WorldWideScience

Sample records for carbon nanoclusters formed

  1. Platinum nano-cluster thin film formed on glassy carbon and the application for methanol oxidation

    International Nuclear Information System (INIS)

    Chang, Gang; Oyama, Munetaka; Hirao, Kazuyuki

    2007-01-01

    As an interesting platinum nanostructured material, a Pt nano-cluster film (PtNCF) attached on glassy carbon (GC) is reported. Through the reduction of PtCl 4 2- by ascorbic acid in the presence of GC substrate, a Pt thin continuous film composed of small nano-clusters which had a further agglomerated nanostructure of small grains could be attached on the GC surface. It was found that the electrocatalytic ability of PtNCF for the methanol oxidation was apparently higher than those of the Pt nano-clusters dispersedly attached on GC or indium in oxides. In addition, the electrocatalytic performance of PtNCF per Pt amount was superior to that of Pt black on GC. These results indicate that, in spite of the continuous nanostructures, nano-grains of PtNCF worked effectively for the catalytic electrolysis. The present PtNCF can be regarded as an interesting thin film material, which can be easily prepared by one-step chemical reduction

  2. Carbon nanotube growth from catalytic nano-clusters formed by hot-ion-implantation into the SiO{sub 2}/Si interface

    Energy Technology Data Exchange (ETDEWEB)

    Hoshino, Yasushi, E-mail: yhoshino@kanagawa-u.ac.jp [Department of Information Sciences, Kanagawa University, 2946 Tsuchiya, Hiratsuka, Kanagawa 259-1293 (Japan); Arima, Hiroki; Yokoyama, Ai; Saito, Yasunao; Nakata, Jyoji [Department of Information Sciences, Kanagawa University, 2946 Tsuchiya, Hiratsuka, Kanagawa 259-1293 (Japan)

    2012-07-01

    We have studied growth of chirality-controlled carbon nanotubes (CNTs) from hot-implantation-formed catalytic nano-clusters in a thermally grown SiO{sub 2}/Si substrate. This procedure has the advantage of high controllability of the diameter and the number of clusters by optimizing the conditions of the ion implantation. In the present study, Co{sup +} ions with ion dose of 8 Multiplication-Sign 10{sup 16} cm{sup -2} are implanted in the vicinity of the SiO{sub 2}/Si interface at 300 Degree-Sign C temperature. The implanted Co atoms located in the SiO{sub 2} layer has an amorphous-like structure with a cluster diameter of several nm. In contrast, implanted Co atoms in the Si substrate are found to take a cobalt silicide structure, confirmed by the high-resolution image of transmission electron microscope. CNTs are grown by microwave-plasma-enhanced chemical vapor deposition. We have confirmed a large amount of vertically-aligned multi-walled CNTs from the Co nano-clusters formed by the hot-ion-implantation near the SiO{sub 2}/Si interface.

  3. The formation of Cr2O3 nanoclusters over graphene sheet and carbon nanotubes

    Science.gov (United States)

    Dabaghmanesh, Samira; Neek-Amal, Mehdi; Partoens, Bart; Neyts, Erik C.

    2017-11-01

    Carbon supported metal oxide nanoparticles hold promise for various future applications in diverse areas including spintronics, catalysis and biomedicine. These applications, however, typically depend on the structure and morphology of the nanoparticles. In this contribution, we employ classical molecular dynamic simulations based on a recently developed force field to study the structural properties of Cr2O3 nanoclusters over graphene and carbon nanotubes. We observe that Cr2O3 nanoclusters tend to aggregate over both freestanding graphene and carbon nanotubes and form larger nanoclusters. These large nanoclusters are characterized by their worm-like shape with a lattice constant similar to that of bulk Cr2O3. We also investigate the structural deformation induced in graphene due to the presence of Cr2O3 nanoclusters.

  4. Definition of the size of nanoclusters of silver and palladium in carbon fiber

    International Nuclear Information System (INIS)

    Volobuev, V.S.; Bashmakov, I.A.; Lukashevich, S.M.; Tolkacheva, E.A.; Tikhonova, T.F.; Lukashevich, M.G.; Kaputskij, F.N.

    2008-01-01

    Size of palladium and silver nanoclusters is carbon matrix prepared by heart treatment of metal-polymer precursor has been determined by means of XR diffractions study. It was shown that the cluster size increases with increasing annealing temperature from 700 to 900 degree Celsius by factor two. No structuring of carbon matrix was observed under clusters forming. (authors)

  5. Optical properties of multicomponent antimony-silver nanoclusters formed in silica by sequential ion implantation

    International Nuclear Information System (INIS)

    Zuhr, R.A.

    1995-11-01

    The linear and nonlinear optical properties of nanometer dimension metal colloids embedded in a dielectric depend explicitly on the electronic structure of the metal nanoclusters. The ability to control the electronic structure of the nanoclusters may make it possible to tailor the optical properties for enhanced performance. By sequential implantation of different metal ion species multi-component nanoclusters can be formed with significantly different optical properties than single element metal nanoclusters. The authors report the formation of multi-component Sb/Ag nanoclusters in silica by sequential implantation of Sb and Ag. Samples were implanted with relative ratios of Sb to Ag of 1:1 and 3:1. A second set of samples was made by single element implantations of Ag and Sb at the same energies and doses used to make the sequentially implanted samples. All samples were characterized using RBS and both linear and nonlinear optical measurements. The presence of both ions significantly modifies the optical properties of the composites compared to the single element nanocluster glass composites. In the sequentially implanted samples the optical density is lower, and the strong surface plasmon resonance absorption observed in the Ag implanted samples is not present. At the same time the nonlinear response of the these samples is larger than for the samples implanted with Sb alone, suggesting that the addition of Ag can increase the nonlinear response of the Sb particles formed. The results are consistent with the formation of multi-component Sb/Ag colloids

  6. Structural and optical properties of 70-keV carbon ion beam synthesized carbon nanoclusters in thermally grown silicon dioxide

    International Nuclear Information System (INIS)

    Poudel, P.R.; Poudel, P.P.; Paramo, J.A.; Strzhemechny, Y.M.; Rout, B.; McDaniel, F.D.

    2015-01-01

    The structural and optical properties of carbon nanoclusters formed in thermally grown silicon dioxide film via the ion beam synthesis process have been investigated. A low-energy (70 keV) carbon ion beam (C - ) at a fluence of 3 x 10 17 atoms/cm 2 was used for implantation into a thermally grown silicon dioxide layer (500 nm thick) on a Si (100) wafer. Several parts of the implanted samples were subsequently annealed in a gas mixture (4 % H 2 + 96 % Ar) at 900 C for different time periods. The as-implanted and annealed samples were characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy, Raman spectroscopy, transmission electron microscopy (TEM), and photoluminescence spectroscopy (PL). The carbon ion implantation depth profile was simulated using a widely used Monte Carlo-based simulation code SRIM-2012. Additionally, the elemental depth profile of the implanted carbon along with host elements of silicon and oxygen were simulated using a dynamic ion-solid interaction code T-DYN, which incorporates the effects of the surface sputtering and gradual change in the elemental composition in the implanted layers due to high-fluence ion implantation. The elemental depth profile obtained from the XPS measurements matches closely to the T-DYN predictions. Raman measurements indicate the formation of graphitic phases in the annealed samples. The graphitic peak (G-peak) was found to be increased with the annealing time duration. In the sample annealed for 10 min, the sizes of the carbon nanoclusters were found to be 1-4 nm in diameter using TEM. The PL measurements at room temperature using a 325-nm laser show broad-band emissions in the ultraviolet to visible range in the as-implanted sample. Intense narrow bands along with the broad bands were observed in the annealed samples. The defects present in the as-grown samples along with carbon ion-induced defect centers in the as-implanted samples are the main contributors to the observed

  7. Structural and optical properties of 70-keV carbon ion beam synthesized carbon nanoclusters in thermally grown silicon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Poudel, P.R. [University of North Texas, Ion Beam Modification and Analysis Laboratory, Department of Physics, Denton, TX (United States); Intel Corporation, Rio Rancho, NM (United States); Poudel, P.P. [University of Kentucky, Department of Chemistry, Lexington, KY (United States); Paramo, J.A.; Strzhemechny, Y.M. [Texas Christian University, Department of Physics and Astronomy, Fort Worth, TX (United States); Rout, B. [University of North Texas, Ion Beam Modification and Analysis Laboratory, Department of Physics, Denton, TX (United States); University of North Texas, Center for Advanced Research and Technology, Denton, TX (United States); McDaniel, F.D. [University of North Texas, Ion Beam Modification and Analysis Laboratory, Department of Physics, Denton, TX (United States)

    2014-09-18

    The structural and optical properties of carbon nanoclusters formed in thermally grown silicon dioxide film via the ion beam synthesis process have been investigated. A low-energy (70 keV) carbon ion beam (C{sup -}) at a fluence of 3 x 10{sup 17} atoms/cm{sup 2} was used for implantation into a thermally grown silicon dioxide layer (500 nm thick) on a Si (100) wafer. Several parts of the implanted samples were subsequently annealed in a gas mixture (4 % H{sub 2} + 96 % Ar) at 900 C for different time periods. The as-implanted and annealed samples were characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy, Raman spectroscopy, transmission electron microscopy (TEM), and photoluminescence spectroscopy (PL). The carbon ion implantation depth profile was simulated using a widely used Monte Carlo-based simulation code SRIM-2012. Additionally, the elemental depth profile of the implanted carbon along with host elements of silicon and oxygen were simulated using a dynamic ion-solid interaction code T-DYN, which incorporates the effects of the surface sputtering and gradual change in the elemental composition in the implanted layers due to high-fluence ion implantation. The elemental depth profile obtained from the XPS measurements matches closely to the T-DYN predictions. Raman measurements indicate the formation of graphitic phases in the annealed samples. The graphitic peak (G-peak) was found to be increased with the annealing time duration. In the sample annealed for 10 min, the sizes of the carbon nanoclusters were found to be 1-4 nm in diameter using TEM. The PL measurements at room temperature using a 325-nm laser show broad-band emissions in the ultraviolet to visible range in the as-implanted sample. Intense narrow bands along with the broad bands were observed in the annealed samples. The defects present in the as-grown samples along with carbon ion-induced defect centers in the as-implanted samples are the main

