical College, Zhengzhou 450052 (China); Sun, Xiao-Hong [Henan Key Laboratory of Laser and Opto-electric Information Technology, School of Information Engineering, Zhengzhou University, Zhengzhou 450052 (China)

    2015-01-01

    An analytic stress-driven nucleation model of nanowires (NWs) and nanoneedles (NNs) growing on a mismatched vicinal substrate is proposed. It is demonstrated that the formation enthalpy of NWs and NNs is a function of three independent variables, the base radius, aspect ratio and miscut angle of the vicinal surface. Theoretical analysis shows that the minimum nucleation barrier of an island decreases with increment of substrate misorientation, which means the nucleation of islands on a vicinal substrate is more favorable than that on a flat substrate.

  4. 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.

  5. Optimum processing conditions for the fabrication of large, single grain Ag-doped YBCO bulk superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Iida, K. [IRC in Superconductivity and Department of Engineering, University of Cambridge, Cavendish Laboratory 19 JJ Thomson Avenue, Cambridge CB3 0HE (United Kingdom)], E-mail: k.iida@ifw-dresden.de; Babu, N.H. [IRC in Superconductivity and Department of Engineering, University of Cambridge, Cavendish Laboratory 19 JJ Thomson Avenue, Cambridge CB3 0HE (United Kingdom); BCAST, Brunel University, West London UB8 3PH (United Kingdom); Pathak, S.; Shi, Y.; Yeoh, W.K. [IRC in Superconductivity and Department of Engineering, University of Cambridge, Cavendish Laboratory 19 JJ Thomson Avenue, Cambridge CB3 0HE (United Kingdom); Miyazaki, T. [Shibaura Institute of Technology, 3-7-5 Toyosu, Koto-ku, Tokyo 135-8548 (Japan); SRL-ISTEC, 1-10-13 Shinonome, Koto-ku, Tokyo 135-0062 (Japan); Sakai, N. [SRL-ISTEC, 1-10-13 Shinonome, Koto-ku, Tokyo 135-0062 (Japan); Murakami, M. [Shibaura Institute of Technology, 3-7-5 Toyosu, Koto-ku, Tokyo 135-8548 (Japan); Cardwell, D.A. [IRC in Superconductivity and Department of Engineering, University of Cambridge, Cavendish Laboratory 19 JJ Thomson Avenue, Cambridge CB3 0HE (United Kingdom)

    2008-06-15

    A pseudo Time-Temperature-Transformation (TTT) diagram has been constructed for the optimum melt processing conditions for the fabrication of large, single grain Ag-doped Y-Ba-Cu-O (YBCO/Ag) bulk superconductors. The thermal conditions for the formation of homogeneous nuclei have been investigated and the boundary between this region and that for no grain nucleation has been mapped as a function of holding time. YBCO/Ag bulk samples grow typically in the form of single grains when the processing temperature profile lies within the 'no nucleation' region of the pseudo TTT diagram. However, by studying the YBCO/Ag growth process, some samples have been grown in the form of single grains by employing a temperature profile within the homogeneous grain nucleation region of the phase diagram. Such growth may be achieved when the YBCO/Ag phase constitutes the majority of the volume of the pellet before the growth temperature reaches that at the nucleation boundary. A large, single YBCO/Ag grain of diameter 30 mm has been fabricated successfully based on these studies by both cold-seeding and seeded infiltration growth techniques.

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. Effect of Ge Content on the Formation of Ge Nanoclusters in Magnetron-Sputtered GeZrOx-Based Structures.

    Science.gov (United States)

    Khomenkova, L; Lehninger, D; Kondratenko, O; Ponomaryov, S; Gudymenko, O; Tsybrii, Z; Yukhymchuk, V; Kladko, V; von Borany, J; Heitmann, J

    2017-12-01

    Ge-rich ZrO2 films, fabricated by confocal RF magnetron sputtering of pure Ge and ZrO2 targets in Ar plasma, were studied by multi-angle laser ellipsometry, Raman scattering, Auger electron spectroscopy, Fourier transform infrared spectroscopy, and X-ray diffraction for varied deposition conditions and annealing treatments. It was found that as-deposited films are homogeneous for all Ge contents, thermal treatment stimulated a phase separation and a formation of crystalline Ge and ZrO2. The "start point" of this process is in the range of 640-700 °C depending on the Ge content. The higher the Ge content, the lower is the temperature necessary for phase separation, nucleation of Ge nanoclusters, and crystallization. Along with this, the crystallization temperature of the tetragonal ZrO2 exceeds that of the Ge phase, which results in the formation of Ge crystallites in an amorphous ZrO2 matrix. The mechanism of phase separation is discussed in detail.

  12. Influence of size, shape and core-shell interface on surface plasmon resonance in Ag and Ag@MgO nanoparticle films deposited on Si/SiO x.

    Science.gov (United States)

    D'Addato, Sergio; Pinotti, Daniele; Spadaro, Maria Chiara; Paolicelli, Guido; Grillo, Vincenzo; Valeri, Sergio; Pasquali, Luca; Bergamini, Luca; Corni, Stefano

    2015-01-01

    Ag and Ag@MgO core-shell nanoparticles (NPs) with a diameter of d = 3-10 nm were obtained by physical synthesis methods and deposited on Si with its native ultrathin oxide layer SiO x (Si/SiO x ). Scanning electron microscopy and transmission electron microscopy (TEM) images of bare Ag NPs revealed the presence of small NP aggregates caused by diffusion on the surface and agglomeration. Atomic resolution TEM gave evidence of the presence of crystalline multidomains in the NPs, which were due to aggregation and multitwinning occurring during NP growth in the nanocluster source. Co-deposition of Ag NPs and Mg atoms in an oxygen atmosphere gave rise to formation of a MgO shell matrix surrounding the Ag NPs. The behaviour of the surface plasmon resonance (SPR) excitation in surface differential reflectivity (SDR) spectra with p-polarised light was investigated for bare Ag and Ag@MgO NPs. It was shown that the presence of MgO around the Ag NPs caused a red shift of the plasmon excitation, and served to preserve its existence after prolonged (five months) exposure to air, realizing the possibility of technological applications in plasmonic devices. The Ag NP and Ag@MgO NP film features in the SDR spectra could be reproduced by classical electrodynamics simulations by treating the NP-containing layer as an effective Maxwell Garnett medium. The simulations gave results in agreement with the experiments when accounting for the experimentally observed aggregation.

  13. Unraveling the "pressure effect" in nucleation.

    Science.gov (United States)

    Wedekind, Jan; Hyvärinen, Antti-Pekka; Brus, David; Reguera, David

    2008-09-19

    The influence of the pressure of a chemically inert carrier gas on the nucleation rate is one of the biggest puzzles in the research of gas-liquid nucleation. Experiments can show a positive effect, a negative effect, or no effect at all. The same experiment may show both trends for the same substance depending on temperature, or for different substances at the same temperature. We show how this ambiguous effect naturally arises from the competition of two contributions: nonisothermal effects and pressure-volume work. Our model clarifies seemingly contradictory experimental results and quantifies the variation of the nucleation ability of a substance in the presence of an ambient gas. Our findings are corroborated by molecular dynamics simulations and might have important implications since nucleation in experiments, technical applications, and nature practically always occurs in the presence of an ambient gas.

  14. 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.

  15. 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

  16. 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.

  17. 寡聚核苷酸保护的银纳米簇的生成及其在生物成像中的应用%DNA-templated Formation of the Fluorescent Silver Nanocluster and Its Application in Bioimaging

    Institute of Scientific and Technical Information of China (English)

    嘎鲁; 陈朝军; 赵岩; 布仁

    2013-01-01

    文中以寡聚核苷酸、硼氰化钠(NaBH4)、硝酸银(AgNO3)为原料合成了寡聚核苷酸保护的银纳米簇,将寡聚核苷酸保护的银纳米簇与细胞结合进行成像分析,并采用荧光光谱、MALDI TOF MS、TEM及LSCM对寡聚核苷酸保护的银纳米簇进行了测试分析.质谱测试结果表明,寡聚核苷酸保护的银纳米簇中含有10个银原子.投射电镜观察发现寡聚核苷酸保护的银纳米簇颗粒大小基本小于2nm.荧光共聚焦的细胞成像结果发现寡聚核苷酸保护的银纳米簇能进入细胞并进行原位标记成像.细胞毒性试验表明该银纳米簇无毒性.%A novel kind of silver nanocluster was synthesized simply by mixing DNA template with silver ions and NaBH4. Fluorescence assay, MALDI TOF MS, LSCM, and TEM were used to characterize the silver nanocluster. It was found that after formation of the silver nanocluster, the silver cluster have 10 silver atom and fluorescence properties. So, it has potential applications in the field of biological imaging. The MTT assay demonstrated that the silver nanocluster has only little affect on the cytotoxicity to the cells.

  18. 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

  19. Nucleation Kinetics of Cis-Entacapone

    OpenAIRE

    Škalec Šamec, D.; Meštrović, E.; Sander, A.

    2012-01-01

    The solubility curve and the metastable zone width for the system cis-entacapone –2-propanol have been determined in defined process conditions. These results along with values of induction period for the constant feed concentration at different levels of supersaturation were used for evaluating interfacial energy according to the classical nucleation theory. The results obtained were used for calculation of the critical nucleus size, nucleation rate, and prediction of crystal growth mecha...

  20. Direct simulations of homogeneous bubble nucleation: Agreement with classical nucleation theory and no local hot spots.

    Science.gov (United States)

    Diemand, Jürg; Angélil, Raymond; Tanaka, Kyoko K; Tanaka, Hidekazu

    2014-11-01

    We present results from direct, large-scale molecular dynamics simulations of homogeneous bubble (liquid-to-vapor) nucleation. The simulations contain half a billion Lennard-Jones atoms and cover up to 56 million time steps. The unprecedented size of the simulated volumes allows us to resolve the nucleation and growth of many bubbles per run in simple direct micro-canonical simulations while the ambient pressure and temperature remain almost perfectly constant. We find bubble nucleation rates which are lower than in most of the previous, smaller simulations. It is widely believed that classical nucleation theory (CNT) generally underestimates bubble nucleation rates by very large factors. However, our measured rates are within two orders of magnitude of CNT predictions; only at very low temperatures does CNT underestimate the nucleation rate significantly. Introducing a small, positive Tolman length leads to very good agreement at all temperatures, as found in our recent vapor-to-liquid nucleation simulations. The critical bubbles sizes derived with the nucleation theorem agree well with the CNT predictions at all temperatures. Local hot spots reported in the literature are not seen: Regions where a bubble nucleation event will occur are not above the average temperature, and no correlation of temperature fluctuations with subsequent bubble formation is seen.

  1. Bacterial ice nucleation: significance and molecular basis.

    Science.gov (United States)

    Gurian-Sherman, D; Lindow, S E

    1993-11-01

    Several bacterial species are able to catalyze ice formation at temperatures as warm as -2 degrees C. These microorganisms efficiently catalyze ice formation at temperatures much higher than most organic or inorganic substances. Because of their ubiquity on the surfaces of frost-sensitive plants, they are responsible for initiating ice formation, which results in frost injury. The high temperature of ice catalysis conferred by bacterial ice nuclei makes them useful in ice nucleation-limited processes such as artificial snow production, the freezing of some food products, and possibly in future whether modification schemes. The rarity of other ice nuclei active at high subfreezing temperature, and the ease and sensitivity with which ice nuclei can be quantified, have made the use of a promoterless bacterial ice nucleation gene valuable as a reporter of transcription. Target genes to which this promoter is fused can be used in cells in natural habitats. Warm-temperature ice nucleation sites have also been extensively studied at a molecular level. Nucleation sites active at high temperatures (above -5 degrees C) are probably composed of bacterial ice nucleation protein molecules that form functionally aligned aggregates. Models of ice nucleation proteins predict that they form a planar array of hydrogen binding groups that closely complement that of an ice crystal face. Moreover, interdigitation of these molecules may produce a large contiguous template for ice formation.

  2. Silver-colloid-nucleated cytochrome c superstructures encapsulated in silica nanoarchitectures.

    Science.gov (United States)

    Wallace, Jean Marie; Dening, Brett M; Eden, Kristin B; Stroud, Rhonda M; Long, Jeffrey W; Rolison, Debra R

    2004-10-12

    We recently discovered that self-organized superstructures of the heme protein cytochrome c (cyt. c) are nucleated in buffer by gold nanoparticles. The protein molecules within the superstructure survive both silica sol-gel encapsulation and drying from supercritical carbon dioxide to form air-filled biocomposite aerogels that exhibit gas-phase binding activity for nitric oxide. In this investigation, we report that viable proteins are present in biocomposite aerogels when the nucleating metal nanoparticle is silver rather than gold. Silver colloids were synthesized via reduction of an aqueous solution of Ag+ using either citrate or borohydride reductants. As determined by transmission electron microscopy and UV-visible absorption spectroscopy, the silver nanoparticles vary in size and shape depending on the synthetic route, which affects the fraction of cyt. c that survives the processing necessary to form a biocomposite aerogel. Silver colloids synthesized via the citrate preparation are polydisperse, with sizes ranging from 1 to 100 nm, and lead to low cyt. c viability in the dried bioaerogels (approximately 15%). Protein superstructures nucleated at approximately 10-nm Ag colloids prepared via the borohydride route, including citrate stabilization of the borohydride-reduced metal, retain significant protein viability within the bioaerogels (approximately 45%).

  3. Catalysis by Nanostructures: Methane, Ethylene Oxide, and Propylene Oxide Synthesis on Ag, Cu or Au Nanoclusters

    Science.gov (United States)

    2008-02-07

    well-dispersed on the interior walls of nanotubular TiO2. The TiO2 nanotubes were shown by x-ray diffraction to be entirely anatase . Transmission...oxidation on a doped rutile TiO 2(1 10): Effect of ionic Au in catalysis. Catalysis Lett. 107, 143-147 (2006) 5. S. Chrdtien and H. Metiu, Density...functional study of the charge on Aun clusters (n=l-7) supported on a partially reduced rutile TiO 2(1 10): Are all clusters negatively charged? J. Chem

  4. DNA-stabilized silver nanoclusters and carbon nanoparticles oxide: A sensitive platform for label-free fluorescence turn-on detection of HIV-DNA sequences.

    Science.gov (United States)

    Ye, Yu-Dan; Xia, Li; Xu, Dang-Dang; Xing, Xiao-Jing; Pang, Dai-Wen; Tang, Hong-Wu

    2016-11-15

    Based on the remarkable difference between the interactions of carbon nanoparticles (CNPs) oxide with single-stranded DNA (ssDNA) and double-stranded DNA (dsDNA), and the fact that fluorescence of DNA-stabilized silver nanoclusters (AgNCs) can be quenched by CNPs oxide, DNA-functionalized AgNCs were applied as label-free fluorescence probes and a novel fluorescence resonance energy transfer (FRET) sensor was successfully constructed for the detection of human immunodeficiency virus (HIV) DNA sequences. CNPs oxide were prepared with the oxidation of candle soot, hence it is simple, time-saving and low-cost. The strategy of dual AgNCs probes was applied to improve the detection sensitivity by using dual- probe capturing the same target DNA in a sandwich mode and as the fluorescence donor, and using CNPs oxide as the acceptor. In the presence of target DNA, a dsDNA hybrid forms, leading to the desorption of the ssDNA-AgNCs probes from CNPs oxide, and the recovering of fluorescence of the AgNCs in a HIV-DNA concentration-dependent manner. The results show that HIV-DNA can be detected in the range of 1-50nM with a detection limit of 0.40nM in aqueous buffer. The method is simple, rapid and sensitive with no need of labeled fluorescent probes, and moreover, the design of fluorescent dual-probe makes full use of the excellent fluorescence property of AgNCs and further improves the detection sensitivity.

  5. 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.

  6. Silicon nanowire arrays coated with electroless Ag for increased surface-enhanced Raman scattering

    Directory of Open Access Journals (Sweden)

    Fan Bai

    2015-05-01

    Full Text Available The ordered Ag nanorod (AgNR arrays are fabricated through a simple electroless deposition technique using the isolated Si nanowire (SiNW arrays as the Ag-grown scaffold. The AgNR arrays have the single-crystallized structure and the plasmonic crystal feature. It is found that the formation of the AgNR arrays is strongly dependent on the filling ratio of SiNWs. A mechanism is proposed based on the selective nucleation and the synergistic growth of Ag nanoparticles on the top of the SiNWs. Moreover, the special AgNR arrays grown on the substrate of SiNWs exhibit a detection sensitivity of 10−15M for rhodamine 6G molecules, which have the potential application to the highly sensitive surface-enhanced Raman scattering sensors.

  7. Superheating and melting behaviors of Ag clusters with Ni coating studied by molecular dynamics and experiments

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Using molecular dynamics with embedded-atom-type interatomicpotentials, we simulated the melting behavior of a spherical Ag3055 cluster coated with Ni. The semi-coherent Ag/Ni interface formed at low temperatures acts as an effective barrier against the surface melting and leads to a substantial superheating of the Ag cluster. The melting point was found to be about 100 K above the equilibrium melting point of the bulk Ag crystal (1230 K±15 K) and about 290 K above that (1040 K) of the free Ag3055 cluster. A superheating of 70 K was observed in the high-temperature differential scanning calorimetry measurement for Ag particles with a mean size of 30 nm embedded in Ni matrix prepared by means of melt-spinning. Melting is initiated locally at the defective interfacial area and then propagates inwards, suggesting a heterogeneously nucleated melting event at the Ag/Ni interface.

  8. Influence of the surface properties on bactericidal and fungicidal activity of magnetron sputtered Ti–Ag and Nb–Ag thin films

    Energy Technology Data Exchange (ETDEWEB)

    Wojcieszak, D., E-mail: damian.wojcieszak@pwr.edu.pl [Faculty of Microsystem Electronics and Photonics, Wroclaw University of Technology, Janiszewskiego 11/17, 50-372 Wrocław (Poland); Mazur, M.; Kaczmarek, D. [Faculty of Microsystem Electronics and Photonics, Wroclaw University of Technology, Janiszewskiego 11/17, 50-372 Wrocław (Poland); Mazur, P. [Institute of Experimental Physics, University of Wrocław, Max Born 9, 50-204 Wrocław (Poland); Szponar, B. [Institute of Immunology and Experimental Therapy, Polish Academy of Sciences, Rudolfa Weigla 12, 53–114 Wrocław (Poland); Domaradzki, J. [Faculty of Microsystem Electronics and Photonics, Wroclaw University of Technology, Janiszewskiego 11/17, 50-372 Wrocław (Poland); Kepinski, L. [Institute of Low Temperature and Structure Research, Polish Academy of Sciences, Okólna 2, 50-422 Wrocław (Poland)

    2016-05-01

    In this study the comparative investigations of structural, surface and bactericidal properties of Ti–Ag and Nb–Ag thin films have been carried out. Ti–Ag and Nb–Ag coatings were deposited on silicon and fused silica substrates by magnetron co-sputtering method using innovative multi-target apparatus. The physicochemical properties of prepared thin films were examined with the aid of X-ray diffraction, grazing incidence X-ray diffraction, scanning electron microscopy, atomic force microscopy and X-ray photoelectron spectroscopy methods. Moreover, the wettability of the surface was determined. It was found that both, Ti–Ag and Nb–Ag thin films were nanocrystalline. In the case of Ag–Ti film presence of AgTi{sub 3} and Ag phases was identified, while in the structure of Nb–Ag only silver occurred in a crystal form. In both cases the average size of crystallites was ca. 11 nm. Moreover, according to scanning electron microscopy and atomic force microscopy investigations the surface of Nb–Ag thin films was covered with Ag-agglomerates, while Ti–Ag surface was smooth and devoid of silver particles. Studies of biological activity of deposited coatings in contact with Bacillus subtilis, Pseudomonas aeruginosa, Enterococcus hirae, Klebisiella pneumoniae, Escherichia coli, Staphylococcus aureus and Candida albicans were performed. It was found that prepared coatings were bactericidal and fungicidal even in a short term-contact, i.e. after 2 h. - Highlights: • Surface and biological properties of Ti–Ag and Nb–Ag thin films were examined. • Ag content was related to sputtering yields and nucleation of Ti and Nb. • For Nb–Ag film the agglomeration of silver at the surface was observed. • Composition and surface topography had an impact on antimicrobial properties. • Fine-grained surface was important in Ag ions release process.

  9. 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.

  10. 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.

  11. 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.

  12. 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...

  13. Nucleation and Growth of Tin in Pb-Free Solder Joints

    Science.gov (United States)

    Gourlay, C. M.; Belyakov, S. A.; Ma, Z. L.; Xian, J. W.

    2015-08-01

    The solidification of Pb-free solder joints is overviewed with a focus on the formation of the βSn grain structure and grain orientations. Three solders commonly used in electronics manufacturing, Sn-3Ag-0.5Cu, Sn-3.5Ag, and Sn-0.7Cu-0.05Ni, are used as case studies to demonstrate that (I) growth competition between primary dendrites and eutectic fronts during growth in undercooled melts is important in Pb-free solders and (II) a metastable eutectic containing NiSn4 forms in Sn-3.5Ag/Ni joints. Additionally, it is shown that the substrate (metallization) has a strong influence on the nucleation and growth of tin. We identify Co, Pd, and Pt substrates as having the potential to control solidification and microstructure formation. In the case of Pd and Pt substrates, βSn is shown to nucleate on the PtSn4 or PdSn4 intermetallic compound (IMC) reaction layer at relatively low undercooling of ~4 K, even for small solder ball diameters down to <200 μm.

  14. Parameterization of homogeneous ice nucleation for cloud and climate models based on classical nucleation theory

    Directory of Open Access Journals (Sweden)

    V. I. Khvorostyanov

    2012-03-01

    Full Text Available A new analytical parameterization of homogeneous ice nucleation is developed based on extended classical nucleation theory including new equations for the critical radii of the ice germs, free energies and nucleation rates as the functions of the temperature and water saturation ratio simultaneously. By representing these quantities as separable products of the analytical functions of the temperature and supersaturation, analytical solutions are found for the integral-differential supersaturation equation and concentration of nucleated crystals. Parcel model simulations are used to illustrate the general behavior of various nucleation properties under various conditions, for justifications of the further key analytical simplifications, and for verification of the resulting parameterization.

    The final parameterization is based upon the values of the supersaturation that determines the current or maximum concentrations of the nucleated ice crystals. The crystal concentration is analytically expressed as a function of time and can be used for parameterization of homogeneous ice nucleation both in the models with small time steps and for substep parameterization in the models with large time steps. The crystal concentration is expressed analytically via the error functions or elementary functions and depends only on the fundamental atmospheric parameters and parameters of classical nucleation theory. The diffusion and kinetic limits of the new parameterization agree with previous semi-empirical parameterizations.