  8. Catalytic hydrolysis of ammonia borane for hydrogen generation using cobalt nanocluster catalyst supported on polydopamine functionalized multiwalled carbon nanotube

    International Nuclear Information System (INIS)

    Arthur, Ernest Evans; Li, Fang; Momade, Francis W.Y.; Kim, Hern

    2014-01-01

    Hydrogen was generated from ammonia borane complex by hydrolysis using cobalt nanocluster catalyst supported on polydopamine functionalized MWCNTs (multi-walled carbon nanotubes). The impregnation-chemical reduction method was used for the preparation of the supported catalyst. The nanocluster catalyst support was formed by in-situ oxidative polymerization of dopamine on the MWCNTs in alkaline solution at room temperature. The structural and physical–chemical properties of the nanocluster catalyst were characterized by FT-IR (Fourier transform infrared spectroscopy), EDX (energy-dispersive X-ray spectroscopy), SEM (scanning electron microscope), XRD (X-ray diffraction) and TEM (transmission electron microscopy). The nanocluster catalyst showed good catalytic activity for the hydrogen generation from aqueous ammonia borane complex. A reusability test to determine the practical usage of the catalyst was also investigated. The result revealed that the catalyst maintained an appreciable catalytic performance and stability in terms of its reusability after three cycle of reuse for the hydrolysis reaction. Also, the activation energy for the hydrolysis of ammonia borane complex was estimated to be 50.41 kJmol −1 , which is lower than the values of some of the reported catalyst. The catalyst can be considered as a promising candidate in developing highly efficient portable hydrogen generation systems such as PEMFC (proton exchange membrane fuel cells). - Highlights: • Co/Pdop-o-MWCNT (Pdop functionalized MWCNT supported cobalt nanocluster) catalyst was synthesized for hydrogen generation. • It is an active catalyst for hydrogen generation via hydrolysis of ammonia borane. • It showed good stability in terms of reusability for the hydrogen generation

  9. Microscopic Fuel Particles Produced by Self-Assembly of Actinide Nanoclusters on Carbon Nanomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Na, Chongzheng [Univ. of Notre Dame, IN (United States)

    2016-10-17

    Many consider further development of nuclear power to be essential for sustained development of society; however, the fuel forms currently used are expensive to recycle. In this project, we sought to create the knowledge and knowhow that are needed to produce nanocomposite materials by directly depositing uranium nanoclusters on networks of carbon-­ based nanomaterials. The objectives of the proposed work were to (1) determine the control of uranium nanocluster surface chemistry on nanocomposite formation, (2) determine the control of carbon nanomaterial surface chemistry on nanocomposite formation, and (3) develop protocols for synthesizing uranium-­carbon nanomaterials. After examining a wide variety of synthetic methods, we show that synthesizing graphene-­supported UO2 nanocrystals in polar ethylene glycol compounds by polyol reduction under boiling reflux can enable the use of an inexpensive graphene precursor graphene oxide in the production of uranium-carbon nanocomposites in a one-­pot process. We further show that triethylene glycol is the most suitable solvent for producing nanometer-­sized UO2 crystals compared to monoethylene glycol, diethylene glycol, and polyethylene glycol. Graphene-­supported UO2 nanocrystals synthesized with triethylene glycol show evidence of heteroepitaxy, which can be beneficial for facilitating heat transfer in nuclear fuel particles. Furthermore, we show that graphene-supported UO2 nanocrystals synthesized by polyol reduction can be readily stored in alcohols, preventing oxidation from the prevalent oxygen in air. Together, these methods provide a facile approach for preparing and storing graphene-supported UO nanocrystals for further investigation and development under ambient conditions.

  10. 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.

  11. Carbon surface diffusion and SiC nanocluster self-ordering

    International Nuclear Information System (INIS)

    Pezoldt, J.; Trushin, Yu.V.; Kharlamov, V.S.; Schmidt, A.A.; Cimalla, V.; Ambacher, O.

    2006-01-01

    The process of the spatial ordering of SiC nanoclusters on the step edges on Si surfaces was studied by means of multi-scale computer simulation. The evolution of cluster arrays on an ideal flat surface and surfaces with terraces of various widths was performed by kinetic Monte Carlo (KMC) simulations based on quantitative studies of potential energy surfaces (PES) by molecular dynamics (MD). PES analysis revealed that certain types of steps act as strong trapping centres for both Si and C adatoms stimulating clusters nucleation. Spatial ordering of the SiC nanoclusters at the terrace edges can be achieved if the parameters of the growth process (substrate temperature, carbon flux) and substrate (steps direction and terrace widths) are adjusted to the surface morphology. Temperature ranges for growth regimes with and without formation of cluster chains were determined. Cluster size distributions and the dependence of optimal terrace width for self ordering on the deposition parameters were obtained

  12. 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.

  13. Calcium carbonate-gold nanocluster hybrid spheres: synthesis and versatile application in immunoassays.

    Science.gov (United States)

    Peng, Juan; Feng, Li-Na; Zhang, Kui; Li, Xing-Hua; Jiang, Li-Ping; Zhu, Jun-Jie

    2012-04-23

    Fluorescent gold nanoclusters (AuNCs) were incorporated into porous calcium carbonate spheres through electrostatic interaction. The resulting CaCO(3)/AuNCs hybrid material exhibited interesting properties, such as porous structure, excellent biocompatibility, good water solubility, and degradability. These properties make the CaCO(3)/AuNCs hybrid material a promising template to assemble horseradish peroxidase/antibody conjugates (HRP-Ab(2)). By using CaCO(3)/AuNCs/HRP-Ab(2) bioconjugates as probes, a versatile immunosensor was developed for fluorescent and electrochemical detection of the cancer biomarker neuron-specific enolase (NSE). The detection limits of the sensor were 2.0 and 0.1 pg mL(-1) for fluorescent and electrochemical detection, respectively. The immunosensor shows high sensitivity and offers an alternative strategy for the detection of other proteins and DNA. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Optical properties of Ag nanoclusters formed by irradiation and annealing of SiO{sub 2}/SiO{sub 2}:Ag thin films

    Energy Technology Data Exchange (ETDEWEB)

    Güner, S., E-mail: sguner@fatih.edu.tr [Department of Physics, Fatih University, 34500 Büyükçekmece, İstanbul (Turkey); Budak, S. [Department of Electrical Engineering and Computer Science, Alabama A and M University, Huntsville, AL 35810 (United States); Gibson, B. [Department of Physics, UAH, Huntsville, AL 35899 (United States); Ila, D. [Department of Chemistry and Physics, Fayetteville St. University, Fayetteville, NC 28301 (United States)

    2014-08-15

    Highlights: • Fabrication of films through the Reactive Electron Beam deposition technique. • Perfect and reproducible Ag nanoclustered host matrix. • Potential technological applicability in thermoelectric devices. - Abstract: We have deposited five periodic SiO{sub 2}/SiO{sub 2} + Ag multi-nano-layered films on fused silica substrates using physical vapor deposition technique. The co-deposited SiO{sub 2}:Ag layers were 2.7–5 nm and SiO{sub 2} buffer layers were 1–15 nm thick. Total thickness was between 30 and 105 nm. Different concentrations of Ag, ranging from 1.5 to 50 molecular% with respect to SiO{sub 2} were deposited to determine relevant rates of nanocluster formation and occurrence of interaction between nanoclusters. Using interferometry as well as in situ thickness monitoring, we measured the thickness of the layers. The concentration of Ag in SiO{sub 2} was measured with Rutherford Backscattering Spectrometry (RBS). To nucleate Ag nanoclusters, 5 MeV cross plane Si ion bombardments were performed with fluence varying between 5 × 10{sup 14} and 1 × 10{sup 16} ions/cm{sup 2} values. Optical absorption spectra were recorded in the range of 200–900 nm in order to monitor the Ag nanocluster formation in the thin films. Thermal annealing treatment at different temperatures was applied as second method to form varying size of nanoclusters. The physical properties of formed super lattice were criticized for thermoelectric applications.

  15. Size-dependent structure of CdSe nanoclusters formed after ion implantation in MgO

    NARCIS (Netherlands)

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

    The band gap as well as the optical and structural properties of semiconductor CdSe nanoclusters change as a function of the nanocluster size. Embedded CdSe nanoclusters in MgO were created by means of sequential Cd and Se ion implantation followed by thermal annealing. Changes during annealing were

  16. A ratiometric nanoprobe based on silver nanoclusters and carbon dots for the fluorescent detection of biothiols

    Science.gov (United States)

    Zhang, Shuming; Lin, Bixia; Yu, Ying; Cao, Yujuan; Guo, Manli; Shui, Lingling

    2018-04-01

    Ratiometric fluorescent probes could eliminate the influence from experimental factors and improve the detection accuracy. In this article, a ratiometric nanoprobe was constructed based on silver nanoclusters (AgNCs) with nitrogen-doped carbon dots (NCDs) and used for the detection of biothiols. The fluorescence peak of AgNCs was observed at 650 nm with excitation wavelength at 370 nm. In order to construct the ratiometric fluorescent probe, NCDs with the excitation and emission wavelengths at 370 nm and 450 nm were selected. After adding AgNCs, the fluorescence of NCDs was quenched. The mechanism of the fluorescence quenching was studied by fluorescence, UV-Vis absorption and the fluorescence lifetime spectra. The results indicated that the quenching could be ascribed to the inner filter effect (IFE). With the addition of biothiols, the fluorescence of AgNCs at 650 nm decreased due to the breakdown of AgNCs, and the fluorescence of NCDs at 450 nm recovered accordingly. Thus, the relationship between the ratio of the fluorescence intensities (I450/I650) and biothiol concentration was used to establish the determination method for biothiols. Cysteine (Cys) was taken as the model of biothiols, and the working curve for Cys was I450/I650 = 0.60CCys - 1.86 (CCys: μmol/L) with the detection limit of 0.14 μmol/L (S/N = 3). Then, the method was used for the detection of Cys in human urine and serum samples with satisfactory accuracy and recovery ratios. Furthermore, the probe could be applied for the visual semi-quantitative determination of Cys by naked eyes.