  15. Molecular Ice Nucleation Activity of Birch Pollen

    Science.gov (United States)

    Felgitsch, Laura; Bichler, Magdalena; Häusler, Thomas; Weiss, Victor U.; Marchetti-Deschmann, Martina; Allmaier, Günter; Grothe, Hinrich

    2015-04-01

    Heterogeneous ice nucleation plays a major part in ecosystem and climate. Due to the triggering of ice cloud formation it influences the radiation balance of the earth, but also on the ground it can be found to be important in many processes of nature. So far the process of heterogeneous ice nucleation is not fully understood and many questions remain to be answered. Biological ice nucleation is hereby from great interest, because it shows the highest freezing temperatures. Several bacteria and fungi act as ice nuclei. A famous example is Pseudomonas syringae, a bacterium in commercial use (Snomax®), which increases the freezing from homogeneous freezing temperatures of approx. -40° C (for small volumes as in cloud droplets) to temperatures up to -2° C. In 2001 it was found that birch pollen can trigger ice nucleation (Diehl et al. 2001; Diehl et al. 2002). For a long time it was believed that this is due to macroscopic features of the pollen surface. Recent findings of Bernhard Pummer (2012) show a different picture. The ice nuclei are not attached on the pollen surface directly, but on surface material which can be easily washed off. This shows that not only the surface morphology, but also specific molecules or molecular structures are responsible for the ice nucleation activity of birch pollen. With various analytic methods we work on elucidating the structure of these molecules as well as the mechanism with which they trigger ice nucleation. To solve this we use various instrumental analytic techniques like Nuclear Magnetic Resonance spectroscopy (NMR), Matrix-Assisted Laser Desorption/Ionization Mass Spectrometry (MALDI-MS), and Gas-phase Electrophoretic Mobility Molecular Analysis (GEMMA). Also standard techniques like various chromatographic separation techniques and solvent extraction are in use. We state here that this feature might be due to the aggregation of small molecules, with agglomerates showing a specific surface structure. Our results

  16. Vapour–to–liquid nucleation: Nucleation theorems for nonisothermal–nonideal case

    Energy Technology Data Exchange (ETDEWEB)

    Malila, J.; McGraw, R.; Napari, I.; Laaksonen, A.

    2010-08-29

    Homogeneous vapour-to-liquid nucleation, a basic process of aerosol formation, is often considered as a type example of nucleation phenomena, while most treatment of the subject introduce several simplifying assumptions (ideal gas phase, incompressible nucleus, isothermal kinetics, size-independent surface free energy...). During last decades, nucleation theorems have provided new insights into properties of critical nuclei facilitating direct comparison between laboratory experiments and molecular simulations. These theorems are, despite of their generality, often applied in forms where the aforementioned assumptions are made. Here we present forms of nucleation theorems that explicitly take into account these effects and allow direct estimation of their importance. Only assumptions are Arrhenius-type kinetics of nucleation process and exclusion carrier gas molecules from the critical nucleus.

  17. Validity of commonly used formula of nucleation work for bubble nucleation

    Science.gov (United States)

    Mori, Atsushi

    2013-08-01

    Nishioka and Kusaka [Journal of Chemical Physics 96 (1992) 5370] showed that the commonly used formula, W=n(μα-μβ)+γA, for work of formation of critical nucleus is derived by integrating the isothermal Gibbs-Duhem relation for the incompressible nucleating phase, such as an incompressible liquid phase nucleation in a vapor phase. In their paper as well as in a subsequent paper [Li, Nishioka, Holcomb, Journal of Crystal Growth 171 (1997) 259] it was stated that the commonly used formula was valid for an incompressible nucleating phase and no longer held for such as a bubble nucleation. In this paper, we will amend this statement; that is, the commonly used formula is shown to hold for incompressible parent phase, such as a bubble nucleation in an incompressible parent phase.

  18. 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.

  19. 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.

  20. 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.

  1. 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

  2. Atmospheric Ion-induced Aerosol Nucleation

    Science.gov (United States)

    Curtius, J.; Lovejoy, E. R.; Froyd, K. D.

    2006-08-01

    Ion-induced nucleation has been suggested to be a potentially important mechanism for atmospheric aerosol formation. Ions are formed in the background atmosphere by galactic cosmic rays. A possible connection between galactic cosmic rays and cloudiness has been However, the predictions of current atmospheric nucleation models are highly uncertain because the models are usually based on the liquid drop model that estimates cluster thermodynamics based on bulk properties (e.g., liquid drop density and surface tension). Sulfuric acid (H2SO4) and water are assumed to be the most important nucleating agents in the free troposphere. Measurements of the molecular thermodynamics for the growth and evaporation of cluster ions containing H2SO4 and H2O were performed using a temperature-controlled laminar flow reactor coupled to a linear quadrupole mass spectrometer as well as a temperature-controlled ion trap mass spectrometer. The measurements were complemented by quantum chemical calculations of the cluster ion structures. The analysis yielded a complete set of H2SO4 and H2O binding thermodynamics extending from molecular cluster ions to the bulk, based on experimental thermodynamics for the small clusters. The data were incorporated into a kinetic aerosol model to yield quantitative predictions of the rate of ion-induced nucleation for atmospheric conditions. The model predicts that the negative ion-H2SO4-H2O nucleation mechanism is an efficient source of new particles in the middle and upper troposphere.

  3. Water-soluble Ag(2)S quantum dots for near-infrared fluorescence imaging in vivo.

    Science.gov (United States)

    Jiang, Peng; Zhu, Chun-Nan; Zhang, Zhi-Ling; Tian, Zhi-Quan; Pang, Dai-Wen

    2012-07-01

    A one-step method for synthesizing water-soluble Ag(2)S quantum dots terminated with carboxylic acid group has been reported. The crystal structure and surface of the prepared Ag(2)S quantum dots were characterized. The prepared Ag(2)S quantum dots exhibited bright photoluminescence and excellent photostabilities. The photoluminescence emissions could be tuned from visible region to near-infrared (NIR) region (from 510 nm to 1221 nm). Ultra-small sized Ag(2)S nanoclusters were synthesized with high initial monomer concentration in the current system. The in vivo imaging experiments of nude mice showed that the NIR photoluminescence of the prepared Ag(2)S quantum dots could penetrate the body of mice. Compared to the conventional NIR quantum dots, the Ag(2)S quantum dots don't contain toxic elements to body (such as Cd and Pb), thus, the prepared Ag(2)S quantum dots could serve as excellent NIR optical imaging probes and would open the opportunity to study nanodiagnostics and imaging in vivo.

  4. Energetic Study of Helium Cluster Nucleation and Growth in 14YWT through First Principles

    Directory of Open Access Journals (Sweden)

    Yingye Gan

    2016-01-01

    Full Text Available First principles calculations have been performed to energetically investigate the helium cluster nucleation, formation and growth behavior in the nano-structured ferritic alloy 14YWT. The helium displays strong affinity to the oxygen:vacancy (O:Vac pair. By investigating various local environments of the vacancy, we find that the energy cost for He cluster growth increases with the appearance of solutes in the reference unit. He atom tends to join the He cluster in the directions away from the solute atoms. Meanwhile, the He cluster tends to expand in the directions away from the solute atoms. A growth criterion is proposed based on the elastic instability strain of the perfect iron lattice in order to determine the maximum number of He atoms at the vacancy site. We find that up to seven He atoms can be trapped at a single vacancy. However, it is reduced to five if the vacancy is pre-occupied by an oxygen atom. Furthermore, the solute atoms within nanoclusters, such as Ti and Y, will greatly limit the growth of the He cluster. A migration energy barrier study is performed to discuss the reduced mobility of the He atom/He cluster in 14YWT.

  5. Energetic Study of Helium Cluster Nucleation and Growth in 14YWT through First Principles

    Energy Technology Data Exchange (ETDEWEB)

    Gan, Yingye [Clemson University; Zhao, Huijuan [Clemson University; Hoelzer, David T [ORNL; Yun, Di [Argonne National Laboratory (ANL); Yun, Di [Shanghai Jiao Tong University, China

    2016-01-01

    First principles calculations have been performed to energetically investigate the helium cluster nucleation, formation and growth behavior in the nano-structured ferritic alloy 14YWT. The helium displays strong affinity to the oxygen:vacancy (O:Vac) pair. By investigating various local environments of the vacancy, we find that the energy cost for He cluster growth increases with the appearance of solutes in the reference unit. He atom tends to join the He cluster in the directions away from the solute atoms. Meanwhile, the He cluster tends to expand in the directions away from the solute atoms. A growth criterion is proposed based on the elastic instability strain of the perfect iron lattice in order to determine the maximum number of He atoms at the vacancy site. We find that up to seven He atoms can be trapped at a single vacancy. However, it is reduced to five if the vacancy is pre-occupied by an oxygen atom. Furthermore, the solute atoms within nanoclusters, such as Ti and Y, will greatly limit the growth of the He cluster. A migration energy barrier study is performed to discuss the reduced mobility of the He atom/He cluster in 14YWT.

  6. Nucleation and structural growth of cluster crystals

    CERN Document Server

    Leitold, Christian

    2016-01-01

    We study the nucleation of crystalline cluster phases in the generalized exponential model with exponent n=4. Due to the finite value of this pair potential for zero separation, at high densities the system forms cluster crystals with multiply occupied lattice sites. Here, we investigate the microscopic mechanisms that lead to the formation of cluster crystals from a supercooled liquid in the low-temperature region of the phase diagram. Using molecular dynamics and umbrella sampling, we calculate the free energy as a function of the size of the largest crystalline nucleus in the system, and compare our results with predictions from classical nucleation theory. Employing bond-order parameters based on a Voronoi tessellation to distinguish different crystal structures, we analyze the average composition of crystalline nuclei. We find that even for conditions where a multiply-occupied fcc crystal is the thermodynamically stable phase, the nucleation into bcc cluster crystals is strongly preferred. Furthermore, w...

  7. Excitation spectra of Ag3-DNA bases complexes: A benchmark study

    Science.gov (United States)

    Maksimov, D. A.; Pomogaev, V. A.; Kononov, A. I.

    2017-04-01

    Assessment of different ab initio and TDDFT methods was studied for calculation of the excitation energies of the complexes of pyrimidine bases with positively charged Ag3+ clusters. Performance of CIS, CIS(D), CC2, ADC(2), MP2, and TDDFT techniques with the use of different hybrid-GGA and meta-hybrid-GGA functionals and basis sets is studied. We found that M06-2X functional shows good accuracy in comparison with the ADC(2) ab initio method and that the geometry optimization approach can strongly affect the excitation spectra of the complexes. Our results may have important implications for further studies of ligand-stabilized silver nanoclusters.

  8. Structure and Plasmonic Properties of Thin PMMA Layers with Ion-Synthesized Ag Nanoparticles

    DEFF Research Database (Denmark)

    Popok, Vladimir; Hanif, Muhammad; Mackova, Anna;

    2015-01-01

    Silver nanoparticles are synthesized in polymethylmethacrylate (PMMA) by 30 keV Ag+ ion implantation with high fluences. The implantation is accompanied by structural and compositional evolution of the polymer as well as sputtering. The latter causes towering of the shallow nucleated Ag nanoparti......Silver nanoparticles are synthesized in polymethylmethacrylate (PMMA) by 30 keV Ag+ ion implantation with high fluences. The implantation is accompanied by structural and compositional evolution of the polymer as well as sputtering. The latter causes towering of the shallow nucleated Ag...... nanoparticles above the surface. The synthesized nanoparticles can be split into two groups: (i) located at the surface and (ii) fully embedded in the shallow layer. These two groups provide corresponding spectral bands related to localized surface plasmon resonance. The bands demonstrate considerable intensity...... making the synthesized composites promising for plasmonic applications....

  9. Cavitation Bubble Nucleation by Energetic Particles

    Energy Technology Data Exchange (ETDEWEB)

    West, C.D.

    1998-12-01

    In the early sixties, experimental measurements using a bubble chamber confirmed quantitatively the thermal spike theory of bubble nucleation by energetic particles: the energy of the slow, heavy alpha decay recoils used in those experiments matched the calculated bubble nucleation energy to within a few percent. It was a triumph, but was soon to be followed by a puzzle. Within a couple of years, experiments on similar liquids, but well below their normal boiling points, placed under tensile stress showed that the calculated bubble nucleation energy was an order of magnitude less than the recoil energy. Why should the theory work so well in the one case and so badly in the other? How did the liquid, or the recoil particle, "know" the difference between the two experiments? Another mathematical model of the same physical process, introduced in 1967, showed qualitatively why different analyses would be needed for liquids with high and low vapor pressures under positive or negative pressures. But, the quantitative agreement between the calculated nucleation energy and the recoil energy was still poor--the former being smaller by a factor of two to three. In this report, the 1967 analysis is extended and refined: the qualitative understanding of the difference between positive and negative pressure nucleation, "boiling" and "cavitation" respectively, is retained, and agreement between the negative pressure calculated to be needed for nucleation and the energy calculated to be available is much improved. A plot of the calculated negative pressure needed to induce bubble formation against the measured value now has a slope of 1.0, although there is still considerable scatter in the individual points.

  10. A unified kinetic approach to binary nucleation

    Energy Technology Data Exchange (ETDEWEB)

    Kevrekidis, P.G. [Department of Physics, Rutgers University, 136 Frelinghuysen Road]|[E.O.H.S.I., Rutgers University]|[UMDNJ, 170 Frelinghuysen Road, Piscataway, New Jersey 08854-8019 (United States); Lazaridis, M. [Norwegian Institute for Air Research (NILU), Instittutvein 18, P. O. Box 100, N-2007 Kjeller (Norway); Drossinos, Y. [European Commission, Joint Research Centre, I-21020 Ispra (Vatican City State, Holy See) (Italy); Georgopoulos, P.G. [E.O.H.S.I., Rutgers University]|[UMDNJ, 170 Frelinghuysen Road, Piscataway, New Jersey 08854 (United States)

    1999-11-01

    Two different methods to calculate the steady-state nucleation rate in heteromolecular systems proposed by Stauffer (1976) and Langer (1969) are analyzed. Their mathematical equivalence is explicitly demonstrated, thereby obtaining a generic expression for the rate of binary nucleation. Its numerical evaluation does not entail rotation of the coordinate system at the saddle point, but it only requires data in the natural coordinate system of number fluctuations, namely molecular impingement rates, the droplet free energy and its second order derivatives at the saddle point, and the total density of condensible vapors. {copyright} {ital 1999 American Institute of Physics.}

  11. Nucleation in an ultra low ionization environment

    DEFF Research Database (Denmark)

    Pedersen, Jens Olaf Pepke; Enghoff, Martin Andreas Bødker; Paling, Sean

    filter in order to reduce the Radon concentration. In this way we have been able to make nucleation experiments with very low ionizing background, meaning that we can rule out ion induced nucleation as a contributing mechanism. Our experimental setup is a 50 L electropolished stainless steel reactor...... at near atmospheric conditions. The chamber contains clean air with the addition of water vapour, ozone, and SO2. Using UV lights at 254 nm ozone is photolyzed, leading to the production of sulphuric acid and thus aerosols. An 18 MBq Caesium-137 gamma ray source with various amounts of lead in front...

  12. 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.

  13. 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

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. Growth and Electronic Properties of Ag Nanoparticles on Reduced CeO2-x(111) Films

    Institute of Scientific and Technical Information of China (English)

    Dan-dan Kong; Yong-he Pan; Guo-dong Wang; Hai-bin Pan; Jun-fa Zhu

    2012-01-01

    Ag nanoparticles grown on reduced CeO2-x thin films have been studied by X-ray photoelectron spectroscopy and resonant photoelectron spectroscopy of the valence band to understand the effect of oxygen vacancies in the CeO2-x thin films on the growth and interfacial electronic properties of Ag.Ag grows as three-dimensional particles on the CeO2-x(111) surface at 300 K.Compared to the fully oxidized ceria substrate surface,Ag favors the growth of smaller particles with a larger particle density on the reduced ceria substrate surface,which can be attributed to the nucleation of Ag on oxygen vacancies.The binding energy of Ag3d increases when the Ag particle size decreases,which is mainly attributed to the final-state screening.The interfacial interaction between Ag and CeO2-x(111) is weak.The resonant enhancement of the 4f level of Ce3+ species in RPES indicates a partial Ce4+→Ce3+ reduction after Ag deposited on reduced ceria surface.The sintering temperature of Ag on CeO 1.85 (111) surface during annealing is a little higher than that of Ag on CeO2 (111) surface,indicating that Ag nanoparticles are more stable on the reduced ceria surface.

  19. Synthesis of gold nano-wire and nano-dumbbell shaped colloids and AuC60 nano-clusters

    Science.gov (United States)

    Landon, Preston B.; Jarvis, Brandon C.; Gilleland, Cody L.; Renfro, Tim; Gutierrez, Jose; Synowczynski, Jennifer; Hirsch, Samuel G.; Glosser, Robert

    2005-08-01

    A technique for the fabrication of colloidal gold nano-wire and nano-dumbbell shaped particles using carbon nanotubes and rod shaped viruses as templates is described. The gold (Au) encapsulation process was accomplished by the precipitation of gold chloride from aqueous solutions. When this process was conducted in the presence of hydroxylated C60, small pieces of phase-separated composites of AuC60 appeared to have formed. These nano-clusters may turn out to be large noble metal analogs of the alkali metal fullerides with the smallest geometrically possible Au aggregate consisting of 55 gold atoms. The existence of noble metal fullerene composites has been previously theorized. The alkali metal fullerides are examples of phase separated solids and have exhibited superconductivity with temperatures as high 33K. The mechanism required for the binding energy between C60 and gold has been observed to exist between C60 and many of the mirror metals (Al, Ag, Au, Cu, Ni). This binding energy is a charge transfer from the metal Fermi level into the C60 LUMO. If this bonding energy, is greater than the metals coagulation energy an Au/C60 size terminated mechanism during the formation of the gold aggregates by the adhesion of C60 to the surface is energetically favorable.

  20. Direct in situ observation of the electron-driven synthesis of Ag filaments on α-Ag2WO4 crystals

    OpenAIRE

    E. Longo; Cavalcante, L. S.; Volanti, D. P.; Gouveia, A. F.; LONGO, V.M.; Varela,J. A.; Orlandi,M. O.; J. de Andrés

    2013-01-01

    In this letter, we report, for the first time, the real-time in situ nucleation and growth of Ag filaments on α-Ag2 WO4 crystals driven by an accelerated electron beam from an electronic microscope under high vacuum. We employed several techniques to characterise the material in depth. By using these techniques combined with first-principles modelling based on density functional theory, a mechanism for the Ag filament formation followed by a subsequent growth process from the nano-to micro-sc...

  1. Translational invariance in nucleation theories: Theoretical formulation

    Energy Technology Data Exchange (ETDEWEB)

    Drossinos, Y.; Kevrekidis, P. G.; Georgopoulos, P. G.

    2001-03-01

    The consequences of spontaneously broken translational invariance on the nucleation-rate statistical prefactor in theories of first-order phase transitions are analyzed. A hybrid, semiphenomenological approach based on field-theoretic analyses of condensation and modern density-functional theories of nucleation is adopted to provide a unified prescription for the incorporation of translational-invariance corrections to nucleation-rate predictions. A connection between these theories is obtained starting from a quantum-mechanical Hamiltonian and using methods developed in the context of studies on Bose-Einstein condensation. An extremum principle is used to derive an integro-differential equation for the spatially nonuniform mean-field order-parameter profile; the appropriate order parameter becomes the square root of the fluid density. The importance of the attractive intermolecular potential is emphasized, whereas the repulsive two-body potential is approximated by considering hard-sphere collisions. The functional form of the degenerate translational eigenmodes in three dimensions is related to the mean-field order parameter, and their contribution to the nucleation-rate prefactor is evaluated. The solution of the Euler-Lagrange variational equation is discussed in terms of either a proposed variational trial function or the complete numerical solution of the associated boundary-value integro-differential problem. Alternatively, if the attractive potential is not explicitly known, an approach that allows its formal determination from its moments is presented.

  2. Nucleation theory and growth of nanostructures

    CERN Document Server

    Dubrovskii, Vladimir G

    2013-01-01

    Semiconductor nanostructures such as nanowires are promising building blocks of future nanoelectronic, nanophotonic and nanosensing devices. Their physical properties are primarily determined by the epitaxy process which is rather different from the conventional thin film growth. This book shows how the advanced nucleation theory can be used in modeling of growth properties, morphology and crystal phase of such nanostructures.

  3. Repeatability and randomness in heterogeneous freezing nucleation

    Directory of Open Access Journals (Sweden)

    G. Vali

    2008-08-01

    Full Text Available This study is aimed at clarifying the relative importance of the specific character of the nuclei and of the duration of supercooling in heterogeneous freezing nucleation by immersed impurities. Laboratory experiments were carried out in which sets of water drops underwent multiple cycles of freezing and melting. The drops contained suspended particles of mixtures of materials; the resulting freezing temperatures ranged from −6°C to −24°C. Rank correlation coefficients between observed freezing temperatures of the drops in successive runs were >0.9 with very high statistical significance, and thus provide strong support for the modified singular model of heterogeneous immersion freezing nucleation. For given drops, changes in freezing temperatures between cycles were relatively small (<1°C for the majority of the events. These frequent small fluctuations in freezing temperatures are interpreted as reflections of the random nature of embryo growth and are associated with a nucleation rate that is a function of a temperature difference from the characteristic temperatures of nuclei. About a sixth of the changes were larger, up to ±5°C, and exhibited some systematic patterns. These are thought to arise from alterations of the nuclei, some being permanent and some transitory. The results are used to suggest ways of describing ice initiation in cloud models that account for both the temperature and the time dependence of freezing nucleation.

  4. Repeatability and randomness in heterogeneous freezing nucleation

    Directory of Open Access Journals (Sweden)

    G. Vali

    2008-02-01

    Full Text Available This study is aimed at clarifying the relative importance of the specific character of the nuclei and of the duration of supercooling in heterogeneous freezing nucleation by immersed impurities. Laboratory experiments were carried out in which sets of water drops underwent multiple cycles of freezing and melting. The drops contained suspended particles of mixtures of materials; the resulting freezing temperatures ranged from −6°C to −24°C. Rank correlation coefficients between observed freezing temperatures of the drops in successive runs were >0.9 with very high statistical significance, and thus provide strong support for the modified singular model of heterogeneous immersion freezing nucleation. For given drops, changes in freezing temperatures between cycles were relatively small (<1°C for the majority of the events. These frequent small fluctuations in freezing temperatures are interpreted as reflections of the random nature of embryo growth and are associated with a nucleation rate that is a function of a temperature difference from the characteristic temperatures of nuclei. About a sixth of the changes were larger, up to ±5°C, and exhibited some systematic patterns. These are thought to arise from alterations of the nuclei, some being permanent and some transitory. The results are used to suggest ways of describing ice initiation in cloud models that account for both the temperature and the time dependence of freezing nucleation.

  5. Heterogeneous nucleation of aspartame from aqueous solutions

    Science.gov (United States)

    Kubota, Noriaki; Kinno, Hiroaki; Shimizu, Kenji

    1990-03-01

    Waiting times, the time from the instant of quenching needed for a first nucleus to appear, were measured at constant supercoolings for primary nucleation of aspartame (α-L-aspartyl-L-phenylalanine methylester) from aqueous solutions, which were sealed into glass ampoules (solution volume = 3.16 cm 3). Since the waiting time became shorter by filtering the solution prior to quenching, the nucleation was concluded to be heterogeneously induced. The measured waiting time consisted of two parts: time needed for the nucleus to grow to a detactable size (growth time) and stochastic time needed for nucleation (true waiting time). The distribution of the true waiting time, is well explained by a stochastic model, in which nucleation is regarded to occur heterogeneously and in a stochastic manner by two kinds of active sites. The active sites are estimated to be located on foreign particles in which such elements as Si, Al and Mg were contained. The amount of each element is very small in the order of magnitude of ppb (mass basis) of the whole solution. The growth time was correlated with the degree of supercooling.