  17. The role of carbon solubility in Fe-C nano-clusters on the growth of small single-walled carbon nanotubes

    Science.gov (United States)

    Curtarolo, Stefano; Awasthy, Neha; Setyawan, Wahyu; Mora, Elena; Tokune, Toshio; Bolton, Kim; Harutyunyan, Avetik

    2008-03-01

    Various diameters of alumina-supported Fe catalysts are used to grow single-walled carbon nanotubes (SWCNTs) with chemical vapor decomposition. We find that the reduction of the catalyst size requires an increase of the minimum temperature necessary for the growth. We address this phenomenon in terms of solubility of C in Fe nanoclusters and, by using first principles calculations, we devise a simple model to predict the behavior of the phases competing for stability in Fe-C nanoclusters at low temperature. We show that, as a function particles size, there are three scenarios compatible with steady state-, limited- and no-growth of SWCNTs, corresponding to unaffected, reduced and no solubility of C in the particles. The result raises previously unknown concerns about the growth feasibility of small and very-long SWCNTs within the current Fe CVD technology, and suggests new strategies in the search of better catalysts. Research supported by Honda R.I. and NSF.

  18. Size-dependent structure of CdSe nanoclusters formed after ion implantation in MgO

    OpenAIRE

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

    2005-01-01

    The band gap as well as the optical and structural properties of semiconductor CdSe nanoclusters change as a function of the nanocluster size. Embedded CdSe nanoclusters in MgO were created by means of sequential Cd and Se ion implantation followed by thermal annealing. Changes during annealing were monitored using optical absorption and positron annihilation spectroscopy. High-resolution TEM on cross-sections after annealing at a temperature of 1300 K showed that clusters with a size below 5...

  19. Synthesis of indium nanoclusters and formation of thin film contacts on plastic substrates for organic and flexible electronics applications

    International Nuclear Information System (INIS)

    Shi, Frank F; Bulkowski, Michal; Hsieh, K C

    2007-01-01

    In this work, we described the processes of synthesizing free-standing indium nanoclusters using inverse micelles and microemulsions as well as synthesizing organic-encapsulated indium nanoclusters using alkanethiols as the organic encapsulants. The synthesized organic-encapsulated indium nanoclusters have demonstrated the feasibilities to be used as plastic compatible soft metal contacts for emerging organic devices. The homogeneously distributed indium nanoclusters with sizes of 10-30 nm have been fabricated on a few different plastic substrates. By changing the alkanethiol carbon chain length and the sizes of the indium nanoclusters, the annealing temperature required to form low-resistance indium thin film conductors has been reduced to 80-100 deg. C, which is acceptable for a variety of organic thin films

  20. 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.

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

    International Nuclear Information System (INIS)

    Rodríguez-Galván, Andrés; Heredia, Alejandro; Amelines-Sarria, Oscar; Rivera, Margarita

    2015-01-01

    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

  2. A highly efficient nano-cluster artificial peroxidase and its direct electrochemistry on a nano complex modified glassy carbon electrode.

    Science.gov (United States)

    Hong, Jun; Wang, Wei; Huang, Kun; Yang, Wei-Yun; Zhao, Ying-Xue; Xiao, Bao-Lin; Gao, Yun-Fei; Moosavi-Movahedi, Zainab; Ghourchian, Hedayatollah; Moosavi-Movahedi, Ali Akbar

    2012-01-01

    A nano-cluster with highly efficient peroxide activity was constructed based on nafion (NF) and cytochrome c (Cyt c). UV-Vis spectrometry and transmission electron microscopy (TEM) methods were utilized for characterization of the nano-structured enzyme or artificial peroxidase (AP). The nano-cluster was composed of a Chain-Ball structure, with an average ball size of about 40 nm. The Michaelis-Menten (K(m)) and catalytic rate (k(cat)) constants of the AP were determined to be 2.5 ± 0.4 µM and 0.069 ± 0.001 s(-1), respectively, in 50 mM PBS at pH 7.0. The catalytic efficiency of the AP was evaluated to be 0.028 ± 0.005 µM(-1) s(-1), which was 39 ± 5% as efficient as the native horseradish peroxidase (HRP). The AP was also immobilized on a functional multi-wall carbon nanotube (MWNCTs)-gold colloid nanoparticles (AuNPs) nano-complex modified glassy carbon (GC) electrode. The cyclic voltammetry of AP on the nano complex modified GC electrode showed a pair of well-defined redox peaks with a formal potential (E°') of -45 ± 2 mV (vs. Ag/AgCl) at a scan rate of 0.05 V/s. The heterogeneous electron transfer rate constant (k(s)) was evaluated to be 0.65 s(-1). The surface concentration of electroactive AP on GC electrode (Γ) was 7 × 10(-10) mol cm(-2). The apparent Michaelis-Menten constant (K(m)(app)) was 0.23 nM.

  3. Size-dependent structure of CdSe nanoclusters formed after ion implantation in MgO

    International Nuclear Information System (INIS)

    Huis, M.A. van; Veen, A. van; Schut, H.; Eijt, S.W.H.; Kooi, B.J.; Hosson, J.Th.M. de

    2005-01-01

    The band gap as well as the optical and structural properties of semiconductor CdSe nanoclusters change as a function of the nanocluster size. Embedded CdSe nanoclusters in MgO were created by means of sequential Cd and Se ion implantation followed by thermal annealing. Changes during annealing were monitored using optical absorption and positron annihilation spectroscopy. High-resolution TEM on cross-sections after annealing at a temperature of 1300 K showed that clusters with a size below 5 nm have the high-pressure rock-salt structure and are in a cube-on-cube orientation relation with MgO, whereas clusters larger than 5 nm adopt the stable wurtzite crystal structure and were observed in two different orientation relations with MgO

  4. Surface Modification of Carbon Nanotube Networked Films with Au Nanoclusters for Enhanced NO2 Gas Sensing Applications

    Directory of Open Access Journals (Sweden)

    M. Penza

    2008-01-01

    Full Text Available Multiwalled carbon nanotube (MWCNT films have been deposited by using plasma-enhanced chemical vapor deposition (PECVD system onto alumina substrates, provided with 6 nm thick cobalt (Co growth catalyst for remarkably improved NO2 gas sensing, at working temperature in the range of 100–250∘C. Functionalization of the MWCNTs with nanoclusters of gold (Au sputtering has been performed to modify the surface of carbon nanotube networked films for enhanced and specific NO2 gas detection up to sub-ppm level. It is demonstrated that the NO2 gas sensitivity of the MWCNT-based sensors depends on Au-loading used as surface-catalyst. The gas response of MWCNT-based chemiresistor is attributed to p-type conductivity in the Au-modified semiconducting MWCNTs with a very good short-term repeatability and faster recovery. The sensor temperature of maximum NO2 sensitivity of the Au-functionalized MWCNTs is found to decrease with increasing Au-loading on their surface, and continuous gas monitoring at ppb level of NO2 is effectively performed with Au-modified MWCNT chemiresistors.

  5. Selection of a carbon-14 fixation form

    International Nuclear Information System (INIS)

    Scheele, R.D.; Burger, L.L.

    1982-09-01

    This report summarizes work on the selection of a disposal form for carbon-14 produced during the production of nuclear power. Carbon compounds were screened on the basis of solubility, thermal stability, resistance to oxidation, cost and availability, compatibility with the selected disposal matrix, leach resistance when incorporated in concrete, and compatibility with capture technologies. Carbonates are the products of the various technologies presently considered for carbon-14 capture. The alkaline earth carbonates exhibit the greatest thermal stabilities, lowest solubilities, lowest raw material cost, and greatest raw material availabilities. When reactions with cement and its impurities are considered, calcium and strontium carbonates are the only alkaline earth carbonates resistant to hydrolysis and reaction with sulfate. Leaching tests of barium, calcium, lead, potassium, and strontium carbonates in concrete showed calcium carbonate concrete to be slightly superior to the other alkaline earth carbonates, and greatly superior to a soluble carbonate, potassium carbonate, and lead carbonate. None of the additives to the concrete reduced the carbonate leaching. Acidic CO 2 -containing waters were found to greatly increase carbonate leaching from concrete. Sea water was found to leach less carbon from carbonate concretes than either distilled water or Columbia River water, which showed nearly equivalent leaching. Based on our work, calcium, barium, and strontium carbonates in concrete are the most suitable waste forms for carbon-14, with calcium carbonate concrete slightly superior to the others. If the waste form is to be exposed to natural waters, sea water will have the lowest leach rate. 6 figures, 7 tables

  6. Method of forming a nanocluster comprising dielectric layer and device comprising such a layer

    NARCIS (Netherlands)

    2009-01-01

    A method of forming a dielectric layer (330) on a further layer (114, 320) of a semiconductor device (300) is disclosed. The method comprises depositing a dielectric precursor compound and a further precursor compound over the further layer (114, 320), the dielectric precursor compound comprising a

  7. Ultra-sensitive determination of epinephrine based on TiO{sub 2}-Au nanoclusters supported on reduced graphene oxide and carbon nanotube hybrid nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jianbo, E-mail: chm_lijianbo@yeah.net; Wang, Xiaojiao; Duan, Huimin; Wang, Yanhui; Luo, Chuannan, E-mail: chm_lijianbo@yeah.net

    2016-07-01

    A highly efficient and sensitive electrochemical sensor for EP based on reduced graphene and multi-walled carbon nanotube hybrid nanocomposites loaded TiO{sub 2}-Au nano-clusters modified glassy carbon electrode was developed. The surface nature and morphology of the nanocomposite film and the electrochemical properties of the sensor were characterized by Raman spectra, X-ray powder diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectra (EDX), Fourier transform infrared spectroscopy (FT-IR), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV), respectively. Carbon nanomaterials were widely used in sensing due to its large electroactive surface area, fast electron transport and strong adsorption capacity. Meanwhile, TiO{sub 2}-Au nano-clusters could accelerate the electron transfer, increase reactive site and extend electrochemical response window. The nanocomposite film could greatly enhance the response sensitivity and decrease the overpotential. The resulting sensor showed an excellent electrocatalytic activity toward EP. Under the optimum conditions (i.e. pH 6.0, 0.1 M PBS, preconcentration for 110 s), Differential pulse voltammetry was employed to detect ultra-trace amounts of EP. The result of a wide linear range of 1.0–300 nM and limited of detection 0.34 nM (S/N = 3) were obtained. The constructed sensor exhibited excellent accuracy and precision, the relative standard deviation (RSD) was less than 5%. The nanocomposite film sensor was successfully used to accurately detect the content of EP in practical samples, and the recoveries for the standards added are 97%–105%. - Highlights: • The three dimensional composite materials rGO/CNTs were successful synthesized. • High conductivity and catalytic activity of TiO{sub 2}-Au nanoclusters were synthesized. • The sensor displays a wide linear range, low detection limit and good stability.