  6. NUCLEATION STUDIES OF GOLD ON CARBON ELECTRODES

    Directory of Open Access Journals (Sweden)

    S. SOBRI

    2008-04-01

    Full Text Available Interest has grown in developing non-toxic electrolytes for gold electrodeposition to replace the conventional cyanide-based bath for long term sustainability of gold electroplating. A solution containing thiosulphate and sulphite has been developed specially for microelectronics applications. However, at the end of the electrodeposition process, the spent electrolyte can contain a significant amount of gold in solution. This study has been initiated to investigate the feasibility of gold recovery from a spent thiosulphate-sulphite electrolyte. We have used flat-plate glassy carbon and graphite electrodes to study the mechanism of nucleation and crystal growth of gold deposition from the spent electrolyte. It was found that at the early stages of reduction process, the deposition of gold on glassy carbon exhibits an instantaneous nucleation of non-overlapping particles. At longer times, the particles begin to overlap and the deposition follows a classic progressive nucleation phenomenon. On the other hand, deposition of gold on graphite does not follow the classical nucleation phenomena.

  7. Seeded Induction Period and Secondary Nucleation of Lithium Carbonate

    Institute of Scientific and Technical Information of China (English)

    SUN Yu-zhu; SONG Xing-fu; WANG Jin; LUO Yan; YU Jian-guo

    2009-01-01

    Seeded nucleation of lithinm carbonate in aqueous solution during reactive crystallization was monitored by FBRM (focused beam reflectance measurement) and PVM (particle video microscope). The impacts of operating variables, such as seed size and loading, stirring speed, on induction period and secondary nucleation were investigated and explained by an adsorption model. The results show that seed surface area plays an important role in secondary nucleation, for more surface area has higher adsorption capacity and consumes more supersaturation on seed growth, thus restrains nucleation better. A method through comparison between pure breakage/attrition and nucleation process was put forward to distinguish attrition-induced and surface-induced nucleations quantitatively, which can reveal the contributions of different nucleation mechanisms. The nucleation processes in different conditions were studied, the principles and valuable experimental data were obtained for seeding approach primarily. FBRM and PVM are useful on-line apparatuses to facilitate seed selection and seeding optimization.

  8. Nucleation Pathways For Freezing Of Two Grades Of Zirconium

    Science.gov (United States)

    Rhim, Won-Kyu; Rulison, Aaron; Bayuzick, Robert; Hofmeister, William; Morton, Craig

    1996-01-01

    Report discusses classical nucleation theory of freezing and describes experimental study of nucleation mechanisms that predominate during freezing of spherical specimens of initially molten zirconium levitated electrostatically in vacuum.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. Control of nucleation and growth in protein crystal growth

    Science.gov (United States)

    Rosenberger, Franz; Meehan, Edward J.

    1988-01-01

    The potential advantages of nucleation and growth control through temperature, rather than the addition of precipitants or removal of solvent, are discussed. A simple light scattering arrangement for the characterization of nucleation and growth conditions in solutions is described. The temperature dependence of the solubility of low ionic strength lysozyme solutions is applied in preliminary nucleation and growth experiments.

  15. TRANSFORMATION KINETICS FOR NUCLEATION ON RANDOM PLANES AND LINES

    Directory of Open Access Journals (Sweden)

    Elena Villa

    2011-11-01

    Full Text Available Birth and growth processes are known in materials science as nucleation and growth processes. In crystalline materials nucleation almost always takes place in an internal crystalline defect. These defects are classified according to their dimensionality: point, line or planar defects. Therefore, investigating nucleation on sets of dimensionality lower than the set in which the transformation takes place is of paramount importance. Cahn (1956 in a classical work derived expressions for transformation kinetics when nucleation took place on random planes and on random straight lines. He used these expressions to describe nucleation in polycrystalline materials. He considered that nucleation on grain faces could be treated as nucleation on random planes and, likewise, nucleation on grain edges could be treated as nucleation on random lines. The present work revisits and generalizes Cahn’s treatment of nucleation on planes and lines. First a general expression for the case of nucleation on lower dimensional sets is obtained. After that general expressions for nucleation on random planes and random lines are given. This paper provides the mathematical basis for the development of more specific expressions to be used in practical applications. Although this work has been done bearing applications to materials science in mind the results obtained here may be applied to birth and growth processes in any field of science.

  16. 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.

  17. Simulation of micro-behaviors including nucleation,growth, and aggregation in particle system

    Institute of Scientific and Technical Information of China (English)

    GU ZhaoLin; SU JunWei; JIAO JianYing; XU X Yun

    2009-01-01

    A new method for the solution of population balance equations (PBE) describing the micro-processes such as nucleation, growth, aggregation of particle swarms in a multiphase system is proposed. The method is based on the fixed pivot moment and allows arbitrary number of moments to be tracked si-multaneously. By expressing PBEs for both batch and continuous operations in a general form, and using weighted residual method to derive the moment equations, different moments can be tracked directly. The numerical density function is assumed to be a summation of several weighted Dirac Delta functions, and the integral and derivative terms in PBEs are transformed to a summation in order to reduce computational cost. Simulations of a batch nucleation-growth process and a continuous ag-gregation-growth process have demonstrated good agreement with the corresponding analytical solu-tions, with relative errors less than 10-8%. Simulation of a combined nucleation-growth-aggregation process, which does not have an analytical solution, is also included, so as to reproduce the mi-cro-behaviors of such a complex system, demonstrating the feasibility and reliability of this method.

  18. Simulation of micro-behaviors including nucleation,growth,and aggregation in particle system

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    A new method for the solution of population balance equations(PBE) describing the micro-processes such as nucleation,growth,aggregation of particle swarms in a multiphase system is proposed.The method is based on the fixed pivot moment and allows arbitrary number of moments to be tracked si-multaneously.By expressing PBEs for both batch and continuous operations in a general form,and using weighted residual method to derive the moment equations,different moments can be tracked directly.The numerical density function is assumed to be a summation of several weighted Dirac Delta functions,and the integral and derivative terms in PBEs are transformed to a summation in order to reduce computational cost.Simulations of a batch nucleation-growth process and a continuous ag-gregation-growth process have demonstrated good agreement with the corresponding analytical solu-tions,with relative errors less than 108%.Simulation of a combined nucleation-growth-aggregation process,which does not have an analytical solution,is also included,so as to reproduce the mi-cro-behaviors of such a complex system,demonstrating the feasibility and reliability of this method.

  19. Surface Nanobubble Nucleation Visualized with TIRF Microscopy

    CERN Document Server

    Chan, Chon U

    2012-01-01

    Nanobubbles are observed with optical microscopy using the total internal reflection fluorescence (TIRF) excitation. We report on TIRF visualization using Rhodamine 6G at 5$\\mu\\,$M concentration which results to strongly contrasted pictures. The preferential absorption and the high spatial resolution allow to detect nanobubbles with diameters of 230\\,nm and above. We present a study of the nucleation dynamics from the water-ethanol-water exchange and report the size distributions. Nanobubble nucleation is observed within 4 min after the exchange, later a stable population of nanobubbles with a surface density of 0.55 bubbles\\,/$\\mu$m$^2$ is formed. Interestingly, unstable, slowly dissolving nanobubbles are observed during the first stage of water-ethanol exchange; only after the ethanol-water exchange stable nanobubbles appear.

  20. Graphite Surface Modification by Heterogeneous Nucleation Process

    Institute of Scientific and Technical Information of China (English)

    CAO Ran; LI Hongxia

    2006-01-01

    Flaky graphite particles were coated by ZrOCl2·8H2O as precursors by heterogeneous nucleation process.The effects of factors such as pH values (2.4-5.1),concentration of the precursor solution (0.005-0.1 mol·L-1 ) , mixing method of graphite and precursor solution on the surface modification of graphite were studied. Result shows that: 1) the preferable technical process for heterogeneous nucleation modified graphite is to mix the graphite suspension and precursor solution with concentration 0. 025 mol·L -1 and then drip ammonia water to adjust the pH value to 3.6; 2)By surface modification, the ZrO2 particles are evenly coated on graphite surface and therefore improve oxidation resistance and dispersion ability of graphite.

  1. Diamond nucleation on surface of C60 thin layers

    Institute of Scientific and Technical Information of China (English)

    杨国伟; 袁放成; 刘大军; 何金田; 张兵临

    1997-01-01

    Diamond nucleation on the surface of C60 thin layers and intermediate layer of Si substrates are studied by scanning electron microscopy (SEM). The cross-section SEM images of diamond films show that diamond grains really nucleate on the surface of C60 thin layers. The SEM images of diamond nucleating sites show the nucleating aggregation of diamond on C60 surfaces. The preferential oriented diamond films are observed. The plasma pre-treatment of C60 sublimating layers is a key factor for diamond nucleation.

  2. 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.

  3. 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.

  4. 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.

  5. Volume versus surface nucleation in freezing aerosols

    Science.gov (United States)

    Sigurbjörnsson, Ómar F.; Signorell, Ruth

    2008-05-01

    The present study puts an end to the ongoing controversy regarding volume versus surface nucleation in freezing aerosols: Our study on nanosized aerosol particles demonstrates that current state of the art measurements of droplet ensembles cannot distinguish between the two mechanisms. The reasons are inherent experimental uncertainties as well as approximations used to analyze the kinetics. The combination of both can lead to uncertainties in the rate constants of two orders of magnitude, with important consequences for the modeling of atmospheric processes.

  6. Nucleation of {sup (4)}R brane universes

    Energy Technology Data Exchange (ETDEWEB)

    Cordero, Ruben [Departamento de FIsica, Escuela Superior de FIsica y Matematicas del IPN, Unidad Adolfo Lopez Mateos, Edificio 9, 07738 Mexico, DF (Mexico); Rojas, EfraIn [Facultad de FIsica e Inteligencia Artificial, Universidad Veracruzana, Sebastian Camacho 5, Xalapa, Veracruz, 91000 (Mexico)

    2004-09-07

    The creation of brane universes induced by a totally antisymmetric tensor living in a fixed background spacetime is presented, where a term involving the intrinsic curvature of the brane is considered. A canonical quantum mechanical approach employing the Wheeler-DeWitt equation is used. The probability nucleation for the brane is calculated by means of the corresponding instanton and the WKB approximation. Some cosmological implications from the model are presented.

  7. Systematic coarse-graining in nucleation theory

    Energy Technology Data Exchange (ETDEWEB)

    Schweizer, M., E-mail: marco.schweizer@math.ethz.ch [Department of Materials, Polymer Physics, ETH Zurich, Vladimir-Prelog-Weg 5, 8093 Zurich (Switzerland); Sagis, L. M. C., E-mail: leonard.sagis@wur.nl [Department of Materials, Polymer Physics, ETH Zurich, Vladimir-Prelog-Weg 5, 8093 Zurich (Switzerland); Food Physics Group, Wageningen University, Bornse Weilanden 9, 6708 WG Wageningen (Netherlands)

    2015-08-21

    In this work, we show that the standard method to obtain nucleation rate-predictions with the aid of atomistic Monte Carlo simulations leads to nucleation rate predictions that deviate 3 − 5 orders of magnitude from the recent brute-force molecular dynamics simulations [Diemand et al., J. Chem. Phys. 139, 074309 (2013)] conducted in the experimental accessible supersaturation regime for Lennard-Jones argon. We argue that this is due to the truncated state space the literature mostly relies on, where the number of atoms in a nucleus is considered the only relevant order parameter. We here formulate the nonequilibrium statistical mechanics of nucleation in an extended state space, where the internal energy and momentum of the nuclei are additionally incorporated. We show that the extended model explains the lack in agreement between the molecular dynamics simulations by Diemand et al. and the truncated state space. We demonstrate additional benefits of using the extended state space; in particular, the definition of a nucleus temperature arises very naturally and can be shown without further approximation to obey the fluctuation law of McGraw and LaViolette. In addition, we illustrate that our theory conveniently allows to extend existing theories to richer sets of order parameters.

  8. Kinetic theory of diffusion-limited nucleation

    Science.gov (United States)

    Philippe, T.; Bonvalet, M.; Blavette, D.

    2016-05-01

    We examine binary nucleation in the size and composition space {R,c} using the formalism of the multivariable theory [N. V. Alekseechkin, J. Chem. Phys. 124, 124512 (2006)]. We show that the variable c drops out of consideration for very large curvature of the new phase Gibbs energy with composition. Consequently nuclei around the critical size have the critical composition, which is derived from the condition of criticality for the canonical variables and is found not to depend on surface tension. In this case, nucleation kinetics can be investigated in the size space only. Using macroscopic kinetics, we determine the general expression for the condensation rate when growth is limited by bulk diffusion, which accounts for both diffusion and capillarity and exhibits a different dependence with the critical size, as compared with the interface-limited regime. This new expression of the condensation rate for bulk diffusion-limited nucleation is the counterpart of the classical interface-limited result. We then extend our analysis to multicomponent solutions.

  9. Images and properties of individual nucleated particles

    Science.gov (United States)

    Németh, Zoltán; Pósfai, Mihály; Nyirő-Kósa, Ilona; Aalto, Pasi; Kulmala, Markku; Salma, Imre

    2015-12-01

    Atmospheric aerosol particles were collected in Budapest, Hungary in April-June onto lacey Formvar substrates by using an electrostatic precipitator during the beginning phase of the particle growth process in ten nucleation and growth events. Median contribution of the nucleated particles - expressed as the concentration of particles with a diameter between 6 and 25 nm to the total particle number concentration - was 55%, and the median electrical mobility diameter of the particles was approximately 20 nm. The sample was investigated using high-resolution transmission electron microscopy (TEM) and electron energy-loss spectroscopy. Major types of individual particles such as soot, sulphate/organic and tar ball particles were identified in the sample. In addition, particles with an optical diameter range of 10-30 nm were also observed. They clearly differed from the other particle types, showed homogeneous contrast in the bright-field TEM images, and evaporated within tens of seconds when exposed to the electron beam. They were interpreted as representatives of freshly nucleated particles.

  10. [Ag25(SR)18]¯: The ‘Golden’ Silver Nanoparticle

    KAUST Repository

    Joshi, Chakra Prasad

    2015-08-31

    Silver nanoparticles with an atomically precise molecular formula [Ag25(SR)18]¯ (‒SR: thiolate) are synthesized and their single-crystal structure is determined. This synthesized nanocluster is the only silver nanoparticle that has a virtually identical analogue in gold, i.e., [Au25(SR)18]¯, in terms of number of metal atoms, ligand count, super-atom electronic configuration, and atomic arrangement. Furthermore, both [Ag25(SR)18]¯ and its gold analogue share a number of features in their optical absorption spectra. This unprecedented molecular synthesis in silver to mimic gold offers the first model nanoparticle platform to investigate the centuries-old problem of understanding the fundamental differences between silver and gold in terms of nobility, catalytic activity, and optical property.

  11. A nanoscale temperature-dependent heterogeneous nucleation theory

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Y. Y. [Nanosurface Science and Engineering Research Institute, College of Mechatronics and Control Engineering, Shenzhen University, Shenzhen, 518060 Guangdong (China); Yang, G. W., E-mail: stsygw@mail.sysu.edu.cn [State Key Laboratory of Optoelectronic Materials and Technologies, Nanotechnology Research Center, School of Materials Science and Engineering, School of Physics and Engineering, Sun Yat-Sen University, Guangzhou, 510275 Guangdong (China)

    2015-06-14

    Classical nucleation theory relies on the hypothetical equilibrium of the whole nucleation system, and neglects the thermal fluctuations of the surface; this is because the high entropic gains of the (thermodynamically extensive) surface would lead to multiple stable states. In fact, at the nanometer scale, the entropic gains of the surface are high enough to destroy the stability of the thermal equilibrium during nucleation, comparing with the whole system. We developed a temperature-dependent nucleation theory to elucidate the heterogeneous nucleation process, by considering the thermal fluctuations based on classical nucleation theory. It was found that the temperature not only affected the phase transformation, but also influenced the surface energy of the nuclei. With changes in the Gibbs free energy barrier, nucleation behaviors, such as the nucleation rate and the critical radius of the nuclei, showed temperature-dependent characteristics that were different from those predicted by classical nucleation theory. The temperature-dependent surface energy density of a nucleus was deduced based on our theoretical model. The agreement between the theoretical and experimental results suggested that the developed nucleation theory has the potential to contribute to the understanding and design of heterogeneous nucleation at the nanoscale.

  12. 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

  13. 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.

  14. "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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. Magnetism of FePt Nanoclusters in Polyimide

    Directory of Open Access Journals (Sweden)

    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.

  4. 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.

  5. AGS experiments - 1994, 1995, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Depken, J.C.

    1997-01-01

    This report contains the following information on the Brookhaven AGS Accelerator complex: FY 1996 AGS schedule as run; FY 1997 AGS schedule (working copy); AGS beams 1997; AGS experimental area FY 1994 physics program; AGS experimental area FY 1995 physics program; AGS experimental area FY 1996 physics program; AGS experimental area FY 1997 physics program (in progress); a listing of experiments by number; two-phage summaries of each experiment begin here, also ordered by number; listing of publications of AGS experiments begins here; and listing of AGS experimenters begins here.

  6. 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.

  7. 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.

  8. 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 ...

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

    DEFF Research Database (Denmark)

    Antunes, Paula Soares Martins; Watterson, Daniel; Parmvi, Mattias

    2015-01-01

    -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...

  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...... 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. Kinetics of intermetallic compound formation in thermally evaporated Ag-In bilayers

    Science.gov (United States)

    Rossi, P. J.; Zotov, N.; Mittemeijer, E. J.

    2016-10-01

    The kinetics of intermetallic compound (IMC) formation in thermally evaporated Ag-In bilayers, with In on top of Ag, was investigated using X-ray diffractometry, applied to the surfaces of the bilayer specimens, as well as scanning electron microscopy, applied to cross-sections of the bilayer specimens, prepared by a focused ion beam instrument. IMC formation was followed at room temperature as well as at elevated temperatures of 50 ° C , 60 ° C , and 70 ° C . Two distinct growth regimes were observed coinciding with the availability of pure In. The AgIn2 IMC nucleated initially, followed by nucleation of the Ag2In IMC. The growth of AgIn2 was found to be controlled by both diffusional processes as well as interfacial reactions. The growth of the Ag2In IMC is dominantly diffusion-controlled. An interdiffusion coefficient of D = 1.1 ± 3.9 . 10 - 4 cm 2 s - 1 exp ( - 60.5 ± 9.2 kJ mol - 1 R - 1 T - 1 ) was obtained for the Ag2In IMC. The observations were discussed in terms of the interplay of thermodynamic and kinetic constraints.

  12. Inorganic Nanoparticle Nucleation on Polymer Matrices

    Science.gov (United States)

    Kosteleski, Adrian John

    The introduction of inorganic nanoparticles into organic materials enhances both the mechanical and chemical properties of the material. Metallic nanoparticles, like silver and gold, have been introduced into polymers for use as antimicrobial coatings or dielectric materials, respectively. The challenge in creating these materials currently is the difficulty to homogeneously disperse the particles throughout the polymer matrix. The uneven dispersion of nanoparticles can lead to less than optimal quality and undesired properties. By creating a polymer nanocomposite material with well-controlled size inorganic materials that are evenly dispersed throughout the polymer matrix; we can improve the materials performance and properties. The objective for this research is to use polymer networks for the in situ mineralization of silver and other metallic materials to create intricate inorganic structures. The work performed here studied the ability to nucleate silver nanoparticles using poly (acrylic acid) (PAA) as the templating agent. Ionic silver was chemically reduced by sodium borohydride (NaBH4) in the presence of PAA. The effect of varying reactant concentrations of silver, NaBH 4, and PAA on particle size was studied. Reaction conditions in terms of varying temperature and pH levels of the reaction solution were monitored to observe the effect of silver nanoparticle size, shape, and concentration. By monitoring the UV spectra over time the reaction mechanism of the silver reduction process was determined to be an autocatalytic process: a period of slow, continuous nucleation followed by rapid, autocatalytic growth. The reaction kinetics for this autocatalytic process is also reported. PAA was crosslinked both chemically and physically to 3 biopolymers; ELP, an elastin like peptide, cotton fabrics, and calcium alginate hydrogels. Various compositions of PAA were physically crosslinked with calcium alginate gels to design an antimicrobial hydrogel for use in wound

  13. The ice nucleation activity of biological aerosols

    Science.gov (United States)

    Grothe, H.; Pummer, B.; Bauer, H.; Bernardi, J.

    2012-04-01

    Primary Biological Aerosol Particles (PBAPs), including bacteria, spores and pollen may be important for several atmospheric processes. Particularly, the ice nucleation caused by PBAPs is a topic of growing interest, since their impact on ice cloud formation and thus on radiative forcing, an important parameter in global climate is not yet fully understood. In laboratory model studies we investigated the ice nucleation activity of selected PBAPs. We studied the immersion mode freezing using water-oil emulsion, which we observed by optical microscopy. We particularly focused on pollen. We show that pollen of different species strongly differ in their ice nucleation behavior. The average freezing temperatures in laboratory experiments range from 240 K to 255 K. As the most efficient nuclei (silver birch, Scots pine and common juniper pollen) have a distribution area up to the Northern timberline, their ice nucleation activity might be a cryoprotective mechanism. For comparison the ice nucleation activity of Snomax, fungal spores, and mushrooms will be discussed as well. In the past, pollen have been rejected as important atmospheric IN, as they are not as abundant in the atmosphere as bacteria or mineral dust and are too heavy to reach higher altitudes. However, in our experiments (Pummer et al. 2011) it turned out that water, which had been in contact with pollen and then been separated from the bodies, nucleates as good as the pollen grains themselves. So the ice nuclei have to be easily-suspendable macromolecules (100-300 kDa) located on the pollen. Once extracted, they can be distributed further through the atmosphere than the heavy pollen grains and so augment the impact of pollen on ice cloud formation even in the upper troposphere. It is widely known, that material from the pollen, like allergens and sugars, can indeed leave the pollen body and be distributed independently. The most probable mechanism is the pollen grain bursting by rain, which releases

  14. The growth of AgGaTe{sub 2} layers on glass substrates with Ag{sub 2}Te buffer layer by closed space sublimation method

    Energy Technology Data Exchange (ETDEWEB)

    Uruno, Aya; Usui, Ayaka; Takeda, Yuji; Inoue, Tomohiro [Department of Electrical Engineering and Bioscience, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo 169-8555 (Japan); Kobayashi, Masakazu [Department of Electrical Engineering and Bioscience, Waseda University, 3-4-1 Okubo, Shinjuku, Tokyo 169-8555 (Japan); Kagami Memorial Research Institute for Materials Science and Technology, Waseda University, 2-8-26 Nishiwaseda, Shinjuku, Tokyo 169-0051 (Japan)

    2015-06-15

    The AgGaTe{sub 2} layer growth was performed by the closed space sublimation method on the Mo/glass substrate. The Ag{sub 2}Te buffer layer was inserted between AgGaTe{sub 2} and Mo layers, to improve the quality of grown layers. Crystallographic properties were analyzed by x-ray diffraction (XRD), and the surface morphologies were analyzed by scanning electron microscopy (SEM). The Ag{sub 2}Te layer grown on the Mo/glass exhibited a membrane filter structure from the SEM observation. XRD spectra of layers grown with and without the buffer layer were compared. The AgGaTe{sub 2} layer with the Ag{sub 2}Te buffer layer exhibited peaks originating from AgGaTe{sub 2}, and a very strong diffraction peak of 112 was observed. On the other hand, it was cleared that the layer grown without the buffer layer exhibited no strong peaks associated with AgGaTe{sub 2}, but Ga-Te compounds. From this, crystallographic properties of the AgGaTe{sub 2} layer were drastically improved by the insertion of the Ag{sub 2}Te buffer layer. Moreover, the surface morphology exhibited a smooth surface when the Ag{sub 2}Te buffer layer was inserted. The nucleation site density of AgGaTe{sub 2} was probably increased since the membrane filter structure exhibited numbers of kinks at the edge. Chemical reaction between Ga and Mo was also eliminated. It was cleared that the insertion of the buffer layer and its surface morphology were an important parameter to grow high quality AgGaTe{sub 2} layers. (copyright 2015 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. Influence of aerosol lifetime on the interpretation of nucleation experiments with respect to the first nucleation theorem

    Directory of Open Access Journals (Sweden)

    S. Ehrhart

    2013-04-01

    Full Text Available The SAWNUC microphysical aerosol nucleation model is used to study the effect of reactor walls on the interpretation of nucleation experiments with respect to nucleation theory. This work shows that loss processes, such as wall losses, influence the interpretation of nucleation experiments, especially at low growth rates and short lifetime of freshly nucleated particles. In these cases the power dependency of the formation rates, determined at a certain particle size, with respect to H2SO4 does not correspond to the approximate number of H2SO4 molecules in the critical cluster as expected by the first nucleation theorem. Observed ∂log(J/∂log([H2SO4] therefore can vary widely for identical nucleation conditions but different sink terms.

  16. 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.

  17. 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.

  18. Influence of silver content on rifampicin adsorptivity for magnetite/Ag/rifampicin nanoparticles

    Science.gov (United States)

    Ivashchenko, Olena; Coy, Emerson; Peplinska, Barbara; Jarek, Marcin; Lewandowski, Mikołaj; Załęski, Karol; Warowicka, Alicja; Wozniak, Anna; Babutina, Tatiana; Jurga-Stopa, Justyna; Dolinsek, Janez; Jurga, Stefan

    2017-02-01

    Magnetite nanoparticles (NPs) decorated with silver (magnetite/Ag) are intensively investigated due to their application in the biomedical field. We demonstrate that the increase of silver content on the surface of nanoparticles improves the adsorptivity of antibiotic rifampicin as well as antibacterial properties. The use of ginger extract allowed to improve the silver nucleation on the magnetite surface that resulted in an increase of silver content. Physicochemical and functional characterization of magnetite/Ag NPs was performed. Our results show that 5%-10% of silver content in magnetite/Ag NPs is already sufficient for antimicrobial properties against Streptococcus salivarius and Staphylococcus aureus. The rifampicin molecules on the magnetite/Ag NPs surface made the spectrum of antimicrobial activity wider. Cytotoxicity evaluation of the magnetite/Ag/rifampicin NPs showed no harmful action towards normal human fibroblasts, whereas the effect on human embryonic kidney cell viability was time and dose dependent.

  19. Effects of shear flow on phase nucleation and crystallization

    Science.gov (United States)

    Mura, Federica; Zaccone, Alessio

    2016-04-01

    Classical nucleation theory offers a good framework for understanding the common features of new phase formation processes in metastable homogeneous media at rest. However, nucleation processes in liquids are ubiquitously affected by hydrodynamic flow, and there is no satisfactory understanding of whether shear promotes or slows down the nucleation process. We developed a classical nucleation theory for sheared systems starting from the molecular level of the Becker-Doering master kinetic equation and we analytically derived a closed-form expression for the nucleation rate. The theory accounts for the effect of flow-mediated transport of molecules to the nucleus of the new phase, as well as for the mechanical deformation imparted to the nucleus by the flow field. The competition between flow-induced molecular transport, which accelerates nucleation, and flow-induced nucleus straining, which lowers the nucleation rate by increasing the nucleation energy barrier, gives rise to a marked nonmonotonic dependence of the nucleation rate on the shear rate. The theory predicts an optimal shear rate at which the nucleation rate is one order of magnitude larger than in the absence of flow.

  20. Homogeneous vs. heterogeneous nucleation in water-dicarboxylic acid systems

    Directory of Open Access Journals (Sweden)

    A. I. Hienola

    2008-10-01

    Full Text Available Binary heterogeneous nucleation of water-succinic/glutaric/malonic/adipic acid on nanometer-sized particles is investigated within the frame of classical heterogeneous nucleation theory. Homogeneous nucleation is also included for comparison. It is found that the nucleation probabilities depend on the contact angle and on the size of the seed particles. New thermodynamical properties, such as saturation vapor pressure, density and surface tension for all the dicarboxylic acid aqueous solutions are included in the calculations. While the new surface tension and density formulations do not bring any significant difference in the computed nucleation rate for homogeneous nucleation for succinic and glutaric acids, the use of the newly derived equations for the vapor pressure decrease the acid concentrations in gas phase with 3 orders of magnitude. According to our calculations, the binary heterogeneous nucleation of succinic acid-water and glutaric acid-water – although it requires a 3–4 orders of magnitude lower vapor concentrations than the homogeneous nucleation – cannot take place in atmospheric conditions. On the other hand binary homogeneous nucleation of adipic acid-water systems might be possible in conditions occuring in upper boundary layer. However, a more detailed characterization of the interaction between the surface and the molecules of the nucleating vapor should be considered in the future.

  1. Overview: Experimental studies of crystal nucleation: Metals and colloids

    Science.gov (United States)

    Herlach, Dieter M.; Palberg, Thomas; Klassen, Ina; Klein, Stefan; Kobold, Raphael

    2016-12-01

    Crystallization is one of the most important phase transformations of first order. In the case of metals and alloys, the liquid phase is the parent phase of materials production. The conditions of the crystallization process control the as-solidified material in its chemical and physical properties. Nucleation initiates the crystallization of a liquid. It selects the crystallographic phase, stable or meta-stable. Its detailed knowledge is therefore mandatory for the design of materials. We present techniques of containerless processing for nucleation studies of metals and alloys. Experimental results demonstrate the power of these methods not only for crystal nucleation of stable solids but in particular also for investigations of crystal nucleation of metastable solids at extreme undercooling. This concerns the physical nature of heterogeneous versus homogeneous nucleation and nucleation of phases nucleated under non-equilibrium conditions. The results are analyzed within classical nucleation theory that defines the activation energy of homogeneous nucleation in terms of the interfacial energy and the difference of Gibbs free energies of solid and liquid. The interfacial energy acts as barrier for the nucleation process. Its experimental determination is difficult in the case of metals. In the second part of this work we therefore explore the potential of colloidal suspensions as model systems for the crystallization process. The nucleation process of colloids is observed in situ by optical observation and ultra-small angle X-ray diffraction using high intensity synchrotron radiation. It allows an unambiguous discrimination of homogeneous and heterogeneous nucleation as well as the determination of the interfacial free energy of the solid-liquid interface. Our results are used to construct Turnbull plots of colloids, which are discussed in relation to Turnbull plots of metals and support the hypothesis that colloids are useful model systems to investigate crystal

  2. Atmospheric nucleation: highlights of the EUCAARI project and future directions

    Directory of Open Access Journals (Sweden)

    V.-M. Kerminen

    2010-11-01

    Full Text Available Within the project EUCAARI (European Integrated project on Aerosol Cloud Climate and Air Quality interactions, atmospheric nucleation was studied by (i developing and testing new air ion and cluster spectrometers, (ii conducting homogeneous nucleation experiments for sulphate and organic systems in the laboratory, (iii investigating atmospheric nucleation mechanism under field conditions, and (iv applying new theoretical and modelling tools for data interpretation and development of parameterisations. The current paper provides a synthesis of the obtained results and identifies the remaining major knowledge gaps related to atmospheric nucleation. The most important technical achievement of the project was the development of new instruments for measuring sub-3 nm particle populations, along with the extensive application of these instruments in both the laboratory and the field. All the results obtained during EUCAARI indicate that sulphuric acid plays a central role in atmospheric nucleation. However, also vapours other than sulphuric acid are needed to explain the nucleation and the subsequent growth processes, at least in continental boundary layers. Candidate vapours in this respect are some organic compounds, ammonia, and especially amines. Both our field and laboratory data demonstrate that the nucleation rate scales to the first or second power of the nucleating vapour concentration(s. This agrees with the few earlier field observations, but is in stark contrast with classical thermodynamic nucleation theories. The average formation rates of 2-nm particles were found to vary by almost two orders of magnitude between the different EUCAARI sites, whereas the formation rates of charged 2-nm particles varied very little between the sites. Overall, our observations are indicative of frequent, yet moderate, ion-induced nucleation usually outweighed by much stronger neutral nucleation events in the continental lower troposphere. The most concrete

  3. Vacancy-solute interactions during multiple-step ageing of an Al-Cu-Mg-Ag alloy

    Energy Technology Data Exchange (ETDEWEB)

    Ferragut, R. [L-NESS, Dipartimento di Fisica, Politecnico di Milano, Anzani 42, I-22100 Como (Italy)], E-mail: rafael.ferragut@polimi.it; Dupasquier, A. [L-NESS, Dipartimento di Fisica, Politecnico di Milano, Anzani 42, I-22100 Como (Italy); Macchi, C.E. [IFIMAT, UNCentro and CONICET, Pinto 399, B7000GHG Tandil (Argentina); Somoza, A. [IFIMAT, UNCentro and CICPBA, Pinto 399, B7000GHG Tandil (Argentina); Lumley, R.N. [CSIRO Light Metals Flagship, Locked Bag 33, Clayton South, MDC, Vic. 3169 (Australia); Polmear, I.J. [Department of Materials Engineering, Monash University, Melbourne, Vic. 3800 (Australia)

    2009-02-15

    Small additions of Ag and Mg stimulate nucleation of the {omega} phase in artificially aged Al-Cu alloys, after which these elements segregate to the {omega}/matrix interfaces. In this work, positron spectroscopy results show that vacancies accompany the Ag (and Mg) atoms at the interface during precipitate formation, after which they are released back into the matrix and facilitate secondary ageing at ambient temperature.

  4. DNA-mediated silver nanoclusters: synthesis, properties and applications.

    Science.gov (United States)

    Latorre, Alfonso; Somoza, Álvaro

    2012-05-07

    Fluorescent DNA-AgNCs have emerged as an alternative to standard emitters because of their unique properties: high fluorescent quantum yield, photostability, a broad pallet of colors (blue to near-IR), and the fact that their properties are easily modulated by the DNA sequence and environment. Applications as gene, ion, or small-molecule sensors have been reported.

  5. Identification & Characterization of Fungal Ice Nucleation Proteins

    Science.gov (United States)

    Scheel, Jan Frederik; Kunert, Anna Theresa; Kampf, Christopher Johannes; Mauri, Sergio; Weidner, Tobias; Pöschl, Ulrich; Fröhlich-Nowoisky, Janine

    2016-04-01

    Freezing of water at relatively warm subfreezing temperatures is dependent on ice nucleation catalysis facilitated by ice nuclei (IN). These IN can be of various origins and although extensive research was done and progress was achieved, the nature and mechanisms leading to an effective IN are to date still poorly understood. Some of the most important processes of our geosphere like the water cycle are highly dependent on effective ice nucleation at temperatures between -2°C - -8°C, a temperature range which is almost exclusively covered by biological IN (BioIN). BioIN are usually macromolecular structures of biological polymers. Sugars as well as proteins have been reported to serve as IN and the best characterized BioIN are ice nucleation proteins (IN-P) from gram negative bacteria. Fungal strains from Fusarium spp. were described to be effective IN at subfreezing temperatures up to -2°C already 25 years ago and more and more fungal species are described to serve as efficient IN. Fungal IN are also thought to be proteins or at least contain a proteinaceous compound, but to date the fungal IN-P primary structure as well as their coding genetic elements of all IN active fungi are unknown. The aim of this study is a.) to identify the proteins and their coding genetic elements from IN active fungi (F. acuminatum, F. avenaceum, M. alpina) and b.) to characterize the mechanisms by which fungal IN serve as effective IN. We designed an interdisciplinary approach using biological, analytical and physical methods to identify fungal IN-P and describe their biological, chemical, and physical properties.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. {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.

  15. Aerosol nucleation induced by a high energy particle beam

    DEFF Research Database (Denmark)

    Enghoff, Martin Andreas Bødker; Pedersen, Jens Olaf Pepke; Uggerhøj, Ulrik I.

    atmospheric conditions using a 580 MeV electron beam to ionize the volume of the reaction chamber. We find a clear and significant contribution from ion induced nucleation and consider this to be an unambiguous observation of the ion-effect on aerosol nucleation using a particle beam under conditions not far......The effect of ions in aerosol nucleation is a subject where much remains to be discovered. That ions can enhance nucleation has been shown by theory, observations, and experiments. However, the exact mechanism still remains to be determined. One question is if the nature of the ionization affects...... the nucleation. This is an essential question since many experiments have been performed using radioactive sources that ionize differently than the cosmic rays which are responsible for the majority of atmospheric ionization. Here we report on an experimental study of sulphuric acid aerosol nucleation under near...

  16. Heterogeneous ice nucleation: bridging stochastic and singular freezing behavior

    Directory of Open Access Journals (Sweden)

    D. Niedermeier

    2011-01-01

    Full Text Available Heterogeneous ice nucleation, a primary pathway for ice formation in the atmosphere, has been described alternately as being stochastic, in direct analogy with homogeneous nucleation, or singular, with ice nuclei initiating freezing at deterministic temperatures. We present an idealized model that bridges these stochastic and singular descriptions of heterogeneous ice nucleation. This "soccer ball" model treats statistically similar particles as being covered with surface sites (patches of finite area characterized by different nucleation barriers, but with each surface site following the stochastic nature of ice embryo formation. The model provides a phenomenological explanation for seemingly contradictory experimental results obtained in our research groups. We suggest that ice nucleation is fundamentally a stochastic process but that for realistic atmospheric particle populations this process can be masked by the heterogeneity of surface properties. Full evaluation of the model will require experiments with well characterized ice nucleating particles and the ability to vary both temperature and waiting time for freezing.

  17. Using silver nanocluster/graphene nanocomposite to enhance photoelectrochemical activity of CdS:Mn/TiO2 for highly sensitive signal-on immunoassay.

    Science.gov (United States)

    Song, Jie; Wang, Jiamian; Wang, Xiuyun; Zhao, Wei; Zhao, Yanqiu; Wu, Shuo; Gao, Zhanming; Yuan, Jingli; Meng, Changgong

    2016-06-15

    A highly sensitive signal-on photoelectrochemical (PEC) immunosensor was fabricated here using CdS:Mn/TiO2 as photoelectrochemical sensing platform, and silver nanoclusters and graphene naocomposites (AgNCs-GR) as signal amplification tags. The immunosensor was constructed based on the specific sandwich immunoreaction, and the photo-to-current conversion efficiency of the isolated protein modified CdS:Mn/TiO2 matrix was improved based on the synergistic effect of AgNCs-GR. Under irradiation, the photogenerated electrons from the AgNCs at a higher conduction band edge level could be transport to the CdS:Mn/TiO2 matrix with the assistance of highly conductive graphene nanosheets, as well as recycle the trapped excitons in the defects-rich CdS:Mn/TiO2 interface. The electron transport and exciton recycle reduced the possibility of electron-hole recombination and greatly improved the photo-to-current conversion efficiency of the sensing matrix. Based on the signal enhancement, a signal-on PEC immunosensors was fabricated for the detection of carcinoembryonic antigen (CEA), a model analyte related to many malignant diseases. Under optimal conditions, the as-prepared immunosensor showed excellent analytical performance, with a wide linear range from 1.0 pg/mL to 100 ng/mL and a low limit of detection of 1.0 pg/mL. The signal-on mode provided 2.48 times higher sensitivity compared with signal-off mode. This strategy demonstrated good accuracy and high selectivity for practical sample analysis, thus may have great application prospective in the prediction and early diagnosis of diseases.

  18. The role of Ag precipitates in Cu-12 wt% Ag

    Energy Technology Data Exchange (ETDEWEB)

    Yao, D.W.; Song, L.N. [Department of Materials Science and Engineering, Zhejiang University, Zheda Road No.38, Hangzhou, Zhejiang 310027 (China); Dong, A.P.; Wang, L.T. [China Railway Construction Electrification Bureau Group Co.,Ltd., Beijing 100036 (China); Zhang, L. [School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083 (China); Meng, L., E-mail: mengliang@zju.edu.cn [Department of Materials Science and Engineering, Zhejiang University, Zheda Road No.38, Hangzhou, Zhejiang 310027 (China)

    2012-12-15

    The Cu-12 wt% Ag was prepared to investigate the role of Ag precipitates on the properties of the alloy. Two kinds of heat treatment procedures were adopted to produce different amount of Ag precipitates in the Cu-12 wt% Ag. The microstructure of Ag precipitates was systematically observed by optical microscopy and electron microscopy. The Cu-12 wt% Ag with more Ag precipitates exhibits higher strength and lower electrical conductivity. More Ag precipitates results in more phase interface and less Ag atoms dissolved in Cu matrix. By comparing the strengthening effect and electron scattering effect of phase interface and dissolved Ag atoms, it is conclude that the interface between Cu matrix and Ag precipitates could significantly block dislocation movement and enhance electron scattering in Cu-Ag alloys.

  19. Effects of rapid solidification on the microstructure and microhardness of a lead-free Sn-3.5Ag solder

    Institute of Scientific and Technical Information of China (English)

    SHEN Jun; LIU Yongchang; Han Yajing; GAO Houxiu

    2006-01-01

    A lead-free Sn-3.5Ag solder was prepared by rapid solidification technology. The high solidification rate, obtained by rapid cooling, promotes nucleation, and suppresses the growth of Ag3Sn intermetallic compounds (IMCs) in Ag-rich zone, yielding fine Ag3Sn nanoparticulates with spherical morphology in the matrix of the solder. The large amount of tough homogeneously-dispersed IMCs helps to improve the surface area per unit volume and obstructs the dislocation lines passing through the solder, which fits with the dispersion-strengthening theory. Hence, the rapidly-solidified Sn-3.5Ag solder exhibits a higher microhardness when compared with a slowly-solidified Sn-3.5Ag solder.

  20. Epitaxial Nucleation on Rationally Designed Peptide Functionalized Interface

    Science.gov (United States)

    2011-07-19

    in order to generate intricate biomimetic architectures , matrix mediated nucleation needs to be a multi- step process,23 This hypothesis is known as... tectonic ” nucleation and growth,24 and we apply our biomimetic interfacially confined peptide to explore this phenomenon at an addressable air...template functional hybrid materials. Figure 2. Tectonic hypothesis for nucleation and growth. 23 Figure 3. Objectives and progress. Progress in

  1. Comment on evidence for surface-initiated homogenous nucleation

    Directory of Open Access Journals (Sweden)

    J. E. Kay

    2003-01-01

    Full Text Available We investigate theoretical, laboratory, and atmospheric evidence for a recently proposed hypothesis: homogenous ice nucleation occurs at the surface, not in the volume, of supercooled water drops. Using existing thermodynamic arguments, laboratory experiments, and atmospheric data, we conclude that ice embryo formation at the surface cannot be confirmed or disregarded. Ice nucleation rates measured as a function of drop size in an air ambient could help distinguish between volume and surface nucleation rates.

  2. Interpretation of dc and ac conductivity of Ag{sub 2}O–SeO{sub 2}–MoO{sub 3} glass-nanocomposite-semiconductor

    Energy Technology Data Exchange (ETDEWEB)

    Bhattacharya, Sanjib, E-mail: sanjib_ssp@yahoo.co.in [Department of Engineering Sciences and Humanities, Siliguri Institute of Technology, Darjeeeling 734009, West Bengal (India); Kundu, Ranadip [Department of Engineering Sciences and Humanities, Siliguri Institute of Technology, Darjeeeling 734009, West Bengal (India); Department of Mechanical Engineering, Jadavpur University, Jadavpur, Kolkata 700032 (India); Das, Anindya Sundar [Department of Mechanical Engineering, Jadavpur University, Jadavpur, Kolkata 700032 (India); Department of Electronics and Communication Engineering, Regent Education and Research Foundation, Barrackpore, Kolkata 7000121 (India); Roy, Debasish [Department of Mechanical Engineering, Jadavpur University, Jadavpur, Kolkata 700032 (India)

    2015-07-15

    Highlights: • Polaron hopping. • Dc and ac conductivity. • Mott's model and Greave's model. • Ag{sub 2}MoO{sub 4}, Ag{sub 2}Mo{sub 2}O{sub 7} and Ag{sub 6}Mo{sub 10}O{sub 33} nanoparticles and SeO{sub 3} and SeO{sub 4} nanoclusters. • XRD and FESEM studies. - Abstract: A new type of semiconducting glass-nanocomposites 0.3Ag{sub 2}O–0.7 (xMoO{sub 3}–(1 − x) SeO{sub 2}) is prepared by melt-quenching route. The formation of Ag{sub 2}MoO{sub 4}, Ag{sub 2}Mo{sub 2}O{sub 7} and Ag{sub 6}Mo{sub 10}O{sub 33} nanoparticles and SeO{sub 3} and SeO{sub 4} nanoclusters in glass-nanocomposites has been confirmed from X-ray diffraction (XRD) and field emission scanning electron microscopic (FESEM) studies. Fourier transform infrared (FTIR) spectroscopy is employed to find out Se−O stretching vibration as well as stretching vibrations of Mo{sub 2}O{sub 7}{sup 2−} ions. The dc conductivity of them is studied on the light of polaron hopping approach in a wide temperature range. At low temperatures, variable range hopping model (Mott's model) is employed to analyze the conductivity data. Greave's model is used to predict temperature dependent variable range hopping in the high temperature region. Frequency dependent ac conductivity is well explained on the basis of tunneling. I–V characteristics of the as-prepared samples have also been investigated.

  3. Electrochemistry and the mechanisms of nucleation and growth of neodymium during electroreduction from LiCl–KCl eutectic salts on Mo substrate

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Hao [Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001 (China); Department of Chemical and Materials Engineering, University of Idaho, Moscow, ID 83844 (United States); Pesic, Batric, E-mail: pesic@uidaho.edu [Department of Chemical and Materials Engineering, University of Idaho, Moscow, ID 83844 (United States)

    2015-03-15

    The electrochemical behavior of NdCl{sub 3} was studied on a Mo electrode in molten LiCl–KCl eutectic salts. The electroreduction of Nd(III)/Nd(0) involved two reaction steps, as confirmed by three different electrochemical techniques. In the first reaction step, Nd(III) is converted into soluble Nd(II), which undergoes further reduction into metallic Nd(0) in the second reaction step. The standard reaction rate constants for each reaction step were determined by Nicholson method. The rate constant values were used in Matsuda-Ayabe’s criteria for testing the electrochemical reversibility. Accordingly, both reaction steps were quasi-reversible redox reactions. The nucleation mechanisms of neodymium metal deposited on a Mo substrate were predicted by using Scharifker–Hill model, and tested for the first time by scanning electron microscopy (SEM) studies of the electrode surface. The SEM studies confirmed that for the low initial concentration of NdCl{sub 3}, neodymium nucleates and grows progressively, while for higher NdCl{sub 3} concentrations, the related mechanism is instantaneous. Both are governed by the aggregative growth mechanisms based on surface mobility of formed nanoclusters.