  8. Some properties of solid helium and helium nanoclusters using the effective HFD-like interaction potential: Adsorption and desorption inside carbon nanotube

    Science.gov (United States)

    Abbaspour, M.; Akbarzadeh, H.; Banihashemi, S. Z.; Sotoudeh, A.

    2018-02-01

    We have calculated the zero equation of state of solid helium using a two-body Hartree-Fock dispersion (HFD)-like potential from molecular dynamics (MD) simulation. To take many-body forces into account, our simple and accurate empirical expression is used with the HFD-like potential without requiring an expensive three-body calculation. This potential model also includes the quantum effects for helium at low temperatures. The results indicate that our effective HFD-like potential improves the prediction of the classical two-body results to get better agreement with experiment than many other two-body and three-body potentials of helium reported in the literature. We have also simulated the adsorption and desorption processes of the (He)55, (He)147, (He)309, (He)561, and (He)923 icosahedral nanoclusters confined into the different armchair and zigzag CNTs from 0 to 50 K using our effective model. We have observed an interesting phenomenon at 0 K for helium. The nanoclusters adsorb to the inner CNT wall as a melting process. But, the heavier noble gas clusters (such as Ne and Xe) show the different behavior than the He clusters. They form a multilayered solid structure into the CNT at zero temperature and adsorb into the inner wall of the CNT at higher temperatures. Our results for He clusters show that the absolute value of the adsorption energy increases as the size of the nanocluster increases. The desorption process begins at a certain temperature and represents itself by a jump in the configurational energy values. We have also investigated the structural and dynamical properties of the confined helium nanoclusters during the adsorption and desorption processes at different temperatures.

  9. Electronic Switch in the Carbon-Centered [Re12CS17(CN6] n−Nanocluster

    Directory of Open Access Journals (Sweden)

    Gabuda SP

    2009-01-01

    Full Text Available Abstract An abrupt change in internuclear Re–Re distances between {Re6} subunits in the carbon-centered [Re12μ6-CS17(CN6] n−complexes caused by the change of the oxidation state (n = 6, 8 is first theoretically shown to be possibly controlled by an external electric field.13C NMR signal is shown to change over ~400 ppm (~37G for μ6-C atom together withn. Thereby, the metal cluster [Re12μ6-CS17(CN6] n−can be considered as a perspective model of a molecular switch.

  10. Radiation-sustained nanocluster metastability in oxide dispersion strengthened materials

    Science.gov (United States)

    Ribis, J.; Bordas, E.; Trocellier, P.; Serruys, Y.; de Carlan, Y.; Legris, A.

    2015-12-01

    ODS materials constitute a new promising class of structural materials for advanced fission and fusion energy application. These Fe-Cr based ferritic steels contain ultra-high density of dispersion-strengthening nanoclusters conferring excellent mechanical properties to the alloy. Hence, guarantee the nanocluster stability under irradiation remain a critical issue. Nanoclusters are non-equilibrium multicomponent compounds (YTiCrO) forming through a complex nucleation pathway during the elaboration process. In this paper, it is proposed to observe the response of these nanoclusters when the system is placed far from equilibrium by means of ion beam. The results indicate that the Y, Ti, O and Cr atoms self-organized so that nanoclusters coarsened but maintain their non-equilibrium chemical composition. It is discussed that the radiation-sustained nanocluster metastability emerges from cooperative effects: radiation-induced Ostwald ripening, permanent creation of vacancies in the clusters, and fast Cr diffusion mediated by interstitials.

  11. Radiation-sustained nanocluster metastability in oxide dispersion strengthened materials

    International Nuclear Information System (INIS)

    Ribis, J.; Bordas, E.; Trocellier, P.; Serruys, Y.; Carlan, Y. de; Legris, A.

    2015-01-01

    ODS materials constitute a new promising class of structural materials for advanced fission and fusion energy application. These Fe–Cr based ferritic steels contain ultra-high density of dispersion-strengthening nanoclusters conferring excellent mechanical properties to the alloy. Hence, guarantee the nanocluster stability under irradiation remain a critical issue. Nanoclusters are non-equilibrium multicomponent compounds (YTiCrO) forming through a complex nucleation pathway during the elaboration process. In this paper, it is proposed to observe the response of these nanoclusters when the system is placed far from equilibrium by means of ion beam. The results indicate that the Y, Ti, O and Cr atoms self-organized so that nanoclusters coarsened but maintain their non-equilibrium chemical composition. It is discussed that the radiation-sustained nanocluster metastability emerges from cooperative effects: radiation-induced Ostwald ripening, permanent creation of vacancies in the clusters, and fast Cr diffusion mediated by interstitials.

  12. Forming foam structures with carbon foam substrates

    Science.gov (United States)

    Landingham, Richard L.; Satcher, Jr., Joe H.; Coronado, Paul R.; Baumann, Theodore F.

    2012-11-06

    The invention provides foams of desired cell sizes formed from metal or ceramic materials that coat the surfaces of carbon foams which are subsequently removed. For example, metal is located over a sol-gel foam monolith. The metal is melted to produce a metal/sol-gel composition. The sol-gel foam monolith is removed, leaving a metal foam.

  13. Electrodeposition of gold nanoclusters on overoxidized polypyrrole film modified glassy carbon electrode and its application for the simultaneous determination of epinephrine and uric acid under coexistence of ascorbic acid

    Energy Technology Data Exchange (ETDEWEB)

    Li Jing [Department of Chemistry, University of Science and Technology of China, Hefei 230026 (China); Lin Xiangqin [Department of Chemistry, University of Science and Technology of China, Hefei 230026 (China)]. E-mail: xqlin@ustc.edu.cn

    2007-07-23

    A novel biosensor was fabricated by electrochemical deposition of gold nanoclusters on ultrathin overoxidized polypyrrole (PPyox) film, formed a nano-Au/PPyox composite on glassy carbon electrode (nano-Au/PPyox/GCE). The properties of the nanocomposite have been characterized by field emission scanning electron microscope (FE-SEM), X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (XRD) and electrochemical investigations. The nano-Au/PPyox/GCE had strongly catalytic activity toward the oxidation of epinephrine (EP), uric acid (UA) and ascorbic acid (AA), and resolved the overlapping voltammetric response of EP, UA and AA into three well-defined peaks with a large anodic peak difference. The catalytic peak currents obtained from differential pulse voltammetry increased linearly with increasing EP and UA concentrations in the range of 3.0 x 10{sup -7} to 2.1 x 10{sup -5} M and 5.0 x 10{sup -8} to 2.8 x 10{sup -5} M with a detection limit of 3.0 x 10{sup -8} and 1.2 x 10{sup -8} M (s/n = 3), respectively. The results showed that the modified electrode can selectively determine EP and UA in the coexistence of a large amount of AA. In addition, the sensor exhibited excellent sensitivity, selectivity and stability. The nano-Au/PPyox/GCE has been applied to determination of EP in epinephrine hydrochloride injection and UA in urine samples with satisfactory results.

  14. Amorphous calcium carbonate particles form coral skeletons

    Science.gov (United States)

    Mass, Tali; Giuffre, Anthony J.; Sun, Chang-Yu; Stifler, Cayla A.; Frazier, Matthew J.; Neder, Maayan; Tamura, Nobumichi; Stan, Camelia V.; Marcus, Matthew A.; Gilbert, Pupa U. P. A.

    2017-09-01

    Do corals form their skeletons by precipitation from solution or by attachment of amorphous precursor particles as observed in other minerals and biominerals? The classical model assumes precipitation in contrast with observed “vital effects,” that is, deviations from elemental and isotopic compositions at thermodynamic equilibrium. Here, we show direct spectromicroscopy evidence in Stylophora pistillata corals that two amorphous precursors exist, one hydrated and one anhydrous amorphous calcium carbonate (ACC); that these are formed in the tissue as 400-nm particles; and that they attach to the surface of coral skeletons, remain amorphous for hours, and finally, crystallize into aragonite (CaCO3). We show in both coral and synthetic aragonite spherulites that crystal growth by attachment of ACC particles is more than 100 times faster than ion-by-ion growth from solution. Fast growth provides a distinct physiological advantage to corals in the rigors of the reef, a crowded and fiercely competitive ecosystem. Corals are affected by warming-induced bleaching and postmortem dissolution, but the finding here that ACC particles are formed inside tissue may make coral skeleton formation less susceptible to ocean acidification than previously assumed. If this is how other corals form their skeletons, perhaps this is how a few corals survived past CO2 increases, such as the Paleocene-Eocene Thermal Maximum that occurred 56 Mya.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ribis, J., E-mail: joel.ribis@cea.fr [DEN-Service de Recherches Métallurgiques Appliquées, CEA, Université Paris-Saclay, F-91191, Gif-sur-Yvette (France); Thual, M.A. [LLB, CEA, CNRS, Université Paris-Saclay, CEA Saclay, 91191, Gif-sur-Yvette (France); Guilbert, T.; Carlan, Y. de [DEN-Service de Recherches Métallurgiques Appliquées, CEA, Université Paris-Saclay, F-91191, Gif-sur-Yvette (France); Legris, A. [UMET, CNRS/UMR 8207, Bât. C6, Univ. Lille 1, 59655 Villeneuve d’Ascq (France)

    2017-02-15

    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-0.3Y{sub 2}O{sub 3} 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 Y{sub 2}Ti{sub 2}O{sub 7}-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. - Highlights: • The nanoclusters display a f.c.c. cubic symmetry and a non-equilibrium YTiCrO chemical composition. • During thermal annealing the coherent nanocluster transform into semi-coherent pyrochlore particles. • A Cr ring is observed around the relaxed pyrochlore type particles.