  4. The effects of nucleation and solidification mechanisms on the microstructure and thermomechanical response of tin silver copper solder joints

    Science.gov (United States)

    Arfaei, Babak

    This work examines the nucleation mechanism of Sn in SnAgCu alloys and its effect on the microstructure of those solder joints. The nucleation rate of Sn in a SAC alloy was obtained by simultaneous calorimetric examination of the isothermal solidification of 88 flip chip Sn-Ag-Cu solder joints. Qualitative agreement with classic nucleation theory was observed, although it was concluded that the spherical cap model cannot be applied to explain the structure of nucleus. It was shown that the solidification temperature significantly affects the microstructure; samples that undercooled less than approximately 40oC revealed one or three large Sn grains, while interlaced twinning was observed in the samples that solidified at lower temperatures. In order to better understand the effect of microstructure on the thermomechanical properties of solder joints, a study of the dependence of room temperature shear fatigue lifetime on Sn grain number and orientation was conducted. This study examined the correlations of variations in fatigue life of solder balls with the microstructure of Sn-Ag-Cu solder. The mean fatigue lifetime was found to be significantly longer for samples with multiple Sn grains than for samples with single Sn grains. For single grain samples, correlations between Sn grain orientation (with respect to the loading direction) and lifetime were observed, providing insight on early failures in SnAgCu solder joints. Correlations between the lifetimes of single Sn grained, SAC205 solder joints with differences in Ag3Sn and Cu6Sn5 precipitate microstructures were investigated. It was found that Ag3Sn precipitates were highly segregated from Cu6Sn 5 precipitates on a length scale of approximately twenty microns. Furthermore, large (factor of two) variations of the Sn dendrite arm size were observed within given samples. Such variations in values of dendrite arm size within a single sample were much larger than observed variations of this parameter between

  5. Earthquake nucleation in weak subducted carbonates

    Science.gov (United States)

    Kurzawski, Robert M.; Stipp, Michael; Niemeijer, André R.; Spiers, Christopher J.; Behrmann, Jan H.

    2016-09-01

    Ocean-floor carbonate- and clay-rich sediments form major inputs to subduction zones, especially at low-latitude convergent plate margins. Therefore, knowledge of their frictional behaviour is fundamental for understanding plate-boundary earthquakes. Here we report results of mechanical tests performed on simulated fault gouges prepared from ocean-floor carbonates and clays, cored during IODP drilling offshore Costa Rica. Clay-rich gouges show internal friction coefficients (that is, the slope of linearized shear stress versus normal stress data) of μint = 0.44 - 0.56, irrespective of temperature and pore-fluid pressure (Pf). By contrast, μint for the carbonate gouge strongly depends on temperature and pore-fluid pressure, with μint decreasing dramatically from 0.84 at room temperature and Pf = 20 MPa to 0.27 at T = 140 °C and Pf = 120 MPa. This effect provides a fundamental mechanism of shear localization and earthquake generation in subduction zones, and makes carbonates likely nucleation sites for plate-boundary earthquakes. Our results imply that rupture nucleation is prompted by a combination of temperature-controlled frictional instability and temperature- and pore-pressure-dependent weakening of calcareous fault gouges.

  6. Thermodynamics of ice nucleation in liquid water.

    Science.gov (United States)

    Wang, Xin; Wang, Shui; Xu, Qinzhi; Mi, Jianguo

    2015-01-29

    We present a density functional theory approach to investigate the thermodynamics of ice nucleation in supercooled water. Within the theoretical framework, the free-energy functional is constructed by the direct correlation function of oxygen-oxygen of the equilibrium water, and the function is derived from the reference interaction site model in consideration of the interactions of hydrogen-hydrogen, hydrogen-oxygen, and oxygen-oxygen. The equilibrium properties, including vapor-liquid and liquid-solid phase equilibria, local structure of hexagonal ice crystal, and interfacial structure and tension of water-ice are calculated in advance to examine the basis for the theory. The predicted phase equilibria and the water-ice surface tension are in good agreement with the experimental data. In particular, the critical nucleus radius and free-energy barrier during ice nucleation are predicted. The critical radius is similar to the simulation value, suggesting that the current theoretical approach is suitable in describing the thermodynamic properties of ice crystallization.

  7. Theoretical analysis of bubble nucleation in GASAR materials

    Institute of Scientific and Technical Information of China (English)

    刘源; 李言祥

    2003-01-01

    Nucleation of gaseous hydrogen bubbles is the initial stage of GASAR process. Through the theoretical analysis, it has been identified that heterogeneous nucleation of bubbles as caps on the solid surfaces of impurities is impossible and only the heterogeneous nucleation in pits and cracks in impurities is the most feasible way in the GASAR process. The results also show that the probability of bubble nucleation progressively decreases from Al, Cu and Ni to Fe molten metal, which is the result of the increasing adhesion work of liquid metal on alumina.

  8. 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

  9. 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.

  10. Optically active red-emitting Cu nanoclusters originating from complexation and redox reaction between copper(ii) and d/l-penicillamine

    Science.gov (United States)

    Long, Tengfei; Guo, Yanjia; Lin, Min; Yuan, Mengke; Liu, Zhongde; Huang, Chengzhi

    2016-05-01

    Despite a significant surge in the number of investigations into both optically active Au and Ag nanostructures, there is currently only limited knowledge about optically active Cu nanoclusters (CuNCs) and their potential applications. Here, we have succeeded in preparing a pair of optically active red-emitting CuNCs on the basis of complexation and redox reaction between copper(ii) and penicillamine (Pen) enantiomers, in which Pen serves as both a reducing agent and a stabilizing ligand. Significantly, the CuNCs feature unique aggregation induced emission (AIE) characteristics and therefore can serve as pH stimuli-responsive functional materials. Impressively, the ligand chirality plays a dramatic role for the creation of brightly emissive CuNCs, attributed to the conformation of racemic Pen being unfavorable for the electrostatic interaction, and thus suppressing the formation of cluster aggregates. In addition, the clusters display potential toward cytoplasmic staining and labelling due to the high photoluminescence (PL) quantum yields (QYs) and remarkable cellular uptake, in spite that no chirality-dependent effects in autophagy and subcellular localization are observed in the application of chiral cluster enantiomer-based cell imaging.Despite a significant surge in the number of investigations into both optically active Au and Ag nanostructures, there is currently only limited knowledge about optically active Cu nanoclusters (CuNCs) and their potential applications. Here, we have succeeded in preparing a pair of optically active red-emitting CuNCs on the basis of complexation and redox reaction between copper(ii) and penicillamine (Pen) enantiomers, in which Pen serves as both a reducing agent and a stabilizing ligand. Significantly, the CuNCs feature unique aggregation induced emission (AIE) characteristics and therefore can serve as pH stimuli-responsive functional materials. Impressively, the ligand chirality plays a dramatic role for the creation of

  11. Phase field theory of interfaces and crystal nucleation in a eutectic system of fcc structure: I. Transitions in the one-phase liquid region.

    Science.gov (United States)

    Tóth, Gyula I; Gránásy, László

    2007-08-21

    The phase field theory (PFT) has been applied to predict equilibrium interfacial properties and nucleation barrier in the binary eutectic system Ag-Cu using double well and interpolation functions deduced from a Ginzburg-Landau expansion that considers fcc (face centered cubic) crystal symmetries. The temperature and composition dependent free energies of the liquid and solid phases are taken from CALculation of PHAse Diagrams-type calculations. The model parameters of PFT are fixed so as to recover an interface thickness of approximately 1 nm from molecular dynamics simulations and the interfacial free energies from the experimental dihedral angles available for the pure components. A nontrivial temperature and composition dependence for the equilibrium interfacial free energy is observed. Mapping the possible nucleation pathways, we find that the Ag and Cu rich critical fluctuations compete against each other in the neighborhood of the eutectic composition. The Tolman length is positive and shows a maximum as a function of undercooling. The PFT predictions for the critical undercooling are found to be consistent with experimental results. These results support the view that heterogeneous nucleation took place in the undercooling experiments available at present. We also present calculations using the classical droplet model [classical nucleation theory (CNT)] and a phenomenological diffuse interface theory (DIT). While the predictions of the CNT with a purely entropic interfacial free energy underestimate the critical undercooling, the DIT results appear to be in a reasonable agreement with the PFT predictions.

  12. 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

  13. 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

  14. Growth of Ag thin films on ZnO(0 0 0 -1) investigated by AES and STM

    Energy Technology Data Exchange (ETDEWEB)

    Duriau, E. [Interuniversity Microelectronic Center (IMEC), SPDT-MCA, Kapeldreef 75, B-3001 Leuven (Belgium); Agouram, S. [Dpto. Fisica Aplicada y Electromagnetismo c/Dr. Moliner no. 50, 46100 Burjassot, Valencia (Spain); Laboratoire de Physique des Materiaux Electroniques (LPME), University of Namur, Rue de Bruxelles 61, B-5000 Namur (Belgium); Morhain, C. [Centre de Recherche sur l' HeteroEpitaxie et ses Applications (CRHEA), CNRS, Rue Bernard Gregory, F-06560 Valbonne Sophia-Antipolis (France); Seldrum, T. [Laboratoire de Physique des Materiaux Electroniques (LPME), University of Namur, Rue de Bruxelles 61, B-5000 Namur (Belgium); Sporken, R. [Laboratoire de Physique des Materiaux Electroniques (LPME), University of Namur, Rue de Bruxelles 61, B-5000 Namur (Belgium); Dumont, J. [Laboratoire de Physique des Materiaux Electroniques (LPME), University of Namur, Rue de Bruxelles 61, B-5000 Namur (Belgium)]. E-mail: jacques.dumont@fundp.ac.be

    2006-11-15

    The growth of Ag films on ZnO(0 0 0 -1) has been investigated by Auger electron spectroscopy (AES) and scanning tunneling microscopy (STM). A high density of islands is nucleated at the earliest stages of the growth. An upstepping mechanism causes these islands to coalesce while the uncovered fraction of the ZnO surface remains constant (30%)

  15. AGS experiments: 1993 - 1994 - 1995

    Energy Technology Data Exchange (ETDEWEB)

    Depken, J.C.

    1996-04-01

    This report contains: FY 1995 AGS Schedule as Run; FY 1996-97 AGE Schedule (working copy); AGS Beams 1995; AGS Experimental Area FY 1993 Physics Program; AGS Experimental Area FY 1994 Physics Program; AGS Experimental Area FY 1995 Physics Program; AGS Experimental Area FY 1996 Physics Program (In progress); A listing of experiments by number; Two-page summaries of each experiment begin here, also ordered by number; Listing of publications of AGS experiments begins here; and Listing of AGS experimenters begins here. This is the twelfth edition.

  16. 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

  17. 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.

  18. Trapping crystal nucleation of cholesterol monohydrate

    DEFF Research Database (Denmark)

    Solomonov, I.; Weygand, M.J.; Kjær, K.

    2005-01-01

    Crystalline nucleation of cholesterol at the air-water interface has been studied via grazing incidence x-ray diffraction using synchrotron radiation. The various stages of cholesterol molecular assembly from monolayer to three bilayers incorporating interleaving hydrogen-bonded water layers...... in a monoclinic cholesterol . H2O phase, has been monitored and their structures characterized to near atomic resolution. Crystallographic evidence is presented that this multilayer phase is similar to that of a reported metastable cholesterol phase of undetermined structure obtained from bile before...... transformation to the triclinic phase of cholesterol . H2O, the thermodynamically stable macroscopic form. According to grazing incidence x-ray diffraction measurements and crystallographic data, a transformation from the monoclinic film structure to a multilayer of the stable monohydrate phase involves...

  19. Propane hydrate nucleation: Experimental investigation and correlation

    DEFF Research Database (Denmark)

    Jensen, Lars; Thomsen, Kaj; von Solms, Nicolas

    2008-01-01

    In this work the nucleation kinetics of propane gas hydrate has been investigated experimentally using a stirred batch reactor. The experiments have been performed isothermally recording the pressure as a function of time. Experiments were conducted at different stirring rates, but in the same......) to the aqueous phase was found to reduce the gas dissolution rate slightly. However the induction times were prolonged quite substantially upon addition of PVP.The induction time data were correlated using a newly developed induction time model based on crystallization theory also capable of taking into account...... the presence of additives. In most cases reasonable agreement between the data and the model could be obtained. The results revealed that especially the effective surface energy between propane hydrate and water is likely to change when the stirring rate varies from very high to low. The prolongation...

  20. Preparation and nucleation of spherical metallic droplet

    Directory of Open Access Journals (Sweden)

    Bing-ge Zhao

    2015-03-01

    Full Text Available The preparation and solidification of metallic droplets attract more and more attention for their significance in both engineering and scientific fields. In this paper, the preparation and characterization of Sn-based alloy droplets using different methods such as atomization and consumable electrode direct current arc (CDCA technique are reviewed. The morphology and structure of these droplets were determined by optical microscopy, X-ray diffraction (XRD and scanning electron microscopy (SEM. The solidification behavior of single droplet was systematically studied by means of scanning calorimetry (DSC, and the nucleation kinetics was also calculated. In particular, the development of fast scanning calorimetry (FSC made it possible to investigate the evolution of undercooling under ultrafast but controllable heating and cooling conditions. The combination of CDCA technique and FSC measurements opens up a new door for quantitative studies on droplet solidification, which is accessible to demonstrate some theories by experiments.

  1. Aggregate geometry in amyloid fibril nucleation

    CERN Document Server

    Irbäck, A; Linnemann, N; Linse, B; Wallin, S; 10.1103/PhysRevLett.110.058101

    2013-01-01

    We present and study a minimal structure-based model for the self-assembly of peptides into ordered beta-sheet-rich fibrils. The peptides are represented by unit-length sticks on a cubic lattice and interact by hydrogen bonding and hydrophobicity forces. By Monte Carlo simulations with >100,000 peptides, we show that fibril formation occurs with sigmoidal kinetics in the model. To determine the mechanism of fibril nucleation, we compute the joint distribution in length and width of the aggregates at equilibrium, using an efficient cluster move and flat-histogram techniques. This analysis, based on simulations with 256 peptides in which aggregates form and dissolve reversibly, shows that the main free-energy barriers that a nascent fibril has to overcome are associated with changes in width.

  2. Nucleation at hardness indentations in cold rolled Al

    DEFF Research Database (Denmark)

    Xu, C.L.; Zhang, Yubin; Wu, G.L.

    2015-01-01

    Nucleation of recrystallization near hardness indentations has been investigated in slightly cold rolled high purity aluminium. Samples were cold rolled to 12% and 20% reductions in thickness and indentations were done with two different loads (500 g and 2000 g). The samples were annealed at 300 ...... and stored energy distributions and thus on nucleation are discussed....

  3. Nucleation of ferrite in austenite: the role of crystallography

    NARCIS (Netherlands)

    Landheer, H.

    2010-01-01

    The nucleation mechanisms during solid-state phase transformations in polycrystalline materials are still not completely understood. The nucleation stage has a strong influence on the overall evolution of phase transformations, which determines the final microstructure and thereby the properties of

  4. Local structure of liquid carbon controls diamond nucleation

    NARCIS (Netherlands)

    Ghiringhelli, L.M.; Valeriani, C.; Meijer, E.J.; Frenkel, D.

    2009-01-01

    Diamonds melt at temperatures above 4000 K. There are no measurements of the steady-state rate of the reverse process: diamond nucleation from the melt, because experiments are difficult at these extreme temperatures and pressures. Using numerical simulations, we estimate the diamond nucleation rate

  5. Bubble nucleation in an explosive micro-bubble actuator

    NARCIS (Netherlands)

    Broek, van den D.M.; Elwenspoek, M.C.

    2008-01-01

    Explosive evaporation occurs when a thin layer of liquid reaches a temperature close to the critical temperature in a very short time. At these temperatures spontaneous nucleation takes place. The nucleated bubbles instantly coalesce forming a vapour film followed by rapid growth due to the pressure

  6. Copper Oxidation through Nucleation Sites of Chemical Vapor Deposited Graphene

    DEFF Research Database (Denmark)

    Luo, Birong; Whelan, Patrick Rebsdorf; Shivayogimath, Abhay

    2016-01-01

    We investigate the nucleation defect-triggered oxidation of Cu covered by CVD graphene during postannealing in air. The results reveal that different growth conditions may induce imperfect nucleation of graphene, and cause creation of defects near the nucleation point such as pin holes...... and amorphous carbon. These defects would serve as a pathway for the diffusion of 02 during thermal annealing, allowing oxidation of Cu to progress gradually from the nucleation center toward the growth edge. The oxidation process follows the graphene morphology closely; the shape of the oxidized area of Cu has...... a striking resemblance to that of the graphene flakes. Our work demonstrates that inferior graphene nucleation in CVD processes can compromise the oxidation resistance of a graphene-coated Cu substrate, and indirectly reveal the structure and integrity of graphene, which is of fundamental importance...

  7. Molecular Dynamics Simulation of Bubble Nucleation in Explosive Boiling

    Institute of Scientific and Technical Information of China (English)

    ZOU Yu; HUAI Xiu-Lan; LIANG Shi-Qiang

    2009-01-01

    Molecular dynamics (MD) simulation is carried out for the bubble nucleation of liquid nitrogen in explosive boiling. The heat is transferred into the simulation system by rescaling the velocity of the molecules. The results indicate that the initial equilibrium temperature of liquid and molecular cluster size affect the energy conversion in the process of bubble nucleation. The potential energy of the system violently varies at the beginning of the bubble nucleation, and then varies around a fixed value. At the end of bubble nucleation, the potential energy of the system slowly increases. In the bubble nucleation of explosive boiling, the lower the initial equilibrium temperature, the larger the size of the molecular cluster, and the more the heat transferred into the system of the simulation cell, causing the increase potential energy in a larger range.

  8. Nucleation of protein crystals in a wide continuous supersaturation gradient.

    Science.gov (United States)

    Penkova, A; Chayen, N; Saridakis, E; Nanev, Chr N

    2002-10-01

    By using a supersaturation gradient along a protein solution contained in a glass capillary tube, we modified the classical double pulse technique, thus substantially accelerating the procedure of measurement of nucleation parameters. Data for the number of crystal nuclei, n vs nucleation time, t, were obtained for hen-egg-white lysozyme, chosen as a model because of the availability of reliable solubility data in the literature. The stationary nucleation rate and the nucleation time lag have been measured. Quantitative data for the work required for nucleus formation (A(k) = 4.3 x 10 (-1)3 erg) and the size of the critical cluster (three molecules) were also obtained. Besides, it was observed that Ostwald ripening seems to play an important role for nucleation times longer than 150 min. Using the same technique, semi-quantitative investigations were performed with porcine pancreatic trypsin.

  9. Aerosol nucleation induced by a high energy particle beam

    DEFF Research Database (Denmark)

    Enghoff, Martin Andreas Bødker; Pedersen, Jens Olaf Pepke; Uggerhøj, Ulrik I.

    2011-01-01

    We have studied sulfuric acid aerosol nucleation in an atmospheric pressure reaction chamber using a 580 MeV electron beam to ionize the volume of the reaction chamber. We find a clear contribution from ion-induced nucleation and consider this to be the first unambiguous observation of the ion......-effect on aerosol nucleation using a particle beam under conditions that resemble the Earth's atmosphere. By comparison with ionization using a gamma source we further show that the nature of the ionizing particles is not important for the ion-induced component of the nucleation. This implies that inexpensive...... ionization sources - as opposed to expensive accelerator beams - can be used for investigations of ion-induced nucleation....

  10. Prediction of the solidification structure of casting and heterogeneous nucleation

    Institute of Scientific and Technical Information of China (English)

    K. Ohsasa; H. Shirosawa; T. Narita

    2003-01-01

    The frequency of heterogeneous nucleation during the solidification of Al-Si binary alloy was estimated by comparing ex-perimentally obtained macrostructures of castings with numerically simulated ones. A molten alloy was unidirectionally solidifiedfrom a water-cooled copper chill in an adiabatic mold. The location of colunmar to equiaxed transition (CET) in the solidified alloyingot was measured. A numerical simulation for grain structure formation based on the Monte Carlo method was carried out, and thefrequency of heterogeneous nucleation in the alloy was evaluated by producing similar structure with the experimental one. The fre-quency of heterogeneous nucleation was expressed as a probabilistic function with an exponential form of undercooling that deter-mines the probability of nucleation event in the simulation. The value of the exponent is regarded as the nucleation parameter. Thenucleation parameter of Al-Si binary alloy varied with initial Sicontent.

  11. TEM observation on nucleation of Ca a-Sialon

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Ca a-Sialon compacts pressurelessly-sintered to the intermediate temperature (1 450℃) were investigated with TEM for an overall composition Ca1.8Si6.6Al5.4O1.8N14.2. It was found that in most cases, the newly-formed a-Sialon grains had no epitaxial orientation relationship with the Si3N4 particles; only occasionally heteroepitaxial nucleation of a-Sialon on a-Si3N4 was detected. Further EDAX analysis revealed a much higher Ca concentration in the non-epi- taxially nucleated a-Sialon than in the heteroepitaxially nucleated a-Sialon. Thus a possible correlation between the concentration of metal cations in the a-Sialon structure and the nucleation mechanism has been proposed, i.e. a-Sialon compositions with higher Ca concentration show a stronger trend of non-epitaxial nucleation.

  12. Observations on the nucleation of ice VII in compressed water

    Science.gov (United States)

    Stafford, Samuel J. P.; Chapman, David J.; Bland, Simon N.; Eakins, Daniel E.

    2017-01-01

    Water can freeze upon multiple shock compression, but the window material determines the pressure of the phase transition. Several plate impact experiments were conducted with liquid targets on a single-stage gas gun, diagnosed simultaneously using photonic doppler velocimetry (PDV) and high speed imaging through the water. The experiments investigated why silica windows instigate freezing above 2.5 GPa whilst sapphire windows do not until 7 GPa. We find that the nucleation of ice occurs on the surfaces of windows and can be affected by the surface coating suggesting the surface energy of fused silica, likely due to hydroxyl groups, encourages nucleation of ice VII crystallites. Aluminium coatings prevent nucleation and sapphire surfaces do not nucleate until approximately 6.5 GPa. This is believed to be the threshold pressure for the homogeneous nucleation of water.

  13. Temperature dependence of heterogeneous nucleation: Extension of the Fletcher model

    Science.gov (United States)

    McGraw, Robert; Winkler, Paul; Wagner, Paul

    2015-04-01

    Recently there have been several cases reported where the critical saturation ratio for onset of heterogeneous nucleation increases with nucleation temperature (positive slope dependence). This behavior contrasts with the behavior observed in homogeneous nucleation, where a decreasing critical saturation ratio with increasing nucleation temperature (negative slope dependence) seems universal. For this reason the positive slope dependence is referred to as anomalous. Negative slope dependence is found in heterogeneous nucleation as well, but because so few temperature-dependent measurements have been reported, it is not presently clear which slope condition (positive or negative) will become more frequent. Especially interesting is the case of water vapor condensation on silver nanoparticles [Kupc et al., AS&T 47: i-iv, 2013] where the critical saturation ratio for heterogeneous nucleation onset passes through a maximum, at about 278K, with higher (lower) temperatures showing the usual (anomalous) temperature dependence. In the present study we develop an extension of Fletcher's classical, capillarity-based, model of heterogeneous nucleation that explicitly resolves the roles of surface energy and surface entropy in determining temperature dependence. Application of the second nucleation theorem, which relates temperature dependence of nucleation rate to cluster energy, yields both necessary and sufficient conditions for anomalous temperature behavior in the extended Fletcher model. In particular it is found that an increasing contact angle with temperature is a necessary, but not sufficient, condition for anomalous temperature dependence to occur. Methods for inferring microscopic contact angle and its temperature dependence from heterogeneous nucleation probability measurements are discussed in light of the new theory.