  16. Deposition and characterization of Pt nanocluster films by means of gas aggregation cluster source

    Energy Technology Data Exchange (ETDEWEB)

    Kylián, Ondřej, E-mail: ondrej.kylian@gmail.com; Prokeš, Jan; Polonskyi, Oleksandr; Čechvala, Juraj; Kousal, Jaroslav; Pešička, Josef; Hanuš, Jan; Biederman, Hynek

    2014-11-28

    In this study we report on the deposition of Pt nanocluster films prepared by gas aggregation source that was operated with argon as working gas. The aim of this study was optimization of deposition process as well as determination of properties of deposited nanocluster films and their temporal stability. It was found that the production of Pt nanoclusters reached maximum value for pressure of 100 Pa and increases monotonously with magnetron current. The deposition rate at optimized deposition conditions was 0.7 nm of the Pt nanocluster film per second. Deposited films were porous and composed of 4 nm Pt nanoclusters. The nanoclusters were metallic and no sights of their oxidation were observed after 1 year on open air as witnessed by X-ray photoelectron spectroscopy. Regarding the electrical properties, a dramatic decrease of the resistivity was observed with increasing amount of deposited nanoclusters. This decrease saturated for the films approximately 50 nm thick. Such behavior indicates transition between different mechanisms of electrical conductivity: charge hopping for thin discontinuous films and current conduction through conducting path formed when higher amount of nanoclusters is deposited. Different mechanisms of electrical conduction for thin and thick layers of Pt were confirmed by subsequent investigation of temperature dependence of resistivity. In addition, no changes in resistivity were observed after one year on open air that confirms stability of produced Pt nanocluster films. - Highlights: • Pt nanocluster films were deposited by gas aggregation nanocluster source. • Conditions leading to effective deposition of Pt nanocluster films were found. • Deposited nanocluster films have good temporal stability. • Electrical properties of Pt films were found to depend on their thickness.

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

    Science.gov (United States)

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

    2016-09-14

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

  18. Planktic foraminifera form their shells via metastable carbonate phases

    OpenAIRE

    Jacob, D. E.; Wirth, R.; Agbaje, O. B. A.; Branson, O.; Eggins, S. M.

    2017-01-01

    The calcium carbonate shells of planktic foraminifera provide our most valuable geochemical archive of ocean surface conditions and climate spanning the last 100 million years, and play an important role in the ocean carbon cycle. These shells are preserved in marine sediments as calcite, the stable polymorph of calcium carbonate. Here, we show that shells of living planktic foraminifers Orbulina universa and Neogloboquadrina dutertrei originally form from the unstable calcium carbonate polym...

  19. Ab initio Investigation of Helium in Vanadium Oxide Nanoclusters

    Science.gov (United States)

    Danielson, Thomas; Tea, Eric; Hin, Celine

    Nanostructured ferritic alloys (NFAs) are strong candidate materials for the next generation of fission reactors and future fusion reactors. They are characterized by a large number density of oxide nanoclusters dispersed throughout a BCC iron matrix, where current oxide nanoclusters are primarily comprised of Y-Ti-O compounds. The oxide nanoclusters provide the alloy with high resistance to neutron irradiation, high yield strength and high creep strength at the elevated temperatures of a reactor environment. In addition, the oxide nanoclusters serve as trapping sites for transmutation product helium providing substantially increased resistance to catastrophic cracking and embrittlement. Although the mechanical properties and radiation resistance of the existing NFAs is promising, the problem of forming large scale reactor components continues to present a formidable challenge due to the high hardness and unpredictable fracture behavior of the alloys. An alternative alloy has been previously proposed and fabricated where vanadium is added in order to form vanadium oxide nanoclusters that serve as deflection sites for crack propagation. Although experiments have shown evidence that the fracture behavior of the alloys is improved, it is unknown whether or not the vanadium oxide nanoclusters are effective trapping sites for helium. We present results obtained using density functional theory investigating the thermodynamic stability of helium with the vanadium oxide matrix to make a comparison of trapping effectiveness to traditional Y-Ti-O compounds.

  20. 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.

  1. An asymmetric supercapacitor with ultrahigh energy density based on nickle cobalt sulfide nanocluster anchoring multi-wall carbon nanotubes hybrid

    Science.gov (United States)

    Wen, Ping; Fan, Mingjin; Yang, Desuo; Wang, Yan; Cheng, Hualei; Wang, Jinqing

    2016-07-01

    The development of novel electrode materials with high energy density and long cycling life is critical to realize electrochemical capacitive energy storage for practical applications. In this paper, the hybrids of nickle cobalt sulfide/multi-wall carbon nanotubes (NiCo2S4/MWCNTs) with different contents of MWCNTs are prepared using a facile one-pot solvothermal reaction. As novel active materials for supercapacitors, the electrochemistry tests show that the hybrid of NiCo2S4/MWCNTs-5 is able to deliver a high specific capacitance of 2080 F g-1 at the current density of 1 A g-1, even superior rate capability of 61% capacitance retention after a 20-fold increase in current densities, when the content of MWCNTs is up to 5%. More importantly, an asymmetric supercapacitor assembled by NiCo2S4/MWCNTs-5 as positive electrode and reduced graphene oxide (rGO) as negative electrode delivers a high energy density of 51.8 Wh Kg-1 at a power density of 865 W kg-1, and 85.7% of its initial capacitance is retained at the current density of 4 A g-1 after 5000 charge-discharge cycles, exhibiting potential prospect for practical applications.

  2. Multilayered nanoclusters of platinum and gold: insights on electrodeposition pathways, electrocatalysis, surface and bulk compositional properties

    CSIR Research Space (South Africa)

    Mkwizu, TS

    2013-06-01

    Full Text Available Electrochemical, surface and bulk compositional properties of multilayered nanoclusters of Pt and Au, electrochemically deposited on glassy carbon under conditions involving sequential surface–limited redox–replacement reactions (performed at open...

  3. Carbon nanotubes and methods of forming same at low temperature

    Science.gov (United States)

    Biris, Alexandru S.; Dervishi, Enkeleda

    2017-05-02

    In one aspect of the invention, a method for growth of carbon nanotubes includes providing a graphitic composite, decorating the graphitic composite with metal nanostructures to form graphene-contained powders, and heating the graphene-contained powders at a target temperature to form the carbon nanotubes in an argon/hydrogen environment that is devoid of a hydrocarbon source. In one embodiment, the target temperature can be as low as about 150.degree. C. (.+-.5.degree. C.).

  4. 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.

  5. Activated carbon fibers and engineered forms from renewable resources

    Science.gov (United States)

    Baker, Frederick S

    2013-02-19

    A method of producing activated carbon fibers (ACFs) includes the steps of providing a natural carbonaceous precursor fiber material, blending the carbonaceous precursor material with a chemical activation agent to form chemical agent-impregnated precursor fibers, spinning the chemical agent-impregnated precursor material into fibers, and thermally treating the chemical agent-impregnated precursor fibers. The carbonaceous precursor material is both carbonized and activated to form ACFs in a single step. The method produces ACFs exclusive of a step to isolate an intermediate carbon fiber.

  6. Expansion-limited aggregation of nanoclusters in a single-pulse laser-produced plume

    International Nuclear Information System (INIS)

    Gamaly, E. G.; Madsen, N. R.; Rode, A. V.; Golberg, D.

    2009-01-01

    Formation of carbon nanoclusters in a single-laser-pulse created ablation plume was studied both in vacuum and in a noble gas environment at various pressures. The developed theory provides cluster radius dependence on combination of laser parameters, properties of ablated material, and type and pressure of an ambient gas in agreement with experiments. The experiments were performed on carbon nanoclusters formed by laser ablation of graphite targets with 12 picosecond 532 nm laser pulses at MHz-range repetition rate in a broad range of ambient He, Ar, Kr, and Xe gas pressures from 2x10 -2 to 1500 Torr. The experimental results confirmed our theoretical prediction that the average size of the nanoparticles depends weakly on the type of the ambient gas used, and is determined exclusively by the single laser pulse parameters even at the repetition rate as high as 28 MHz with the time gap 36 ns between the pulses. The most important finding relates to the fact that in vacuum the cluster size is mainly determined by hydrodynamic expansion of the plume while in the ambient gas it is controlled by atomic diffusion in the gas. We demonstrate that the ultrashort pulses can be used for production of clusters with the size less than the critical value, which separates the particles with properties drastically different from those of a material in a bulk. The presented results of experiments on formation of carbon nanoclusters are in close agreement with the theoretical scaling. The developed theory is applicable for cluster formation from any monatomic material, such as silicon for example.

  7. Pt, Co–Pt and Fe–Pt alloy nanoclusters encapsulated in virus capsids

    International Nuclear Information System (INIS)

    Okuda, M; Eloi, J-C; Jones, S E Ward; Schwarzacher, W; Verwegen, M; Cornelissen, J J L M

    2016-01-01

    Nanostructured Pt-based alloys show great promise, not only for catalysis but also in medical and magnetic applications. To extend the properties of this class of materials, we have developed a means of synthesizing Pt and Pt-based alloy nanoclusters in the capsid of a virus. Pure Pt and Pt-alloy nanoclusters are formed through the chemical reduction of [PtCl 4 ] − by NaBH 4 with/without additional metal ions (Co or Fe). The opening and closing of the ion channels in the virus capsid were controlled by changing the pH and ionic strength of the solution. The size of the nanoclusters is limited to 18 nm by the internal diameter of the capsid. Their magnetic properties suggest potential applications in hyperthermia for the Co–Pt and Fe–Pt magnetic alloy nanoclusters. This study introduces a new way to fabricate size-restricted nanoclusters using virus capsid. (paper)

  8. Generalized rate-equation analysis of excitation exchange between silicon nanoclusters and erbium ions

    International Nuclear Information System (INIS)

    Kenyon, A. J.; Wojdak, M.; Ahmad, I.; Loh, W. H.; Oton, C. J.

    2008-01-01

    We discuss the use of rate equations to analyze the sensitization of erbium luminescence by silicon nanoclusters. In applying the general form of second-order coupled rate-equations to the Si nanocluster-erbium system, we find that the photoluminescence dynamics cannot be described using a simple rate equation model. Both rise and fall times exhibit a stretched exponential behavior, which we propose arises from a combination of a strongly distance-dependent nanocluster-erbium interaction, along with the finite size distribution and indirect band gap of the silicon nanoclusters. Furthermore, the low fraction of erbium ions that can be excited nonresonantly is a result of the small number of ions coupled to nanoclusters

  9. Thermal Oxidation of a Carbon Condensate Formed in High-Frequency Carbon and Carbon-Nickel Plasma Flow

    Science.gov (United States)

    Churilov, G. N.; Nikolaev, N. S.; Cherepakhin, A. V.; Dudnik, A. I.; Tomashevich, E. V.; Trenikhin, M. V.; Bulina, N. G.

    2018-02-01

    We have reported on the comparative characteristics of thermal oxidation of a carbon condensate prepared by high-frequency arc evaporation of graphite rods and a rod with a hollow center filled with nickel powder. In the latter case, along with different forms of nanodisperse carbon, nickel particles with nickel core-carbon shell structures are formed. It has been found that the processes of the thermal oxidation of carbon condensates with and without nickel differ significantly. Nickel particles with the carbon shell exhibit catalytic properties with respect to the oxidation of nanosized carbon structures. A noticeable difference between the temperatures of the end of the oxidation process for various carbon nanoparticles and nickel particles with the carbon shell has been established. The study is aimed at investigations of the effect of nickel nanoparticles on the dynamics of carbon condensate oxidation upon heating in the argon-oxygen flow.

  10. Atomically Precise Nanocluster Assemblies Encapsulating Plasmonic Gold Nanorods.

    Science.gov (United States)

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

    2018-04-01

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

  11. Effect of cold rolling on the formation and distribution of nanoclusters during pre-aging in an Al–Mg–Si alloy

    International Nuclear Information System (INIS)

    Serizawa, A.; Sato, T.; Miller, M.K.

    2013-01-01

    The effect of high densities of dislocations on the formation behavior of two types of nano-scale clusters (nanoclusters), which are formed at room temperature or during pre-aging at ∼373 K in an Al–Mg–Si alloy, was investigated by atom probe tomography. Cold rolling was applied to modify the formation behavior and/or the characteristics of the nanoclusters and also the precipitation sequence, which involve both nanoclusters and a strengthening phase to improve the bake-hardening response. Nanoclusters formed during pre-aging tended to form along the dislocations. Cold rolling accelerated the preferential formation of the nanoclusters, whereas the number density of the nanoclusters decreased by cold rolling before pre-aging. However, the number density of the nanoclusters was considerably higher than that of the β″ phase. Cold rolling before pre-aging enhanced the age-hardenability the most compared with other processes such as the contemporary pre-aging process. It is considered that the nanoclusters along dislocations lead to the preferential transformation to the β″ phase and then the rapid growth of the β″ phase. The nanoclusters formed on dislocations are effective in improving the bake-hardening response for the duration of the bake-hardening process. The kinetics and the distribution of the nanoclusters were found to be affected by the dislocations which were induced by cold rolling.

  12. Planktic foraminifera form their shells via metastable carbonate phases.

    Science.gov (United States)

    Jacob, D E; Wirth, R; Agbaje, O B A; Branson, O; Eggins, S M

    2017-11-02

    The calcium carbonate shells of planktic foraminifera provide our most valuable geochemical archive of ocean surface conditions and climate spanning the last 100 million years, and play an important role in the ocean carbon cycle. These shells are preserved in marine sediments as calcite, the stable polymorph of calcium carbonate. Here, we show that shells of living planktic foraminifers Orbulina universa and Neogloboquadrina dutertrei originally form from the unstable calcium carbonate polymorph vaterite, implying a non-classical crystallisation pathway involving metastable phases that transform ultimately to calcite. The current understanding of how planktic foraminifer shells record climate, and how they will fare in a future high-CO 2 world is underpinned by analogy to the precipitation and dissolution of inorganic calcite. Our findings require a re-evaluation of this paradigm to consider the formation and transformation of metastable phases, which could exert an influence on the geochemistry and solubility of the biomineral calcite.

  13. Mechanism behind the formation of self-assembled nano-sized clusters in diamond-like carbon nanocomposite.

    Science.gov (United States)

    Foong, Yuan Mei; Koh, Angel Ting Ting; Niu, Lifang; Chua, Daniel Hock Chuan

    2011-12-01

    Many studies have shown that Diamond-like carbon (DLC) films with diversified material properties are obtainable through doping process but the presence of the dopants were reported to form independent nanoclusters within the carbon matrix. Using combined analysis from theoretical estimations (Saha's equation and coefficient of absorption, alpha(p)), Transport of Ions In Matter (TRIM) simulation and experimental results, this work examined the mechanism behind the formation of self-assembled nanoclusters in DLC nanocomposite. We showed that the presence of metal dopants increased the heat dissipation on DLC, which allowed the energetic metal species to diffuse and enhance the formation of nanoclusters that increased the surface roughness of the films. In addition, TRIM and X-ray Photoelectron Spectroscopy (XPS) hinted the presence of energetic species may force the carbon ions to react with the interface to form silicon carbide bonds, which may be a more dominant factor compared to internal stress reduction in improving the adhesion strength of DLC.

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

    DEFF Research Database (Denmark)

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

    2007-01-01

    This paper reports the formation of Ge nanoclusters in silica glass thin films deposited by plasma-enhanced chemical vapor deposition (PECVD). We studied the samples by transmission electron microscopy (TEM) and Raman spectroscopy after annealing. TEM investigation shows that the Ge nanoclusters...... at two areaswere formed by different mechanisms. The Ge nanoclusters formed in a single row along the interface of a silicon substrate and the silica glass film by annealing during high-temperature heat treatment. Ge nanoclusters did not initially form in the bulk of the film but could be subsequently...... formed by the electron-beam irradiation. The interface between the silicon substrate and the silica glass film was investigated by Raman spectroscopy. The shift of the Raman peaks around 286.8 cm−1 and 495 cm−1 suggests that the interface is a Si1−xGex alloy film and that the composition x varies along...

  15. Encapsulation of nanoclusters in dried gel materials via an inverse micelle/sol gel synthesis

    Science.gov (United States)

    Martino, Anthony; Yamanaka, Stacey A.; Kawola, Jeffrey S.; Showalter, Steven K.; Loy, Douglas A.

    1998-01-01

    A dried gel material sterically entrapping nanoclusters of a catalytically active material and a process to make the material via an inverse micelle/sol-gel synthesis. A surfactant is mixed with an apolar solvent to form an inverse micelle solution. A salt of a catalytically active material, such as gold chloride, is added along with a silica gel precursor to the solution to form a mixture. To the mixture are then added a reducing agent for the purpose of reducing the gold in the gold chloride to atomic gold to form the nanoclusters and a condensing agent to form the gel which sterically entraps the nanoclusters. The nanoclusters are normally in the average size range of from 5-10 nm in diameter with a monodisperse size distribution.

  16. Organization of copper nanoclusters in Langmuir–Blodgett films

    Indian Academy of Sciences (India)

    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.

  17. Creep Forming of Carbon-Reinforced Ceramic-Matrix Composites

    Science.gov (United States)

    Vaughn, Wallace L.; Scotti, Stephan J.; Ashe, Melissa P.; Connolly, Liz

    2007-01-01

    A set of lecture slides describes an investigation of creep forming as a means of imparting desired curvatures to initially flat stock plates of carbon-reinforced ceramic-matrix composite (C-CMC) materials. The investigation is apparently part of a continuing effort to develop improved means of applying small CCMC repair patches to reinforced carbon-carbon leading edges of aerospace vehicles (e.g., space shuttles) prior to re-entry into the atmosphere of the Earth. According to one of the slides, creep forming would be an intermediate step in a process that would yield a fully densified, finished C-CMC part having a desired size and shape (the other steps would include preliminary machining, finish machining, densification by chemical vapor infiltration, and final coating). The investigation included experiments in which C-CMC disks were creep-formed by heating them to unspecified high temperatures for time intervals of the order of 1 hour while they were clamped into single- and double-curvature graphite molds. The creep-formed disks were coated with an oxidation- protection material, then subjected to arc-jet tests, in which the disks exhibited no deterioration after exposure to high-temperature test conditions lasting 490 seconds.

  18. The new carbon forms in the scientific instrumentation

    International Nuclear Information System (INIS)

    Saniger B, J.M.

    1999-01-01

    Applications in the development of scientific instrumentation of some of the new forms of carbon are discussed in this work. A short revision is presented of the remaining technical problems of the applications of diamond thin films as active semiconductor elements; heat sinks; X-ray, UV and particle detectors; surface acoustic wave devices, etc. Some advances in the improvement of the surface quality and textural design of diamond films are also presented. On the other hand, the possible implications of carbon nano tubes in scientific instrumentation are also discussed mainly for the development of electronic nano devices. Finally, other promising applications of carbon nano tubes as nano tips for atomic force and scanning tunneling microscopes, as well as nano-host structures for the synthesis of metallic carbide and nitride nano wires are also presented. (Author)

  19. Off-gas treatment carbon footprint calculator : form and function

    Energy Technology Data Exchange (ETDEWEB)

    Kessell, L. [Good EarthKeeping Organization Inc., Corona, CA (United States); Squire, J.; Crosby, K. [Haley and Aldrich Inc., Boston, MA (United States)

    2008-07-01

    Carbon footprinting is the measurement of the impact on the environment in terms of the amount of greenhouse gases produced, measured in units of carbon dioxide released directly and indirectly by an individual, organization, process, event or product. This presentation discussed an off-gas treatment carbon footprint calculator. The presentation provided a review of off-gas treatment technologies and presented a carbon footprint model. The model included: form and function; parameters; assumptions; calculations; and off-gas treatment applications. Parameters of the model included greenhouse gases listed in the Kyoto Protocol to the United Nations Framework Convention on Climate Change, such as carbon dioxide, methane, nitrous oxide, sulfur hexafluoride, hydrofluorocarbons, and perfluorocarbons. Assumptions of the model included stationary combustion emissions; mobile combustion emissions; indirect emissions; physical or chemical processing emissions; fugitive emissions; and de minimus emissions. The presentation also examined resource conservation and discussed three greenhouse gas footprint case studies. It was concluded that the model involved a calculator with standard calculations with clearly defined assumptions with boundaries. tabs., figs.

  20. 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.

  1. Alternative waste form development - low-temperature pyrolytic carbon coatings

    International Nuclear Information System (INIS)

    Oma, K.H.; Rusin, J.M.; Kidd, R.W.; Browning, M.F.