  14. Probing Individual Ice Nucleation Events with Environmental Scanning Electron Microscopy

    Science.gov (United States)

    Wang, Bingbing; China, Swarup; Knopf, Daniel; Gilles, Mary; Laskin, Alexander

    2016-04-01

    Heterogeneous ice nucleation is one of the processes of critical relevance to a range of topics in the fundamental and the applied science and technologies. Heterogeneous ice nucleation initiated by particles proceeds where microscopic properties of particle surfaces essentially control nucleation mechanisms. Ice nucleation in the atmosphere on particles governs the formation of ice and mixed phase clouds, which in turn influence the Earth's radiative budget and climate. Heterogeneous ice nucleation is still insufficiently understood and poses significant challenges in predictive understanding of climate change. We present a novel microscopy platform allowing observation of individual ice nucleation events at temperature range of 193-273 K and relative humidity relevant for ice formation in the atmospheric clouds. The approach utilizes a home built novel ice nucleation cell interfaced with Environmental Scanning Electron Microscope (IN-ESEM system). The IN-ESEM system is applied for direct observation of individual ice formation events, determining ice nucleation mechanisms, freezing temperatures, and relative humidity onsets. Reported microanalysis of the ice nucleating particles (INP) include elemental composition detected by the energy dispersed analysis of X-rays (EDX), and advanced speciation of the organic content in particles using scanning transmission x-ray microscopy with near edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS). The performance of the IN-ESEM system is validated through a set of experiments with kaolinite particles with known ice nucleation propensity. We demonstrate an application of the IN-ESEM system to identify and characterize individual INP within a complex mixture of ambient particles.

  15. Aging kinetics in the Cu-8 wt.% Al alloy with Ag additions

    Energy Technology Data Exchange (ETDEWEB)

    Adorno, A.T.; Guerreiro, M.R.; Silva, R.A.G

    2003-05-12

    The influence of additions of 2, 4, 6, 8, 10 and 12 wt.% Ag in the isothermal aging kinetics of the Cu-8 wt.% Al alloy was studied using microhardness measurements, differential scanning calorimetry, optical and scanning electron microscopy and X-ray diffractometry. The results indicate that the presence of silver is responsible for the shift of the equilibrium concentration to higher Al contents, allowing the formation of the {gamma}{sub 1} phase (Al{sub 4}Cu{sub 9}) in this alloy. For Ag additions up to 6% the dominant kinetic process is Ag precipitation and for additions from 8 to 12% Ag the nucleation of the perlitic phase dominates.

  16. 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.

  17. 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.

  18. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

    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 0nanoclusters 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.

  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. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. The nucleation kinetics of ammonium metavanadate precipitated by ammonium chloride

    Science.gov (United States)

    Du, Guangchao; Sun, Zhaohui; Xian, Yong; Jing, Han; Chen, Haijun; Yin, Danfeng

    2016-05-01

    The nucleation kinetics of ammonium metavanadate (NH4VO3) was investigated under conditions of the simulated process for precipitation of NH4VO3 from the vanadium-containing solution. Induction periods for the nucleation of NH4VO3 were experimentally determined as a function of supersaturation at temperatures from 30 to 45 °C. Using the classical nucleation theory, the interfacial tension between NH4VO3 and supersaturated solution, the nucleation rate and critical radius of nucleus for the homogeneous nucleation of NH4VO3 were estimated. With temperature increasing, the calculated interfacial tension gradually decreased from 29.78 mJ/m2 at 30 °C to 23.66 mJ/m2 at 45 °C. The nucleation rate was found to proportionally increase but the critical radius of nucleus exponentially decreased, with increase in supersaturation ratio at a constant temperature. The activation energy for NH4VO3 nucleation was obtained from the relationship between temperature and induction period, ranging from 79.17 kJ/mol at S=25 to 115.50 kJ/mol at S=15. FT-IR and Raman spectrum indicated that the crystals obtained in the precipitation process were NH4VO3.

  8. Structure of supersaturated solution and crystal nucleation induced by diffusion

    Science.gov (United States)

    Ooshima, Hiroshi; Igarashi, Koichi; Iwasa, Hideo; Yamamoto, Ren

    2013-06-01

    The effect of a seed crystal on nucleation of L-alanine from a quiescent supersaturated solution was investigated. When a seed crystal was not used, nucleation did not occur at least for 5 h. When a seed crystal was introduced into the supersaturated solution with careful attention to avoid convection of the solution, fine crystals appeared at the place far from the seed crystal. At that time, there was no convection at the place that fine crystals appeared. Namely, there was no possibility that those fine crystals came from the surface of seed crystal. We supposed that nucleation was induced by directional diffusion of solute molecules caused by growth of the seed crystal. In order to prove this hypothesis, we designed an experiment using an apparatus composed of two compartments divided by a dialysis membrane that L-alanine molecules could freely permeate. Two supersaturated solutions having a supersaturation ratio of 1.2 and a smaller ratio were placed in the two compartments in the absence of seed crystals. This apparatus allowed the directional diffusion of solute molecules between two solutions. Nucleation occurred within 30 min. The frequency of nucleation among 7-times repeated experiments was in proportion to the difference of supersaturation ratio between the two solutions. This result poses a new mechanism of the secondary nucleation that the directional diffusion caused by growth of existing crystals induces nucleation.

  9. Bubble nucleation in polymer–CO2 mixtures.

    Science.gov (United States)

    Xu, Xiaofei; Cristancho, Diego E; Costeux, Stéphane; Wang, Zhen-Gang

    2013-10-28

    We combine density-functional theory with the string method to calculate the minimum free energy path of bubble nucleation in two polymer–CO2 mixture systems, poly(methyl methacrylate) (PMMA)–CO2 and polystyrene (PS)–CO2. Nucleation is initiated by saturating the polymer liquid with high pressure CO2 and subsequently reducing the pressure to ambient condition. Below a critical temperature (Tc), we find that there is a discontinuous drop in the nucleation barrier as a function of increased initial CO2 pressure (P0), as a result of an underlying metastable transition from a CO2-rich-vapor phase to a CO2-rich-liquid phase. The nucleation barrier is generally higher for PS–CO2 than for PMMA–CO2 under the same temperature and pressure conditions, and both higher temperature and higher initial pressure are required to lower the nucleation barrier for PS–CO2 to experimentally relevant ranges. Classical nucleation theory completely fails to capture the structural features of the bubble nucleus and severely underestimates the nucleation barrier.

  10. Heterogeneous nucleation of protein crystals on fluorinated layered silicate.

    Directory of Open Access Journals (Sweden)

    Keita Ino

    Full Text Available Here, we describe an improved system for protein crystallization based on heterogeneous nucleation using fluorinated layered silicate. In addition, we also investigated the mechanism of nucleation on the silicate surface. Crystallization of lysozyme using silicates with different chemical compositions indicated that fluorosilicates promoted nucleation whereas the silicates without fluorine did not. The use of synthesized saponites for lysozyme crystallization confirmed that the substitution of hydroxyl groups contained in the lamellae structure for fluorine atoms is responsible for the nucleation-inducing property of the nucleant. Crystallization of twelve proteins with a wide range of pI values revealed that the nucleation promoting effect of the saponites tended to increase with increased substitution rate. Furthermore, the saponite with the highest fluorine content promoted nucleation in all the test proteins regardless of their overall net charge. Adsorption experiments of proteins on the saponites confirmed that the density of adsorbed molecules increased according to the substitution rate, thereby explaining the heterogeneous nucleation on the silicate surface.

  11. Do protein crystals nucleate within dense liquid clusters?

    Science.gov (United States)

    Maes, Dominique; Vorontsova, Maria A; Potenza, Marco A C; Sanvito, Tiziano; Sleutel, Mike; Giglio, Marzio; Vekilov, Peter G

    2015-07-01

    Protein-dense liquid clusters are regions of high protein concentration that have been observed in solutions of several proteins. The typical cluster size varies from several tens to several hundreds of nanometres and their volume fraction remains below 10(-3) of the solution. According to the two-step mechanism of nucleation, the protein-rich clusters serve as locations for and precursors to the nucleation of protein crystals. While the two-step mechanism explained several unusual features of protein crystal nucleation kinetics, a direct observation of its validity for protein crystals has been lacking. Here, two independent observations of crystal nucleation with the proteins lysozyme and glucose isomerase are discussed. Firstly, the evolutions of the protein-rich clusters and nucleating crystals were characterized simultaneously by dynamic light scattering (DLS) and confocal depolarized dynamic light scattering (cDDLS), respectively. It is demonstrated that protein crystals appear following a significant delay after cluster formation. The cDDLS correlation functions follow a Gaussian decay, indicative of nondiffusive motion. A possible explanation is that the crystals are contained inside large clusters and are driven by the elasticity of the cluster surface. Secondly, depolarized oblique illumination dark-field microscopy reveals the evolution from liquid clusters without crystals to newly nucleated crystals contained in the clusters to grown crystals freely diffusing in the solution. Collectively, the observations indicate that the protein-rich clusters in lysozyme and glucose isomerase solutions are locations for crystal nucleation.

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. 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...

  17. 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.

  18. Synthesis and sensing integration: A novel enzymatic reaction modulated Nanoclusters Beacon (NCB) "Illumination" strategy for label-free biosensing and logic gate operation.

    Science.gov (United States)

    Hong, Lu; Zhou, Fu; Wang, Guangfeng; Zhang, Xiaojun

    2016-12-15

    A novel fluorescent label-free "turn-on" NAD(+) and adenosine triphosphate (ATP) biosensing strategy is proposed by fully exploiting ligation triggered Nanocluster Beacon (NCB). In the presence of the target, the split NCB was brought to intact, which brought the C-rich sequence and enhancer sequence in close proximity resulting in the lightening of dark DNA/AgNCs ("On" mode). Further application was presented for logic gate operation and aptasensor construction. The feasibility was investigated by Ultraviolet-visible spectroscopy (UV-vis), Fluorescence, lifetime and High Resolution Transmission Electron Microscopy (HRTEM) etc. The strategy displayed good performance in the detection of NAD(+) and ATP, with the detection limit of 0.002nM and 0.001mM, the linear range of 10-1000nM and 0.003-0.01mM, respectively. Due to the DNA/AgNCs as fluorescence reporter, the completely label-free fluorescent strategy boasts the features of simplicity and low cost, and showing little reliance on the sensing environment. Meanwhile, the regulation by overhang G-rich sequence not relying on Förster energy transfer quenching manifests the high signal-to-background ratios (S/B ratios). This method not only provided a simple, economical and reliable fluorescent NAD(+) assay but also explored a flexible G-rich sequence regulated NCB probe for the fluorescent biosensors. Furthermore, this sensing mode was expanded to the application of a logic gate design, which exhibited a high performance for not only versatile biosensors construction but also for molecular computing application.

  19. Twin nucleation and migration in FeCr single crystals

    Energy Technology Data Exchange (ETDEWEB)

    Patriarca, L. [Politecnico di Milano, Department of Mechanical Engineering, Via La Masa 34, I-20156 Milano (Italy); Abuzaid, Wael [Department of Mechanical Science and Engineering, University of Illinois at Urbana-Champaign, 1206 W. Green St., Urbana, IL 61801 (United States); Sehitoglu, Huseyin, E-mail: huseyin@illinois.edu [Department of Mechanical Science and Engineering, University of Illinois at Urbana-Champaign, 1206 W. Green St., Urbana, IL 61801 (United States); Maier, Hans J. [Lehrstuhl fuer Werkstoffkunde (Materials Science), University of Paderborn, 33095 Paderborn (Germany); Chumlyakov, Y. [Physics of Plasticity and Strength of Materials Laboratory, Siberian Physical and Technical Institute, 634050 Tomsk (Russian Federation)

    2013-01-15

    Tension and compression experiments were conducted on body-centered cubic Fe -47.8 at pct. Cr single crystals. The critical resolved shear stress (CRSS) magnitudes for slip nucleation, twin nucleation and twin migration were established. We show that the nucleation of slip occurs at a CRSS of about 88 MPa, while twinning nucleates at a CRSS of about 191 MPa with an associated load drop. Following twin nucleation, twin migration proceeds at a CRSS that is lower than the initiation stress ( Almost-Equal-To 114-153 MPa). The experimental results of the nucleation stresses indicate that the Schmid law holds to a first approximation for the slip and twin nucleation cases, but to a lesser extent for twin migration particularly when considerable slip strains preceded twinning. The CRSSs were determined experimentally using digital image correlation (DIC) in conjunction with electron back scattering diffraction (EBSD). The DIC measurements enabled pinpointing the precise stress on the stress-strain curves where twins or slip were activated. The crystal orientations were obtained using EBSD and used to determine the activated twin and slip systems through trace analysis. - Highlights: Black-Right-Pointing-Pointer Digital image correlation allows to capture slip/twin initiation for bcc FeCr. Black-Right-Pointing-Pointer Crystal orientations from EBSD allow slip/twin system indexing. Black-Right-Pointing-Pointer Nucleation of slip always precedes twinning. Black-Right-Pointing-Pointer Twin growth is sustained with a lower stress than required for nucleation. Black-Right-Pointing-Pointer Twin-slip interactions provide high hardening at the onset of plasticity.

  20. Growth and characterization of ZnO multipods on functional surfaces with different sizes and shapes of Ag particles

    Institute of Scientific and Technical Information of China (English)

    A Kamalianfar; S A Halim; Mahmoud Godarz Naseri; M Navasery; Fasih Ud Din; J A M Zahedi; Kasra Behzad

    2013-01-01

    Three-dimensional ZnO multipods are successfully synthesized on functional substrates using the vapor transport method in a quartz tube.The functional surfaces,which include two different distributions of Ag nanoparticles and a layer of commercial Ag nanowires,are coated onto silicon substrates before the growth of ZnO nanostructures.The structures and morphologies of the ZnO/Ag heterostructures are investigated using X-ray diffraction and field emission scanning electron microscopy.The sizes and shapes of the Ag particles affect the growth rates and initial nucleations of the ZnO structures,resulting in different numbers and shapes of multipods.They also influence the orientation and growth quality of the rods.The optical properties are studied by photoluminescence,UV-vis,and Raman spectroscopy.The results indicate that the surface plasmon resonance strongly depends on the sizes and shapes of the Ag particles.

  1. CTAB-mediated synthesis and characterization of ZnO/Ag core–shell nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Majid; Wei, Chengsha; Chen, Mingming; Tao, Jiaojiao; Huang, Ningdong; Qi, Zeming, E-mail: zmqi@ustc.edu.cn; Li, Liangbin

    2014-11-05

    Graphical abstract: Simplified schematic process for ZnO NRs/Ag nanocomposites. - Highlights: • A new simple and facile approach to synthesize ZnO NRs/Ag core–shell nanocomposite. • The annealing improves the crystallinity and bond strength between Ag and ZnO. • CTAB and AgNO3 greatly affect the formation of ZnO NRs/Ag core–shell. • Strong interfacial interaction between Ag nanoparticles and ZnO nanorods. - Abstract: In this paper, ZnO/Ag core–shell hybrid nanocomposites have been prepared by a very simple chemical methodology. ZnO nanorods were employed as core material for Ag seeds, and subsequent nucleation and growth of Ag nanoparticle by a cationic surfactant cetyltrimethylammonium bromide (CTAB) formed the ZnO NRs/Ag core–shell nanocomposites. In addition, their morphology, microstructure and optical properties have been characterized by X-ray diffraction, Raman Spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, UV–Vis absorption and photoluminescence spectroscopy. It was found that face-center-cubic Ag nanoparticles with an average diameter of 20 nm were coated onto the surface of hexagonal phase ZnO nanorods with a minimum of 0.09 mmol concentration of CTAB. The excitonic absorption band and surface plasmon absorption band of the ZnO NRs/Ag nanocomposites revealed red-shifts relative to pure ZnO nanorods and metallic Ag nanoparticles. The coating of Ag nanoparticles onto the ZnO nanorods show red-shift in the near band edge (NBE) luminescence spectra and a reasonable detraction in the deep level emission (DLE) spectra compared with the pure ZnO nanorods. These interpretations demonstrated the strong interfacial interaction between Ag nanoparticles and ZnO nanorods. Furthermore, the annealing of ZnO NRs/Ag nanocomposite at 200 °C was done and improvement occurs in the crystallinity and binding strength of Ag nanoparticles.

  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. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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 

  9. 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.

  10. 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.

  11. 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.

  12. Nucleation of insulin crystals in a wide continuous supersaturation gradient.

    Science.gov (United States)

    Penkova, Anita; Dimitrov, Ivaylo; Nanev, Christo

    2004-11-01

    Modifying the classical double pulse technique, by using a supersaturation gradient along an insulin solution contained in a glass capillary tube, we found conditions appropriate for the direct measurement of nucleation parameters. The nucleation time lag has been measured. Data for the number of crystal nuclei versus the nucleation time were obtained for this hormone. Insulin was chosen as a model protein because of the availability of solubility data in the literature. A comparison with the results for hen-egg-white lysozyme, HEWL was performed.

  13. Estimation of the nucleation rate by differential scanning calorimetry

    Science.gov (United States)

    Kelton, Kenneth F.

    1992-01-01

    A realistic computer model is presented for calculating the time-dependent volume fraction transformed during the devitrification of glasses, assuming the classical theory of nucleation and continuous growth. Time- and cluster-dependent nucleation rates are calculated by modeling directly the evolving cluster distribution. Statistical overlap in the volume fraction transformed is taken into account using the standard Johnson-Mehl-Avrami formalism. Devitrification behavior under isothermal and nonisothermal conditions is described. The model is used to demonstrate that the recent suggestion by Ray and Day (1990) that nonisothermal DSC studies can be used to determine the temperature for the peak nucleation rate, is qualitatively correct for lithium disilicate, the glass investigated.

  14. Direct imaging of quantum wires nucleated at diatomic steps

    OpenAIRE

    Molina, Sergio I.; Varela, María; Sales, David L; Ben, Teresa; Pizarro, J.; Galindo, P. L.; Fuster, David; González Díez, Yolanda; González Sotos, Luisa; Pennycook, Stephen J.

    2007-01-01

    Atomic steps at growth surfaces are important heterogeneous sources for nucleation of epitaxial nano-objects. In the presence of misfit strain, we show that the nucleation process takes place referentially at the upper terrace of the step as a result of the local stress relaxation. Evidence for strain-induced nucleation comes from the direct observation by postgrowth, atomic resolution, Z-contrast imaging of an InAs-rich region in a nanowire located on the upper terrace surface of an interfac...

  15. Nucleation and growth of geological faults

    Directory of Open Access Journals (Sweden)

    D. Stoyan

    2011-08-01

    Full Text Available We present a new model of fault nucleation and growth based on the Weibull theory, already widely used in fracture research engineering. We propose that, according to a birth-and-growth process, germs (nuclei are born at random instants at random spatial locations and then grow with time. This leads to a satisfactory formulation of fault length distribution, different from classical statistical laws. Especially, this formulation reconciles previous analyses of fault datasets displaying power-law and/or exponential behaviors. The Weibull parameters can be statistically estimated in a simple way. We show that the model can be successfully fitted to natural data in Kenya and Ethiopia. In contrast to existing descriptive models developed for geological fault systems, such as fractal approaches, the Weibull theory allows to characterize the strength of the material, i.e. its resistance to deformation. Since this model is very general, we expect that it can be applied in many situations, and for simulations of geological fracture processes. The model is independent of deformation intensity and type and therefore allows a better constraint of the seismic risk in threatened regions.

  16. Nucleation and undercooling of metal melt

    Institute of Scientific and Technical Information of China (English)

    坚增运; 常芳娥; 马卫红; 严文; 杨根仓; 周尧和

    2000-01-01

    The effects of thermodynamic and dynamic factors on nucleation process have been integrated in a theoretical formula representing the dependence of undercooling on parameters concerned. Moreover, a method to determine the kind and amount of the most effective catalyst in an undercooled melt has been acquired. The results show that the undercooling increases with the decreasing surface area of the most effective catalyst and the increasing cooling rate as the kind of the most effective catalyst is constant. It increases to a maximum value when the ratio of the surface area of catalyst ( Sv V) to the cooling rate of melt ( Rc) decreases to a critical value. The maximum undecooling not only depends on the ratio of non-dimensional factor of activation energy for an atom to diffuse (φ) to non-dimensional factor of driving force for nucleus to form (ψ), but also depends on the contact angle of the most effective catalyst; the smaller the ratio of φ to ψ, the higher the maximum undercooling, but it does not

  17. Nucleation and undercooling of metal melt

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The effects of thermodynamic and dynamic factors on nucleation process have been integrated in a theoretical formula representing the dependence of undercooling on parameters concerned. Moreover, a method to determine the kind and amount of the most effective catalyst in an undercooled melt has been acquired. The results show that the undercooling increases with the decreasing surface area of the most effective catalyst and the increasing cooling rate as the kind of the most effective catalyst is constant. It increases to a maximum value when the ratio of the surface area of catalyst (SvV) to the cooling rate of melt (Rc) decreases to a critical value. The maximum undecooling not only depends on the ratio of non-dimensional factor of activation energy for an atom to diffuse (φ) to non-dimensional factor of driving force for nucleus to form (ψ), but also depends on the contact angle of the most effective catalyst; the smaller the ratio of φ to ψ, the higher the maximum undercooling, but it does not exceed the value of 2/3 melting point; the smaller the contact angle of the most effective catalyst, the lower the maximum undercooling, and the smaller the requisite value of SvV/Rc for the maximum undercooling also.

  18. 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.

  19. Direct laser planting of hybrid Au-Ag/C nanostructures - nanoparticles, flakes and flowers

    CERN Document Server

    Manshina, Alina; Bashouti, Muhammad; Povolotskiy, Alexey; Petrov, Yuriy; Koshevoy, Igor; Christiansen, Silke; Tunik, Sergey; Leuchs, Gerd

    2015-01-01

    We demonstrate a new approach for forming hybrid metal/carbonaceous nanostructures in a controlled direct laser planting process. Au-Ag nanoclusters in amorphous or crystalline carbonaceous matrices are formed with different morphology: nanoparticles, nanoflakes, and nanoflowers. In contrast to other generation techniques our approach is simple, involving only a single laser-induced process transforming supramolecular complexes dissolved in solvent such as acetone, acetophenone, or dichloroethane into hybrid nanostructures in the laser-affected area of the substrate. The morphology of the hybrid nanostructures can be steered by controlling the deposition parameters, the composition of the liquid phase and the type of substrate, amorphous or crystalline. The carbonaceous phase of the hybrid nanostructures consists of hydrogenated amorphous carbon in the case of nanoparticles and of crystalline orthorhombic graphite of nanoscale thickness in the case of flakes and flowers. To the best of our knowledge this is t...

  20. 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.

  1. Laboratory Studies of Ice Nucleation on Volcanic Ash

    Science.gov (United States)

    Tolbert, M. A.; Schill, G. P.; Genareau, K. D.

    2014-12-01

    Ice nucleation on volcanic ash controls both ash aggregation and cloud glaciation, which affect human respiratory health, atmospheric transport, and global climate. We have performed laboratory studies of the depositional and immersion freezing efficiency of three distinct samples of volcanic ash using Raman Microscopy coupled to an environmental cell. Ash from the Fuego (Basaltic Ash, Guatemala), Soufriere Hills (Andesetic Ash, Montserrat), and Taupo (Rhyolitic Ash, New Zealand) volcanoes were chosen to represent different geographical locations and silica content. All ash samples were quantitatively analyzed for both percent crystallinity and mineralogy using X-ray diffraction. We find that all three samples of volcanic ash are excellent depositional ice nuclei, nucleating ice at ice saturation ratios of 1.05 ± 0.1. For immersion freezing, however, only the Taupo ash exhibited efficient heterogeneous ice nucleation activity. Similar to recent studies on mineral dust, we suggest that the mineralogy of volcanic ash may dictate its ice nucleation activity in the immersion mode.