    1981-01-01

    Although several chemical vapor deposition (CVD) - coated waste forms have been successfully produced, some major disadvantages associated with the high-temperature fluidized-bed CVD coating process exist. To overcome these disadvantages, the Pacific Northwest Laboratory has initiated the development of a pyrolytic carbon CVD coating system to coat large waste-form particles at temperatures ranging from 400 to 500/degree/C. This relatively simple system has been used to coat kilogram quantities of simulated waste-glass marbles. Further development of this system could result in a viable process to coat bulk quantities of both glass and ceramic waste forms. This paper discusses various aspects of the development work, including coating techniques, parametric study, and coater equipment. 10 refs

  2. Hypoparathyroidism: what is the best calcium carbonate supplementation intake form?

    Science.gov (United States)

    Gollino, Loraine; Biagioni, Maria Fernanda Giovanetti; Sabatini, Nathalia Regina; Tagliarini, José Vicente; Corrente, José Eduardo; Paiva, Sérgio Alberto Rupp de; Mazeto, Gláucia Maria Ferreira da Silva

    2017-11-15

    In hypoparathyroidism, calcium supplementation using calcium carbonate is necessary for the hypocalcemia control. The best calcium carbonate intake form is unknown, be it associated with feeding, juice or in fasting. The objective was to evaluate the calcium, phosphorus and Calcium×Phosphorus product serum levels of hypoparathyroidism women after total thyroidectomy, following calcium carbonate intake in three different forms. A crossover study was carried out with patients presenting definitive hypoparathyroidism, assessed in different situations (fasting, with water, orange juice, breakfast with a one-week washout). Through the review of clinical data records of tertiary hospital patients from 1994 to 2010, 12 adult women (18 50 years old) were identified and diagnosed with definitive post-thyroidectomy hypoparathyroidism. The laboratory results of calcium and phosphorus serum levels dosed before and every 30min were assessed, for 5h, after calcium carbonate intake (elementary calcium 500mg). The maximum peak average values for calcium, phosphorus and Calcium×Phosphorus product were 8.63mg/dL (water), 8.77mg/dL (orange juice) and 8.95mg/dL (breakfast); 4.04mg/dL (water), 4.03mg/dL (orange juice) and 4.12mg/dL (breakfast); 34.3mg 2 /dL 2 (water), 35.8mg 2 /dL 2 (orange juice) and 34.5mg 2 /dL 2 (breakfast), respectively, and the area under the curve 2433mg/dLmin (water), 2577mg/dLmin (orange juice) and 2506mg/dLmin (breakfast), 1203mg/dLmin (water), 1052mg/dLmin (orange juice) and 1128mg/dLmin (breakfast), respectively. There was no significant difference among the three different tests (p>0.05). The calcium, phosphorus and Calcium×Phosphorus product serum levels evolved in a similar fashion in the three calcium carbonate intake forms. Copyright © 2017 Associação Brasileira de Otorrinolaringologia e Cirurgia Cérvico-Facial. Published by Elsevier Editora Ltda. All rights reserved.

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

    International Nuclear Information System (INIS)

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

    2014-01-01

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

  4. Evolution of embedded lithium nanoclusters in lithium implanted alumina

    International Nuclear Information System (INIS)

    Gaikwad, P.V.; Sharma, S.K.; Mukherjee, S.; Sudarshan, K.; Kshirsagar, A.; Pujari, P.K.

    2016-01-01

    High dose of ion implantation followed by annealing is considered a feasible way to generate thermally stable nanoclusters inside a transparent host matrix. Low energy (50 keV) Li ions have been implanted into single crystals of alumina with different fluence (1 × 10"1"5–1 × 10"1"7 ions/cm"2). The samples have been annealed at temperatures ranging from 500 to 1100 °C in air in step of 100 °C. Depth dependent Doppler broadening measurements have been carried out using high purity germanium detector coupled to a variable energy slow positron beam. Fractional area in the central and wing regions of Doppler broadened annihilation radiation spectrum, namely, S- and W- parameters, were evaluated from each spectrum. Any variation in positron annihilation probability with valence and core electrons which occurs on trapping of positrons at a defect site is reflected in these parameters. The effect of ion fluence and annealing temperature on evolution of defects and formation of embedded Li nanoclusters have been studied by indexing the variation in line shape S- (W-) parameter as a function of positron implantation depth. These studies supplemented by theoretical calculations confirm that with annealing up to 700 °C, vacancy clusters are created due to the aggregation of vacancies wherein Li nanoclusters are formed. On annealing at higher temperature, there is evidence for the breakdown of these Li clusters leaving behind vacancy clusters in the samples. - Highlights: • Embedded Li nanoclusters are efficiently created by annealing Li implanted Al_2O_3 crystal. • Depth dependent DBAR is a suitable method to characterize embedded nanoclusters. • The formation of Li nanoclusters is assisted by vacancy migration to form clusters. • At very high annealing temperature (>1000 °C), Li nanoclusters undergo breakdown. • e"+ annihilation at V_A_l site shows a unique observation i.e. a reduction in S-parameter.

  5. Synthesis of Co–Al layered double hydroxide nanoclusters as reduction nanocatalyst in aqueous media

    Directory of Open Access Journals (Sweden)

    Daisuke Kino

    2017-12-01

    Full Text Available Layered double hydroxides (LDHs have attracted attention as green materials due to their catalytic ability in benign aqueous solvents. We here demonstrate the synthesis of colloidal Co–Al LDH nanoclusters with an average size of <10 nm via a facile liquid-phase reaction for the enhancement of the catalytic activity. To the best of our knowledge, the present LDH is the smallest Co–Al LDH with an extremely large surface area and stability in an aqueous solvent, forming a stable and concentrated colloidal solution as high as 40 g/L. We investigated the formation mechanism, and the catalytic activity of Co–Al LDH nanoclusters. The Co–Al LDH nanoclusters showed 47 times higher rate of the reduction of dye molecules in the aqueous media than standard Co–Al LDH particles with a micrometer size. LDH nanoclusters demonstrated here are promising green nanocatalysts for the aqueous reaction processes.

  6. In Situ Formed Phosphoric Acid/Phosphosilicate Nanoclusters in the Exceptional Enhancement of Durability of Polybenzimidazole Membrane Fuel Cells at Elevated High Temperatures

    DEFF Research Database (Denmark)

    Zhang, Jin; Aili, David; Bradley, John

    2017-01-01

    -meso-silica. The results indicate that the optimum limit of PWA-meso-silica loading in the PA/PBI membranes is 15 wt%. Detaled analysis indicates that the mesoporous structure of the PWA-meso-silica framework disintegrates, forming phosphosilicate phases within the PBI polymeric matrix during fuel cell operation at 200°C......Most recently, we developed a phosphotungstic acid impregnated mesoporous silica (PWA-meso-silica) and phosphoric acid doped polybenzimidazole (PA/PBI) composite membrane for use in high temperature fuel cells and achieved exceptional durability under a constant current load of 200 mA cm−2 at 200°C...... for over 2700 h. In this work, the fundamental role of PWA-meso-silica in enhancing the stability of the PA/PBI membrane has been investigated. The microstructure, the PA uptake, swelling ratio, mechanical property and conductivity of PA/PBI/PWA-meso-silica composite membranes depend on the loading of PWA...

  7. Phenomenological model of nanocluster in polymer matrix

    International Nuclear Information System (INIS)

    Oksengendler, B.L.; Turaeva, N.N.; Azimov, J.; Rashidova, S.Sh.

    2010-01-01

    The phenomenological model of matrix nanoclusters is presented based on the Wood-Saxon potential used in nuclear physics. In frame of this model the following problems have been considered: calculation of width of diffusive layer between nanocluster and matrix, definition of Tamm surface electronic state taking into account the diffusive layer width, receiving the expression for specific magnetic moment of nanoclusters taking into account the interface width. (authors)

  8. Nanocluster production for solar cell applications

    International Nuclear Information System (INIS)

    Al Dosari, Haila M.; Ayesh, Ahmad I.

    2013-01-01

    This research focuses on the fabrication and characterization of silver (Ag) and silicon (Si) nanoclusters that might be used for solar cell applications. Silver and silicon nanoclusters have been synthesized by means of dc magnetron sputtering and inert gas condensation inside an ultra-high vacuum compatible system. We have found that nanocluster size distributions can be tuned by various source parameters, such as the sputtering discharge power, flow rate of argon inert gas, and aggregation length. Quadrupole mass filter and transmission electron microscopy were used to evaluate the size distribution of Ag and Si nanoclusters. Ag nanoclusters with average size in the range of 3.6–8.3 nm were synthesized (herein size refers to the nanocluster diameter), whereas Si nanoclusters' average size was controlled to range between 2.9 and 7.4 nm by controlling the source parameters. This work illustrates the ability of controlling the Si and Ag nanoclusters' sizes by proper optimization of the operation conditions. By controlling nanoclusters' sizes, one can alter their surface properties to suit the need to enhance solar cell efficiency. Herein, Ag nanoclusters were deposited on commercial polycrystalline solar cells. Short circuit current (I SC ), open circuit voltage (V OC ), fill factor, and efficiency (η) were obtained under light source with an intensity of 30 mW/cm 2 . A 22.7% enhancement in solar cell efficiency could be measured after deposition of Ag nanoclusters, which demonstrates that Ag nanoclusters generated in this work are useful to enhance solar cell efficiency

  9. Platinum-gold nanoclusters as catalyst for direct methanol fuel cells.

    Science.gov (United States)

    Giorgi, L; Giorgi, R; Gagliardi, S; Serra, E; Alvisi, M; Signore, M A; Piscopiello, E

    2011-10-01

    Nanosized platinum-gold alloys clusters have been deposited on gas diffusion electrode by sputter deposition. The deposits were characterized by FE-SEM, TEM and XPS in order to verify the formation of alloy nanoparticles and to study the influence of deposition technique on the nanomorphology. The deposition by sputtering process allowed a uniform distribution of metal particles on porous surface of carbon supports. Typical island growth mode was observed with the formation of a dispersed metal nanoclusters (mean size about 5 nm). Cyclic voltammetry was used to determine the electrochemical active surface and the electrocatalytic performance of the PtAu electrocatalysts for methanol oxidation reaction. The data were re-calculated in the form of mass specific activity (MSA). The sputter-catalyzed electrodes showed higher performance and stability compared to commercial catalysts.