  2. Aerosol nucleation in an ultra-low ion density environment

    DEFF Research Database (Denmark)

    Pedersen, Jens Olaf Pepke; Enghoff, Martin Andreas Bødker; Paling, Sean M.;

    2012-01-01

    Ion-induced nucleation has been studied in a deep underground ultra-low background radiation environment where the role of ions can be distinguished from alternative neutral aerosol nucleation mechanisms. Our results demonstrate that ions have a significant effect on the production of small...... sulfuric acid–water clusters over a range of sulfuric acid concentrations although neutral nucleation mechanisms remain evident at low ionization levels. The effect of ions is found both to enhance the nucleation rate of stable clusters and the initial growth rate. The effects of possible contaminations...... are also discussed and are believed to be small, but cannot be excluded. If our results can be extrapolated to conditions that resemble the clean air atmosphere over the Earth's oceans they suggest that ions may dominate the production of small (4nm) aerosols here....

  3. Preface: Special Topic on Nucleation: New Concepts and Discoveries

    Science.gov (United States)

    Kelton, K. F.; Frenkel, Daan

    2016-12-01

    Many phenomena in the world around us depend on infrequent, yet short-lived, events that completely alter how a system subsequently develops in time. In the physical sciences, there are many examples of such crucial "rare events." Among the most important of these are nucleation processes, in which, due to a rare fluctuation, a new phase forms spontaneously within a meta-stable parent phase. Because nucleation processes are both rare and rapid and happen on a microscopic spatial scale, their experimental study is challenging. In recent years, there have been major developments both in the experimental study of nucleation phenomena and in the numerical simulation of such processes. As the articles in this special issue demonstrate, these recent advances in the ability to probe nucleation phenomena have transformed our understanding of the field.

  4. Nucleating quark droplets in the core of magnetars

    CERN Document Server

    Kroff, Daniel

    2014-01-01

    To assess the possibility of homogeneous nucleation of quark matter in magnetars, we investigate the formation of chirally symmetric droplets in a cold and dense environment in the presence of an external magnetic field. As a framework, we use the one-loop effective potential of the two-flavor quark-meson model. Within the thin-wall approximation, we extract all relevant nucleation parameters and provide an estimate for the typical time scales for the chiral phase conversion in magnetized compact star matter. We show how the critical chemical potential, critical radius, correlation length and surface tension are affected, and how their combination to define the nucleation time seems to allow for nucleation of quark droplets in magnetar matter even for not so small values of the surface tension.

  5. Nucleating quark droplets in the core of magnetars

    Science.gov (United States)

    Kroff, D.; Fraga, E. S.

    2015-01-01

    To assess the possibility of homogeneous nucleation of quark matter in magnetars, we investigate the formation of chirally symmetric droplets in a cold and dense environment in the presence of an external magnetic field. As a framework, we use the one-loop effective potential of the two-flavor quark-meson model. Within the thin-wall approximation, we extract all relevant nucleation parameters and provide an estimate for the typical time scales for the chiral phase conversion in magnetized compact star matter. We show how the critical chemical potential, critical radius, correlation length and surface tension are affected, and how their combination to define the nucleation time seems to allow for nucleation of quark droplets in magnetar matter even for not so small values of the surface tension.

  6. Kinetic Monte Carlo simulation of the classical nucleation process

    Science.gov (United States)

    Filipponi, A.; Giammatteo, P.

    2016-12-01

    We implemented a kinetic Monte Carlo computer simulation of the nucleation process in the framework of the coarse grained scenario of the Classical Nucleation Theory (CNT). The computational approach is efficient for a wide range of temperatures and sample sizes and provides a reliable simulation of the stochastic process. The results for the nucleation rate are in agreement with the CNT predictions based on the stationary solution of the set of differential equations for the continuous variables representing the average population distribution of nuclei size. Time dependent nucleation behavior can also be simulated with results in agreement with previous approaches. The method, here established for the case in which the excess free-energy of a crystalline nucleus is a smooth-function of the size, can be particularly useful when more complex descriptions are required.

  7. Dislocation Nucleation and Pileup under a Wedge Contact at Nanoscale

    Directory of Open Access Journals (Sweden)

    Y. F. Gao

    2008-01-01

    Full Text Available Indentation responses of crystalline materials have been found to be radically different at micrometer and nanometer scales. The latter is usually thought to be controlled by the nucleation of dislocations. To explore this physical process, a dislocation mechanics study is performed to determine the conditions for the nucleation of a finite number of dislocations under a two-dimensional wedge indenter, using the Rice-Thomson nucleation criterion. The configurational force on the dislocation consists of the applied force, the image force, and the interaction force between dislocations. Dislocations reach equilibrium positions when the total driving force equals the effective Peierls stress, giving a set of nonlinear equations that can be solved using the Newton-Raphson method. When the apex angle of the wedge indenter increases, the critical contact size for dislocation nucleation increases rapidly, indicating that dislocation multiplication near a blunt wedge tip is extremely difficult. This geometric dependence agrees well with experimental findings.

  8. Ice Nucleation Near the Surfactant-Water Interface

    Science.gov (United States)

    Carlin, Caleb; Cantrell, Will; Taylor, Caroline

    2008-03-01

    Ice nucleation is a fundamental component of the atmospheric mechanisms driving the formation of clouds. Atmospheric nucleation occurs with a variety of compounds and conditions, but understanding the behavior of water is key in all cases. We have used multiscale molecular simulations to study heterogeneous nucleation in clouds, probing the influence of long-chain alcohols on the freezing of water droplets. Ice nucleation occurs at a finite distance from the heterogeneous surface, due to the disruption of the hydrogen bond network in response to the surfactant-water interface. The penetration depth of the disturbance is found to be dependent upon the chain length and surface organization, as well as the acidity of the terminal alcohol group.

  9. Improvement on Diamond Nucleation Treated by Pulsed Arc Discharge Plasma

    Institute of Scientific and Technical Information of China (English)

    马志斌; 万军; 汪建华; 张文文

    2004-01-01

    A technique of improvement on diamond nucleation based on pulsed arc discharge plasma at atmospheric pressure was developed. The pulsed arc discharge was induced respectively by nitrogen, argon and methanol gas. After the arc plasma pretreatment, a nucleation density higher than 1010 cm-2 may be obtained subsequently in chemical vapor deposition (CVD) on a mirror-polished silicon substrate without any other mechanical treatment. The effects of the arc discharge plasma on the diamond nucleation were investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (IR) and Raman spectroscopy. The enhancement of nucleation is postulated to be a result of the formation of carbonlike phase materials or nitrogenation on the substrate surface without surface defect produced by arc discharge.

  10. The role of ammonia in sulfuric acid ion induced nucleation

    Directory of Open Access Journals (Sweden)

    I. K. Ortega

    2008-06-01

    Full Text Available We have developed a new multi-step strategy for quantum chemical calculations on atmospherically relevant cluster structures that makes calculation for large clusters affordable with a good accuracy-to-computational effort ratio. We have applied this strategy to evaluate the relevance of ternary ion induced nucleation; we have also performed calculations for neutral ternary nucleation for comparison. The results for neutral ternary nucleation agree with previous results, and confirm the important role of ammonia in enhancing the growth of sulfuric acid clusters. On the other hand, we have found that ammonia does not enhance the growth of ionic sulfuric acid clusters. The results also confirm that ion-induced nucleation is a barrierless process at high altitudes, but at ground level there exists a barrier due to the presence of a local minimum on the free energy surface.

  11. Atomic scale simulation of carbon nanotube nucleation from hydrocarbon precursors.

    Science.gov (United States)

    Khalilov, Umedjon; Bogaerts, Annemie; Neyts, Erik C

    2015-12-22

    Atomic scale simulations of the nucleation and growth of carbon nanotubes is essential for understanding their growth mechanism. In spite of over twenty years of simulation efforts in this area, limited progress has so far been made on addressing the role of the hydrocarbon growth precursor. Here we report on atomic scale simulations of cap nucleation of single-walled carbon nanotubes from hydrocarbon precursors. The presented mechanism emphasizes the important role of hydrogen in the nucleation process, and is discussed in relation to previously presented mechanisms. In particular, the role of hydrogen in the appearance of unstable carbon structures during in situ experimental observations as well as the initial stage of multi-walled carbon nanotube growth is discussed. The results are in good agreement with available experimental and quantum-mechanical results, and provide a basic understanding of the incubation and nucleation stages of hydrocarbon-based CNT growth at the atomic level.

  12. Availability analysis for heterogeneous nucleation in a uniform electric field

    CERN Document Server

    Saidi, M H

    2003-01-01

    Industrial demands for more compact heat exchangers are a motivation to find new technology features. Electrohydrodynamics (EHD) is introduced as a promising phenomenon for heat transfer enhancement mechanisms. Similar to any new technology, EHD has not been understood completely yet and require more fundamental studies. In boiling phase change phenomena, nucleation is the dominant mechanism in heat transfer. Because of higher performance in heat transfer, nucleate boiling is considered as the main regime in thermal components. Hence, bubble dynamic investigation is a means to evaluate heat transfer. This study investigate bubble formation, including homogeneous and heterogeneous nucleation, from a thermodynamic point of view. Change in availability due to bubble embryo nucleation is discussed. Stability criteria for these systems are theoretically studied and results are discussed considering experimental data. In addition, a conceptual discussion on entropy generation in a thermodynamic system under electri...

  13. Mediating conducting polymer growth within hydrogels by controlling nucleation

    Directory of Open Access Journals (Sweden)

    A. J. Patton

    2015-01-01

    Full Text Available This study examines the efficacy of primary and secondary nucleation for electrochemical polymerisation of conductive polymers within poly(vinyl alcohol methacrylate hydrogels. The two methods of nucleation investigated were a primary heterogeneous mechanism via introduction of conductive bulk metallic glass (Mg64Zn30Ca5Na1 particles and a secondary mechanism via introduction of “pre-polymerised” conducting polymer within the hydrogel (PEDOT:PSS. Evidence of nucleation was not seen in the bulk metallic glass loaded gels, however, the PEDOT:PSS loaded gels produced charge storage capacities over 15 mC/cm2 when sufficient polymer was loaded. These studies support the hypothesis that secondary nucleation is an efficient approach to producing stand-alone conducting hydrogels.

  14. Analysis of nucleation modelling in ductile cast iron

    DEFF Research Database (Denmark)

    Moumeni, Elham; Tutum, Cem Celal; Tiedje, Niels Skat;

    2012-01-01

    Heterogeneous nucleation of nodular graphite at inclusions in ductile iron during eutectic solidification has been investigated. The experimental part of this work deals with casting of ductile iron samples with two different inoculants in four different thicknesses. Chemical analysis...

  15. Characterization of Ice nucleation Bacteria and their Applications

    OpenAIRE

    ZONOURİ, Sheida Sadat; FATEHİNİA, Milad; NURİTABAR, Safoura; MANUCHEHRİ, Sara

    2015-01-01

    Abstract. Supercooled water can remain in liquid state at the temperatures below zero and needs catalysts for changing from liquid to solid state, and accumulation of water molecules causes nucleation and creates ice embryo. Then, other molecules are attached to this core and will make ice crystals “visible”. These catalysts may be inorganic materials, bacteria and/or fungal spores. In this review article, bacteria such as P. Syringae have been studied in ice nucleation process and their indu...

  16. Identification of Different Cobalt Nucleation on Glassy Carbon

    Institute of Scientific and Technical Information of China (English)

    Min GU; Fang Zu YANG; Ling HUANG; Shi Bing YAO; Shao Min ZHOU

    2004-01-01

    The nucleation mechanisms of cobalt from sulfate solutions were studied by utilizing the electrochemical technique, chronoamperometry.It was found that the recorded current-time transients introduced from 1.0 mol/L CoSO4 solution were complexes with unusual shapes.All characteristic features were identified as separate process.The instantaneous or progressive nucleation with 2D or 3D growth exists during the cobalt deposition, depending on the applied potentials.

  17. Effect of nucleating agents on crystallization kinetics of PET

    Directory of Open Access Journals (Sweden)

    2007-04-01

    Full Text Available Effects of three nucleating agents concluding talc, sodium benzoate (SB and an ionomer (Ion., Na+ on crystallization of poly(ethylene terephthalate (PET were studied by differential scanning calorimetry (DSC and polarized optical microscope (POM, the parameters of crystallization kinetics were obtained through Avrami and Ozawa equations. The fold surface free energy σe of pure PET and PET/nucleating agent blends were calculated by Hoffman-Lauritzen theory. The results indicate that the three kinds of nucleating agents increase the crystallization rate constant through promoting their nucleating effect for PET crystallization, among which SB is the best one with the same content. The crystallization mode of PET might shift from three-dimensional growth to two-dimensional growth by the addition of the nucleating agents. The values of σe of PET/nucleating agent blends are much less than that of pure PET, and PET/SB (99:1 blend has the least value of σe (18.2 mJ/m2. The conclusion based on Hoffman theory is similar to the analysis by Avrami and Ozawa equations.

  18. Overview: Understanding nucleation phenomena from simulations of lattice gas models

    Science.gov (United States)

    Binder, Kurt; Virnau, Peter

    2016-12-01

    Monte Carlo simulations of homogeneous and heterogeneous nucleation in Ising/lattice gas models are reviewed with an emphasis on the general insight gained on the mechanisms by which metastable states decay. Attention is paid to the proper distinction of particles that belong to a cluster (droplet), that may trigger a nucleation event, from particles in its environment, a problem crucial near the critical point. Well below the critical point, the lattice structure causes an anisotropy of the interface tension, and hence nonspherical droplet shapes result, making the treatment nontrivial even within the conventional classical theory of homogeneous nucleation. For temperatures below the roughening transition temperature facetted crystals rather than spherical droplets result. The possibility to find nucleation barriers from a thermodynamic analysis avoiding a cluster identification on the particle level is discussed, as well as the question of curvature corrections to the interfacial tension. For the interpretation of heterogeneous nucleation at planar walls, knowledge of contact angles and line tensions is desirable, and methods to extract these quantities from simulations will be mentioned. Finally, also the problem of nucleation near the stability limit of metastable states and the significance of the spinodal curve will be discussed, in the light of simulations of Ising models with medium range interactions.

  19. Rate of Homogeneous Crystal Nucleation in molten NaCl

    CERN Document Server

    Valeriani, C; Frenkel, D; 10.1063/1.1896348

    2009-01-01

    We report a numerical simulation of the rate of crystal nucleation of sodium chloride from its melt at moderate supercooling. In this regime nucleation is too slow to be studied with "brute-force" Molecular Dynamics simulations. The melting temperature of ("Tosi-Fumi") NaCl is $\\sim 1060$K. We studied crystal nucleation at $T$=800K and 825K. We observe that the critical nucleus formed during the nucleation process has the crystal structure of bulk NaCl. Interestingly, the critical nucleus is clearly faceted: the nuclei have a cubical shape. We have computed the crystal-nucleation rate using two completely different approaches, one based on an estimate of the rate of diffusive crossing of the nucleation barrier, the other based on the Forward Flux Sampling and Transition Interface Sampling (FFS-TIS) methods. We find that the two methods yield the same result to within an order of magnitude. However, when we compare the extrapolated simulation data with the only available experimental results for NaCl nucleatio...

  20. A marine biogenic source of atmospheric ice-nucleating particles

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, T. W.; Ladino, L. A.; Alpert, Peter A.; Breckels, M. N.; Brooks, I. M.; Browse, J.; Burrows, Susannah M.; Carslaw, K. S.; Huffman, J. A.; Judd, C.; Kilthau, W. P.; Mason, R. H.; McFiggans, Gordon; Miller, L. A.; Najera, J.; Polishchuk, E. A.; Rae, S.; Schiller, C. L.; Si, M.; Vergara Temprado, J.; Whale, Thomas; Wong, J P S; Wurl, O.; Yakobi-Hancock, J. D.; Abbatt, JPD; Aller, Josephine Y.; Bertram, Allan K.; Knopf, Daniel A.; Murray, Benjamin J.

    2015-09-09

    The formation of ice in clouds is facilitated by the presence of airborne ice nucleating particles1,2. Sea spray is one of the major global sources of atmospheric particles, but it is unclear to what extent these particles are capable of nucleating ice3–11. Here we show that material in the sea surface microlayer, which is enriched in surface active organic material representative of that found in sub-micron sea- spray aerosol12–21, nucleates ice under conditions that occur in mixed-phase clouds and high-altitude ice clouds. The ice active material is likely biogenic and is less than ~0.2 ?m in size. We also show that organic material (exudate) released by a common marine diatom nucleates ice when separated from cells and propose that organic material associated with phytoplankton cell exudates are a candidate for the observed ice nucleating ability of the microlayer samples. By combining our measurements with global model simulations of marine organic aerosol, we show that ice nucleating particles of marine origin are dominant in remote marine environments, such as the Southern Ocean, the North Pacific and the North Atlantic.

  1. Heterostructured Ag3PO4/AgBr/Ag plasmonic photocatalyst with enhanced photocatalytic activity and stability under visible light

    Science.gov (United States)

    Wang, Wan-Sheng; Du, Hong; Wang, Rui-Xia; Wen, Tao; Xu, An-Wu

    2013-03-01

    A heterostructured Ag3PO4/AgBr/Ag plasmonic photocatalyst was prepared by a rational in situ ion exchange reaction between Ag3PO4 micro-cubes and Br- in aqueous solution followed by photoreduction. The photocatalytic activities of obtained photocatalysts were measured by the degradation of methyl orange (MO) and methylene blue (MB) under visible light irradiation (λ >= 400 nm). Compared to AgBr/Ag, Ag3PO4/AgBr heterocrystals and pure Ag3PO4 crystals, the heterostructured Ag3PO4/AgBr/Ag plasmonic photocatalysts exhibit much higher photocatalytic activity and stability. This enhanced photocatalytic activity suggests that the synergetic effects of the heterostructured Ag3PO4/AgBr/Ag and the strong SPR of Ag NPs on the surface result in the high efficiencies of the photocatalytic activity and the improved stability. With the assistance of Ag3PO4/AgBr/Ag heterostructures, only 8 min and 12 min are taken to completely decompose MO and MB molecules under visible-light irradiation, respectively. Furthermore, the photodegradation rate does not show an obvious decrease during ten successive cycles, indicating that our heterostructured Ag3PO4/AgBr/Ag plasmonic photocatalysts are extremely stable under visible-light irradiation.A heterostructured Ag3PO4/AgBr/Ag plasmonic photocatalyst was prepared by a rational in situ ion exchange reaction between Ag3PO4 micro-cubes and Br- in aqueous solution followed by photoreduction. The photocatalytic activities of obtained photocatalysts were measured by the degradation of methyl orange (MO) and methylene blue (MB) under visible light irradiation (λ >= 400 nm). Compared to AgBr/Ag, Ag3PO4/AgBr heterocrystals and pure Ag3PO4 crystals, the heterostructured Ag3PO4/AgBr/Ag plasmonic photocatalysts exhibit much higher photocatalytic activity and stability. This enhanced photocatalytic activity suggests that the synergetic effects of the heterostructured Ag3PO4/AgBr/Ag and the strong SPR of Ag NPs on the surface result in the high

  2. 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

  3. Improved galvanic replacement growth of Ag microstructures on Cu micro-grid for enhanced SERS detection of organic molecules

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Tian-Long [Key Laboratory for Anisotropy and Texture of Materials, School of Materials and Metallurgy, Northeastern University, Shenyang 110819 (China); Advanced Materials Processing Unit, National Institute for Materials Science, Namiki 1–1, Tsukuba, Ibaraki 305-0044 (Japan); Li, Ji-Guang, E-mail: LI.Jiguang@nims.go.jp [Key Laboratory for Anisotropy and Texture of Materials, School of Materials and Metallurgy, Northeastern University, Shenyang 110819 (China); Advanced Materials Processing Unit, National Institute for Materials Science, Namiki 1–1, Tsukuba, Ibaraki 305-0044 (Japan); Sun, Xudong, E-mail: xdsun@mail.neu.edu.cn [Key Laboratory for Anisotropy and Texture of Materials, School of Materials and Metallurgy, Northeastern University, Shenyang 110819 (China); Sakka, Yoshio [Advanced Materials Processing Unit, National Institute for Materials Science, Namiki 1–1, Tsukuba, Ibaraki 305-0044 (Japan)

    2016-04-01

    Galvanic growth of Ag nano/micro-structures on Cu micro-grid was systematically studied for surface-enhanced Raman scattering (SERS) applications. Detailed characterizations via FE-SEM and HR-TEM showed that processing parameters, (reaction time, Ag{sup +} concentration, and PVP addition) all substantially affect thermodynamics/kinetics of the replacement reaction to yield substrates of significantly different microstructures/homogeneities and thus varied SERS performances (sensitivity, enhancement factor, and reproducibility) of the Ag substrates in the detection of R6G analyte. PVP as an additive was shown to notably alter nucleation/growth behaviors of the Ag crystals and promote the deposition of dense and uniform Ag films of nearly monodisperse polyhedrons/nanoplates through suppressing dendrites crystallization. Under optimized synthesis (50 mM of Ag{sup +}, 30 s of reaction, and 700 wt.% of PVP), Ag substrates exhibiting a high Raman signal enhancement factor of ~ 1.1 × 10{sup 6} and a low relative standard deviation of ~ 0.13 in the repeated detection of 10 μM R6G were obtained. The facile deposition and excellent performance reported in this work may allow the Ag microstructures to find wider SERS applications. Moreover, growth mechanisms of the different Ag nano/micro-structures were discussed based on extensive FE-SEM and HR-TEM analysis. - Highlights: • A facile synthetic technique of growing SERS active Ag substrates onto Cu micro-grid has been systematically studied. • Changing processing parameters has yielded Ag crystals of various morphologies and SERS performances. • PVP additive was observed to suppress Ag dendrite crystallization for nearly monodispersed Ag polyhedrons/nanoplates. • PVP modified SERS substrate exhibits excellent EF and RSD values in the repeated detection of 10 μM R6G analyte.

  4. Immersion freezing of ice nucleation active protein complexes

    Science.gov (United States)

    Hartmann, S.; Augustin, S.; Clauss, T.; Wex, H.; Šantl-Temkiv, T.; Voigtländer, J.; Niedermeier, D.; Stratmann, F.

    2013-06-01

    Utilising the Leipzig Aerosol Cloud Interaction Simulator (LACIS), the immersion freezing behaviour of droplet ensembles containing monodisperse particles, generated from a Snomax™ solution/suspension, was investigated. Thereto ice fractions were measured in the temperature range between -5 °C to -38 °C. Snomax™ is an industrial product applied for artificial snow production and contains Pseudomonas syringae} bacteria which have long been used as model organism for atmospheric relevant ice nucleation active (INA) bacteria. The ice nucleation activity of such bacteria is controlled by INA protein complexes in their outer membrane. In our experiments, ice fractions increased steeply in the temperature range from about -6 °C to about -10 °C and then levelled off at ice fractions smaller than one. The plateau implies that not all examined droplets contained an INA protein complex. Assuming the INA protein complexes to be Poisson distributed over the investigated droplet populations, we developed the CHESS model (stoCHastic modEl of similar and poiSSon distributed ice nuclei) which allows for the calculation of ice fractions as function of temperature and time for a given nucleation rate. Matching calculated and measured ice fractions, we determined and parameterised the nucleation rate of INA protein complexes exhibiting class III ice nucleation behaviour. Utilising the CHESS model, together with the determined nucleation rate, we compared predictions from the model to experimental data from the literature and found good agreement. We found that (a) the heterogeneous ice nucleation rate expression quantifying the ice nucleation behaviour of the INA protein complex is capable of describing the ice nucleation behaviour observed in various experiments for both, Snomax™ and P. syringae bacteria, (b) the ice nucleation rate, and its temperature dependence, seem to be very similar regardless of whether the INA protein complexes inducing ice nucleation are attached

  5. Immersion freezing of ice nucleation active protein complexes

    Directory of Open Access Journals (Sweden)

    S. Hartmann

    2013-06-01

    Full Text Available Utilising the Leipzig Aerosol Cloud Interaction Simulator (LACIS, the immersion freezing behaviour of droplet ensembles containing monodisperse particles, generated from a Snomax™ solution/suspension, was investigated. Thereto ice fractions were measured in the temperature range between −5 °C to −38 °C. Snomax™ is an industrial product applied for artificial snow production and contains Pseudomonas syringae} bacteria which have long been used as model organism for atmospheric relevant ice nucleation active (INA bacteria. The ice nucleation activity of such bacteria is controlled by INA protein complexes in their outer membrane. In our experiments, ice fractions increased steeply in the temperature range from about −6 °C to about −10 °C and then levelled off at ice fractions smaller than one. The plateau implies that not all examined droplets contained an INA protein complex. Assuming the INA protein complexes to be Poisson distributed over the investigated droplet populations, we developed the CHESS model (stoCHastic modEl of similar and poiSSon distributed ice nuclei which allows for the calculation of ice fractions as function of temperature and time for a given nucleation rate. Matching calculated and measured ice fractions, we determined and parameterised the nucleation rate of INA protein complexes exhibiting class III ice nucleation behaviour. Utilising the CHESS model, together with the determined nucleation rate, we compared predictions from the model to experimental data from the literature and found good agreement. We found that (a the heterogeneous ice nucleation rate expression quantifying the ice nucleation behaviour of the INA protein complex is capable of describing the ice nucleation behaviour observed in various experiments for both, Snomax™ and P. syringae bacteria, (b the ice nucleation rate, and its temperature dependence, seem to be very similar regardless of whether the INA protein complexes inducing ice

  6. Thermal properties of radiolytically synthesized PVA/Ag nanocomposites

    Directory of Open Access Journals (Sweden)

    Krklješ Aleksandra N.

    2007-01-01

    crystallization was retarded. The half time of melting is non-linearly dependent on the amount of nanofiller. In the range from 0.25 to 1 wt% Ag it slightly increases, because at a low Ag content the nanoparticles act as a heterogeneous nucleation agent during the crystallization process. For large amounts of nanofiller, the half time of melting is markedly higher than for pure PVA. At a higher Ag content, the nanoparticles act as a barrier that restricts the thermal motion of PVA molecular chains and the half time of complete melting increases. The significantly lower melting activation energy of the nanocomposites with high amount of nanofiller compared to pure PVA, calculated by the Kissinger method, indicated that nanoparticles reduced the heat barrier for the melting process. .

  7. On the homogeneous and heterogeneous nucleation of some organic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Hienola, A.

    2008-07-01

    The conversion of a metastable phase into a thermodynamically stable phase takes place via the formation of clusters. Clusters of different sizes are formed spontaneously within the metastable mother phase, but only those larger than a certain size, called the critical size, will end up growing into a new phase. There are two types of nucleation: homogeneous, where the clusters appear in a uniform phase, and heterogeneous, when pre-existing surfaces are available and clusters form on them. The nucleation of aerosol particles from gas-phase molecules is connected not only with inorganic compounds, but also with nonvolatile organic substances found in atmosphere. The question is which ones of the myriad of organic species have the right properties and are able to participate in nucleation phenomena. This thesis discusses both homogeneous and heterogeneous nucleation, having as theoretical tool the classical nucleation theory (CNT) based on thermodynamics. Different classes of organics are investigated. The members of the first class are four dicarboxylic acids (succinic, glutaric, malonic and adipic). They can be found in both the gas and particulate phases, and represent good candidates for the aerosol formation due to their low vapor pressure and solubility. Their influence on the nucleation process has not been largely investigated in the literature and it is not fully established. The accuracy of the CNT predictions for binary water-dicarboxylic acid systems depends significantly on the good knowledge of the thermophysical properties of the organics and their aqueous solutions. A large part of the thesis is dedicated to this issue. We have shown that homogeneous and heterogeneous nucleation of succinic, glutaric and malonic acids in combination with water is unlikely to happen in atmospheric conditions. However, it seems that adipic acid could participate in the nucleation process in conditions occurring in the upper troposphere. The second class of organics is

  8. The adsorption of fungal ice-nucleating proteins on mineral dusts: a terrestrial reservoir of atmospheric ice-nucleating particles

    Science.gov (United States)

    O'Sullivan, Daniel; Murray, Benjamin J.; Ross, James F.; Webb, Michael E.

    2016-06-01

    The occurrence of ice-nucleating particles (INPs) in our atmosphere has a profound impact on the properties and lifetime of supercooled clouds. To date, the identities, sources and abundances of particles capable of nucleating ice at relatively low supercoolings (T > -15 °C) remain enigmatic. While biomolecules such as proteins and carbohydrates have been implicated as important high-temperature INPs, the lack of knowledge on the environmental fates of these species makes it difficult to assess their potential atmospheric impacts. Here we show that such nanoscale ice-nucleating proteins from a common soil-borne fungus (Fusarium avenaceum) preferentially bind to and confer their ice-nucleating properties to kaolinite. The ice-nucleating activity of the proteinaceous INPs is unaffected by adsorption to the clay, and once bound the proteins do not readily desorb, retaining much of the activity even after multiple washings with pure water. The atmospheric implications of the finding that biological residues can confer their ice-nucleating ability to dust particles are discussed.

  9. 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.

  10. 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.

  11. About AgEcon Search

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    <正>AgEcon Search is a free,open access repository of full - text scholarly literature in agricultural and applied economics,inclu-ding working papers,conference papers,and journal articles. AgEcon Search is

  12. 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.

  13. 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.

  14. 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.

  15. Thermodynamic Derivation of the Activation Energy for Ice Nucleation

    Science.gov (United States)

    Barahona, D.

    2015-01-01

    Cirrus clouds play a key role in the radiative and hydrological balance of the upper troposphere. Their correct representation in atmospheric models requires an understanding of the microscopic processes leading to ice nucleation. A key parameter in the theoretical description of ice nucleation is the activation energy, which controls the flux of water molecules from the bulk of the liquid to the solid during the early stages of ice formation. In most studies it is estimated by direct association with the bulk properties of water, typically viscosity and self-diffusivity. As the environment in the ice-liquid interface may differ from that of the bulk, this approach may introduce bias in calculated nucleation rates. In this work a theoretical model is proposed to describe the transfer of water molecules across the ice-liquid interface. Within this framework the activation energy naturally emerges from the combination of the energy required to break hydrogen bonds in the liquid, i.e., the bulk diffusion process, and the work dissipated from the molecular rearrangement of water molecules within the ice-liquid interface. The new expression is introduced into a generalized form of classical nucleation theory. Even though no nucleation rate measurements are used to fit any of the parameters of the theory the predicted nucleation rate is in good agreement with experimental results, even at temperature as low as 190 K, where it tends to be underestimated by most models. It is shown that the activation energy has a strong dependency on temperature and a weak dependency on water activity. Such dependencies are masked by thermodynamic effects at temperatures typical of homogeneous freezing of cloud droplets; however, they may affect the formation of ice in haze aerosol particles. The new model provides an independent estimation of the activation energy and the homogeneous ice nucleation rate, and it may help to improve the interpretation of experimental results and the

  16. AGS Booster prototype magnets

    Energy Technology Data Exchange (ETDEWEB)

    Danby, G.; Jackson, J.; Lee, Y.Y.; Phillips, R.; Brodowski, J.; Jablonski, E.; Keohane, G.; McDowell, B.; Rodger, E.

    1987-03-19

    Prototype magnets have been designed and constructed for two half cells of the AGS Booster. The lattice requires 2.4m long dipoles, each curved by 10/sup 0/. The multi-use Booster injector requires several very different standard magnet cycles, capable of instantaneous interchange using computer control from dc up to 10 Hz.

  17. 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.

  18. Protein structural codes and nucleation sites for protein folding

    Institute of Scientific and Technical Information of China (English)

    Jiang Fan; Li Nan

    2007-01-01

    One of the long-standing controversial arguments in protein folding is Levinthal's paradox. We have recently proposed a new nucleation hypothesis and shown that the nucleation residues are the most conserved sequences in protein. To avoid the complicated effect of tertiary interactions, we limit our search for structural codes to the nucleation residues. Starting with the hypotheses of secondary structure nucleation and conservation of residues important for folding, we have analysed 762 folds classified as unique by SCOP. Segments of 17 residues around the top 20% conserved amino acids are analysed, resulting in approximately 100 clusters each for the main secondary structure classes of helix,sheet and coil. Helical clusters have the longest correlation range, coils the shortest (four residues). Strong specific sequence-structure correlation is observed for coil but not for helix and sheet, suggesting a mapping relationship between the sequence and the structure for coil. We propose that the central sequences in these clusters form 'structural codes',a useful basis set for identifying nucleation sites, protein fragments stable in isolation, and secondary structural patterns in proteins (particularly turns and loops).

  19. Toward a quantitative model of metamorphic nucleation and growth

    Science.gov (United States)

    Gaidies, F.; Pattison, D. R. M.; de Capitani, C.

    2011-11-01

    The formation of metamorphic garnet during isobaric heating is simulated on the basis of the classical nucleation and reaction rate theories and Gibbs free energy dissipation in a multi-component model system. The relative influences are studied of interfacial energy, chemical mobility at the surface of garnet clusters, heating rate and pressure on interface-controlled garnet nucleation and growth kinetics. It is found that the interfacial energy controls the departure from equilibrium required to nucleate garnet if attachment and detachment processes at the surface of garnet limit the overall crystallization rate. The interfacial energy for nucleation of garnet in a metapelite of the aureole of the Nelson Batholith, BC, is estimated to range between 0.03 and 0.3 J/m2 at a pressure of ca. 3,500 bar. This corresponds to a thermal overstep of the garnet-forming reaction of ca. 30°C. The influence of the heating rate on thermal overstepping is negligible. A significant feedback is predicted between chemical fractionation associated with garnet formation and the kinetics of nucleation and crystal growth of garnet giving rise to its lognormal—shaped crystal size distribution.

  20. To the theory of homogeneous nucleation: Cluster energy

    Science.gov (United States)

    Al'Tman, I. S.; Agranovskii, I. E.; Choi, M.; Zagainov, V. A.

    2008-12-01

    An attempt is made to critically analyze the modern state of the theory of homogeneous nucleation as concerns its ability to describe experiments with high accuracy. An analysis of the experimental data led us to conclude that the dependence of the nucleation rate on supersaturation and temperature T was not described by the theory, which underestimates the critical cluster size compared with the Gibbs-Thomson equation. The possibility of applying density functional theory (one of the latest achievements in the theory of homogeneous nucleation) was questioned. Within this theory, the Gibbs-Thomson equation remains valid even outside the classic capillary approximation. It is suggested that, to bring theory in consistency with experiment, certain fundamental propositions of the theory of nucleation should be revised. The inclusion of an additional contribution to the Gibbs energy of a cluster caused by the size dependence of the specific heat capacity of the cluster decreases the critical cluster size compared with the value calculated by the Gibbs-Thomson equation. The calculated dependence of nucleation rate on supersaturation was in agreement with the experimental results.

  1. Nucleation at surfaces: the importance of interfacial energy.

    Science.gov (United States)

    Wu, W; Gerard, D E; Nancollas, G H

    1999-11-01

    The nucleation and growth of stone-forming minerals on the surfaces of other crystalline phases, cellular material, and immobilized macromolecules must be important in the formation of stones in the urinary tract. The nucleation and growth of calcium oxalate monohydrate (COM) crystals were studied using the constant composition kinetics technique, in solution supersaturated with respect to COM (sigmaCOM = 1.44). The solid phases during the reaction were examined by x-ray diffraction, scanning electron microscopy, and diffuse reflectance Fourier transform infrared spectroscopy. Human serum albumin was found to nucleate COM crystals when immobilized on hydroxyapatite (HAP) surfaces. The induction period for nucleation of COM on HAP surfaces preadsorbed with albumin significantly decreased to about 65 min from about 230 min for pure HAP particles. The initial growth rate of COM on pure HAP particles, Rm approximately/= 0.56 X 10(-7) mol/min per m2, was slower than that for HAP surfaces preadsorbed with albumin, 2.14 x 10(-7) mol/min per m2. The surface properties were characterized using contact angle measurements by sessile drop and thin layer wicking. The thermodynamic results suggested that surfaces with high Lewis base parameter values (gamma-) and low interfacial tension with water (gammaSL) are more effective in the nucleation and growth of crystal phases.

  2. Urediospores of Puccinia spp. and other rusts are warm-temperature ice nucleators and harbor ice nucleation active bacteria

    Directory of Open Access Journals (Sweden)

    A. R. Moukahel

    2012-10-01

    Full Text Available In light of various features of the biology of the rust fungi and of the epidemiology of the plant diseases they cause that illustrate the important role of rainfall in their life history, we have characterized the ice nucleation activity (INA of the aerially disseminated spores (urediospores of this group of fungi. Urediospores of this obligate plant parasite were collected from natural infections from 7 species of weeds in France, from coffee in Brazil and from field and greenhouse-grown wheat in France, the USA, Turkey and Syria. Immersion freezing was used to determine freezing onset temperatures and the abundance of ice nuclei in suspensions of washed spores. Microbiological analyses of spores and subsequent tests of the ice nucleation activity of the bacteria associated with spores were deployed to quantify the contribution of bacteria to the ice nucleation activity of the spores. All samples of spores were ice nucleation active having freezing onset temperatures as warm as −4 °C. Spores in most of the samples carried cells of ice nucleation-active strains of the bacterium Pseudomonas syringae (at rates of less than 1 bacterial cell per 100 urediospores, but bacterial INA accounted for only a small fraction of the INA observed in spore suspensions. Changes in the INA of spore suspensions after treatment with lysozyme suggest that the INA of urediospores involves a polysaccharide. Based on data from the literature, we have estimated the concentrations of urediospores in air at cloud height and in rainfall. These quantities are very similar to those reported for other biological ice nucleators in these same substrates. We suggest that air sampling techniques have ignored the spatial and temporal variability of atmospheric concentrations that occur under conditions propitious for precipitation that could increase their local abundance intermittently. Nevertheless, we propose that the relative low abundance of warm-temperature biological

  3. Urediospores of Puccinia spp. and other rusts are warm-temperature ice nucleators and harbor ice nucleation active bacteria

    Science.gov (United States)

    Morris, C. E.; Sands, D. C.; Glaux, C.; Samsatly, J.; Asaad, S.; Moukahel, A. R.; Gonçalves, F. L. T.; Bigg, E. K.

    2012-10-01

    In light of various features of the biology of the rust fungi and of the epidemiology of the plant diseases they cause that illustrate the important role of rainfall in their life history, we have characterized the ice nucleation activity (INA) of the aerially disseminated spores (urediospores) of this group of fungi. Urediospores of this obligate plant parasite were collected from natural infections from 7 species of weeds in France, from coffee in Brazil and from field and greenhouse-grown wheat in France, the USA, Turkey and Syria. Immersion freezing was used to determine freezing onset temperatures and the abundance of ice nuclei in suspensions of washed spores. Microbiological analyses of spores and subsequent tests of the ice nucleation activity of the bacteria associated with spores were deployed to quantify the contribution of bacteria to the ice nucleation activity of the spores. All samples of spores were ice nucleation active having freezing onset temperatures as warm as -4 °C. Spores in most of the samples carried cells of ice nucleation-active strains of the bacterium Pseudomonas syringae (at rates of less than 1 bacterial cell per 100 urediospores), but bacterial INA accounted for only a small fraction of the INA observed in spore suspensions. Changes in the INA of spore suspensions after treatment with lysozyme suggest that the INA of urediospores involves a polysaccharide. Based on data from the literature, we have estimated the concentrations of urediospores in air at cloud height and in rainfall. These quantities are very similar to those reported for other biological ice nucleators in these same substrates. We suggest that air sampling techniques have ignored the spatial and temporal variability of atmospheric concentrations that occur under conditions propitious for precipitation that could increase their local abundance intermittently. Nevertheless, we propose that the relative low abundance of warm-temperature biological ice nucleators in the

  4. Nano-droplet ejection and nucleation of materials submitted to non-thermal plasma filaments

    Science.gov (United States)

    Borra, J.-P.; Jidenko, N.; Dutouquet, C.; Aguerre, O.; Hou, J.; Weber, A.

    2011-11-01

    Methods to induce non-thermal atmospheric pressure plasma filaments are presented with related properties for micro, streamer and prevented spark discharges, respectively, induced in planar Dielectric Barrier Discharges with one electrode covered by dielectric material (mono-DBD) or point-to-plane Corona. Two mechanisms of nano-particles formation are depicted from aerosol size distributions and TEM analysis. 0.1-10 mJ prevented spark discharges produce 10-100 nm droplets ejected from melted craters as well as nucleated primary particles and subsequent 10-100 nm agglomerates, by nucleation and coagulation in expanding vapor jets. With smaller energy per filament, 0.1-10 μJ micro-discharges and 0.1-100 μJ streamers, the initial local vapor fluxes emitted from spots of interaction between plasma filaments and electrodes are reduced. Subsequent smaller primary particle density limits the local coagulation in the vapor plume since 2-10 nm non-agglomerated crystalline metal nano-particles are produced in mono-DBD with Au, Ag and Cu electrode. Besides, the evolution of the aerosol size from primary nano-particles to agglomerates with transit time suggests slow coagulation of these primary metal particles in mono-DBD. Aerosol properties depend on the energy per filament and on the electrode. The final size is controlled by plasma parameters and transit time in and after the plasma. The aim is to underline emerging applications of atmospheric pressure plasmas for the production of tailored particles with tunable size, composition and structure with non-thermal plasma filaments to control the resulting properties of nano-powders and materials. Production rates and related energetic yields are compared.

  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. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  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. 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

  14. 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

  15. Fabrication of nanoporous silver by de-alloying Cu-Zr-Ag amorphous alloys

    Science.gov (United States)

    Wang, Hui; Xiao, Shang-gang; Zhang, Tao

    2016-07-01

    Nanoporous silver (NPS) with a ligament size ranging from 15 to 40 nm was fabricated by de-alloying (Cu50Zr50)100- x Ag x ( x = 10at%, 20at%, 30at%, and 40at%) amorphous ribbons in a mixed aqueous solution of hydrofluoric (HF) acid and nitric acid under free corrosion conditions. Nanoporous silver ligaments and pore sizes were able to be fine-tuned through tailoring the chemical composition, corrosion conditions, and de-alloying time. The ligament size increases with an increase in Ag content and de-alloying time, but decreases with an increase in HF concentration. This phenomenon may be attributed to the dissolution of Zr/Cu and the diffusion, aggregation, nucleation, and recrystallization of Ag, leading to an oriented attachment of adjacent nanocrystals as revealed by TEM analysis.

  16. AGS experiments -- 1991, 1992, 1993. Tenth edition

    Energy Technology Data Exchange (ETDEWEB)

    Depken, J.C.

    1994-04-01

    This report contains: (1) FY 1993 AGS schedule as run; (2) FY 1994--95 AGS schedule; (3) AGS experiments {ge} FY 1993 (as of 30 March 1994); (4) AGS beams 1993; (5) AGS experimental area FY 1991 physics program; (6) AGS experimental area FY 1992 physics program; (7) AGS experimental area FY 1993 physics program; (8) AGS experimental area FY 1994 physics program (planned); (9) a listing of experiments by number; (10) two-page summaries of each experiment; (11) listing of publications of AGS experiments; and (12) listing of AGS experiments.

  17. AGS experiments -- 1995, 1996 and 1997

    Energy Technology Data Exchange (ETDEWEB)

    Depken, J.C.; Presti, P.L.

    1997-12-01

    This report contains (1) FY 1995 AGS schedule as run; (2) FY 1996 AGS schedule as run; (3) FY 1997 AGS schedule as run; (4) FY 1998--1999 AGS schedule (proposed); (5) AGS beams 1997; (6) AGS experimental area FY 1995 physics program; (7) AGS experimental area FY 1996 physics program; (8) AGS experimental area FY 1997 physics program; (9) AGS experimental area FY 1998--1999 physics program (proposed); (10) a listing of experiments by number; (11) two-page summaries of each experiment, in order by number; and (12) listing of publications of AGS experiments.

  18. Pathways to self-organization: crystallization via nucleation and growth

    CERN Document Server

    Jungblut, Swetlana

    2016-01-01

    Crystallization, a prototypical self-organization process during which a disordered state spontaneously transforms into a crystal characterized by a regular arrangement of its building blocks, usually proceeds by nucleation and growth. In the initial stages of the transformation, a localized nucleus of the new phase forms in the old one due to a random fluctuation. Most of these nuclei disappear after a short time, but rarely a crystalline embryo may reach a critical size after which further growth becomes thermodynamically favorable and the entire system is converted into the new phase. In these lecture notes, we will discuss several theoretical concepts and computational methods to study crystallization. More specifically, we will address the rare event problem arising in the simulation of nucleation processes and explain how to calculate nucleation rates accurately. Particular attention is directed towards discussing statistical tools to analyze crystallization trajectories and identify the transition mech...

  19. Laser-nucleated acoustic cavitation in focused ultrasound.

    Science.gov (United States)

    Gerold, Bjoern; Kotopoulis, Spiros; McDougall, Craig; McGloin, David; Postema, Michiel; Prentice, Paul

    2011-04-01

    Acoustic cavitation can occur in therapeutic applications of high-amplitude focused ultrasound. Studying acoustic cavitation has been challenging, because the onset of nucleation is unpredictable. We hypothesized that acoustic cavitation can be forced to occur at a specific location using a laser to nucleate a microcavity in a pre-established ultrasound field. In this paper we describe a scientific instrument that is dedicated to this outcome, combining a focused ultrasound transducer with a pulsed laser. We present high-speed photographic observations of laser-induced cavitation and laser-nucleated acoustic cavitation, at frame rates of 0.5×10(6) frames per second, from laser pulses of energy above and below the optical breakdown threshold, respectively. Acoustic recordings demonstrated inertial cavitation can be controllably introduced to the ultrasound focus. This technique will contribute to the understanding of cavitation evolution in focused ultrasound including for potential therapeutic applications.

  20. Nucleation and electrolytic deposition of lead on model carbon electrodes

    Science.gov (United States)

    Cericola, D.; Spahr, M.

    2016-08-01

    There is a general consensus in the lead acid battery industry for the use of carbon additives as a functional component in the negative paste to boost the battery performance with regards to charge acceptance and cycle life especially for upcoming automotive and energy storage applications. Several mechanisms are discussed in the scientific literature and the affinity of the carbon surfaces to lead species seems to play a key role. With a set of experiments on model carbon electrodes we gave evidence to the fact that some carbon materials promote spontaneous nucleation of lead crystals. We propose a mechanism such that the carbon, as soon as in a lead containing environment, immobilizes some lead on its surface. Such immobilized lead acts as nucleation seed for the deposition of lead when a current is passed through the material. It is therefore possible to differentiate and select the carbon materials based on their ability to form nucleation seeds.