  10. Possibility of superradiance by magnetic nanoclusters

    International Nuclear Information System (INIS)

    Yukalov, V I; Yukalova, E P

    2011-01-01

    The possibility of realizing spin superradiance by an assembly of magnetic nanoclusters is analyzed. The known obstacles for realizing such a coherent radiation by magnetic nanoclusters are their large magnetic anisotropy, strong dephasing dipole interactions, and an essential nonuniformity of their sizes. In order to give a persuasive conclusion, a microscopic theory is developed, providing an accurate description of nanocluster spin dynamics. It is shown that, despite the obstacles, it is feasible to organize such a setup that magnetic nanoclusters would produce strong superradiant emission

  11. Kernel Tuning and Nonuniform Influence on Optical and Electrochemical Gaps of Bimetal Nanoclusters.

    Science.gov (United States)

    He, Lizhong; Yuan, Jinyun; Xia, Nan; Liao, Lingwen; Liu, Xu; Gan, Zibao; Wang, Chengming; Yang, Jinlong; Wu, Zhikun

    2018-03-14

    Fine tuning nanoparticles with atomic precision is exciting and challenging and is critical for tuning the properties, understanding the structure-property correlation and determining the practical applications of nanoparticles. Some ultrasmall thiolated metal nanoparticles (metal nanoclusters) have been shown to be precisely doped, and even the protecting staple metal atom could be precisely reduced. However, the precise addition or reduction of the kernel atom while the other metal atoms in the nanocluster remain the same has not been successful until now, to the best of our knowledge. Here, by carefully selecting the protecting ligand with adequate steric hindrance, we synthesized a novel nanocluster in which the kernel can be regarded as that formed by the addition of two silver atoms to both ends of the Pt@Ag 12 icosohedral kernel of the Ag 24 Pt(SR) 18 (SR: thiolate) nanocluster, as revealed by single crystal X-ray crystallography. Interestingly, compared with the previously reported Ag 24 Pt(SR) 18 nanocluster, the as-obtained novel bimetal nanocluster exhibits a similar absorption but a different electrochemical gap. One possible explanation for this result is that the kernel tuning does not essentially change the electronic structure, but obviously influences the charge on the Pt@Ag 12 kernel, as demonstrated by natural population analysis, thus possibly resulting in the large electrochemical gap difference between the two nanoclusters. This work not only provides a novel strategy to tune metal nanoclusters but also reveals that the kernel change does not necessarily alter the optical and electrochemical gaps in a uniform manner, which has important implications for the structure-property correlation of nanoparticles.

  12. Chiral Gold Nanoclusters: Atomic Level Origins of Chirality.

    Science.gov (United States)

    Zeng, Chenjie; Jin, Rongchao

    2017-08-04

    Chiral nanomaterials have received wide interest in many areas, but the exact origin of chirality at the atomic level remains elusive in many cases. With recent significant progress in atomically precise gold nanoclusters (e.g., thiolate-protected Au n (SR) m ), several origins of chirality have been unveiled based upon atomic structures determined by using single-crystal X-ray crystallography. The reported chiral Au n (SR) m structures explicitly reveal a predominant origin of chirality that arises from the Au-S chiral patterns at the metal-ligand interface, as opposed to the chiral arrangement of metal atoms in the inner core (i.e. kernel). In addition, chirality can also be introduced by a chiral ligand, manifested in the circular dichroism response from metal-based electronic transitions other than the ligand's own transition(s). Lastly, the chiral arrangement of carbon tails of the ligands has also been discovered in a very recent work on chiral Au 133 (SR) 52 and Au 246 (SR) 80 nanoclusters. Overall, the origins of chirality discovered in Au n (SR) m nanoclusters may provide models for the understanding of chirality origins in other types of nanomaterials and also constitute the basis for the development of various applications of chiral nanoparticles. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. 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.

  14. Self-trapping nature of Tl nanoclusters on the Si(111)-7x7 surface

    International Nuclear Information System (INIS)

    Hwang, C G; Kim, N D; Lee, G; Shin, S Y; Kim, J S; Chung, J W

    2008-01-01

    We have studied properties of thallium (Tl) nanoclusters formed on the Si(111)-7x7 surface at room temperature (RT) by utilizing photoemission spectroscopy (PES) and high-resolution electron-energy-loss spectroscopy (HREELS) combined with first principles calculations. Our PES data reveal that the surface states stemming from the Si substrate remain quite inert with Tl adsorption producing no Tl-induced state until saturation at Tl coverage θ=0.21 monolayers. Such a behavior, in sharp contrast with the extremely reactive surface states upon the formation of Na or Li nanoclusters, together with the presence of a unique Tl-induced loss peak in HREELS spectra suggests no strong Si-Tl bonding, and is well understood in terms of gradual filling of Si dangling bonds with increasing θ. Our calculation further indicates the presence of several metastable atomic structures of Tl nanoclusters at RT rapidly transforming from one to another faster than 10 10 flippings per second. We thus conclude that the highly mobile Tl atoms form self-trapped nanoclusters within the attractive basins of the Si substrate at RT with several metastable phases. The mobile and multi-phased nature of Tl nanoclusters not only accounts for all the existing experimental observations available at present, but also provides an example of self-trapping of atoms in a nanometre-scale region

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

    Science.gov (United States)

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

    2017-09-01

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

  16. UV luminescence of dendrimer-encapsulated gold nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-10-15

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

  17. 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

  18. Real-time transmission electron microscope observation of gold nanoclusters diffusing into silicon at room temperature

    International Nuclear Information System (INIS)

    Ishida, Tadashi; Nakajima, Yuuki; Fujita, Hiroyuki; Endo, Junji; Collard, Dominique

    2009-01-01

    Gold diffusion into silicon at room temperature was observed in real time with atomic resolution. Gold nanoclusters were formed on a silicon surface by an electrical discharge between a silicon tip and a gold coated tip inside an ultrahigh-vacuum transmission electron microscope (TEM) specimen chamber. At the moment of the gold nanocluster deposition, the gold nanoclusters had a crystalline structure. The crystalline structure gradually disappeared due to the interdiffusion between silicon and gold as observed after the deposition of gold nanoclusters. The shape of the nanocluster gradually changed due to the gold diffusion into the damaged silicon. The diffusion front between silicon and gold moved toward the silicon side. From the observations of the diffusion front, the gold diffusivity at room temperature was extracted. The extracted activation energy, 0.21 eV, matched the activation energy in bulk diffusion between damaged silicon and gold. This information is useful for optimizing the hybridization between solid-state and biological nanodevices in which gold is used as an adhesive layer between the two devices.

  19. Prospects for using multi-walled carbon nanotubes formed from renewable feedstock in hydrogen energy

    International Nuclear Information System (INIS)

    Onishchenko, D. V.

    2013-01-01

    Mechanoactivation of amorphous carbon synthesized from renewable feedstock promotes formation of multi-walled carbon nanotubes, and the best results were obtained using the feedstock of sphagnum moss. It is shown that the carbon nanotubes formed from different plant feedstock have a high sorption capacity with respect to hydrogen. (author)

  20. The third, molecular, form of carbon: fullerenes, carbon nanotubes and onions. Some physical properties of fullerites

    International Nuclear Information System (INIS)

    Zubov, V.I.

    2004-01-01

    A brief review is presented of the pre-history and discovery of fullerenes (and then carbon nanotubes) that make the third molecular form of carbon, and of various, predominantly physical, properties of fullerites, i.e. of crystals composed of fullerene molecules. Particular attention is being given to the intermolecular forces, especially at orientationally disordered phases. The Girifalco potential is presented for eight fullerenes from C 28 to C 96 and its generalization is made for the interactions between the different fullerene molecules, C m and C n . The thermodynamics properties of the high-temperature modifications of a family of the fullerites, from C 36 up to C 96 , calculated in equilibrium with their saturated vapors on the basis of the correlative method of the unsymmetrized self-consistent field that enables one to take into account the strong anharmonicity of the lattice vibrations, are discussed. The calculations were accomplished up to the temperature of loss of stability (spinodal point) T s . We compare our results with available experimental data. The behaviour of some characteristics is considered in their dependence on the number of atoms in the molecule. Using the Lindermann's melting criterion we estimate a possible melting curve for the C 60 fullerite. (orig.)

  1. Extension of the radiative lifetime of Wannier-Mott excitons in semiconductor nanoclusters

    International Nuclear Information System (INIS)

    Kukushkin, V. A.

    2015-01-01

    The purpose of the study is to calculate the radiative lifetime of Wannier-Mott excitons in three-dimensional potential wells formed of direct-gap narrow-gap semiconductor nanoclusters in wide-gap semiconductors and assumed to be large compared to the exciton radius. Calculations are carried out for the InAs/GaAs heterosystem. It is shown that, as the nanocluster dimensions are reduced to values on the order of the exciton radius, the exciton radiative lifetime becomes several times longer compared to that in a homogeneous semiconductor. The increase in the radiative lifetime is more pronounced at low temperatures. Thus, it is established that the placement of Wannier-Mott excitons into direct-gap semiconductor nanoclusters, whose dimensions are of the order of the exciton radius, can be used for considerable extension of the exciton radiative lifetime

  2. Positron confinement in embedded lithium nanoclusters

    Science.gov (United States)

    van Huis, M. A.; van Veen, A.; Schut, H.; Falub, C. V.; Eijt, S. W.; Mijnarends, P. E.; Kuriplach, J.

    2002-02-01

    Quantum confinement of positrons in nanoclusters offers the opportunity to obtain detailed information on the electronic structure of nanoclusters by application of positron annihilation spectroscopy techniques. In this work, positron confinement is investigated in lithium nanoclusters embedded in monocrystalline MgO. These nanoclusters were created by means of ion implantation and subsequent annealing. It was found from the results of Doppler broadening positron beam analysis that approximately 92% of the implanted positrons annihilate in lithium nanoclusters rather than in the embedding MgO, while the local fraction of lithium at the implantation depth is only 1.3 at. %. The results of two-dimensional angular correlation of annihilation radiation confirm the presence of crystalline bulk lithium. The confinement of positrons is ascribed to the difference in positron affinity between lithium and MgO. The nanocluster acts as a potential well for positrons, where the depth of the potential well is equal to the difference in the positron affinities of lithium and MgO. These affinities were calculated using the linear muffin-tin orbital atomic sphere approximation method. This yields a positronic potential step at the MgO||Li interface of 1.8 eV using the generalized gradient approximation and 2.8 eV using the insulator model.

  3. 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

  4. Application of carbon nanoclusters in electronics

    Science.gov (United States)

    Krachkovskaya, T. M.; Sahadji, G. V.; Emelyanov, A. S.; Silaeva, M. V.

    2018-04-01

    Nanocarbon material (Ugleron and Astralens) is used for the first time for the production of metal porous cathode (MPC). It can be assumed that its implementation in the MPC matrix can change the mechanism and rate of occurrence of three-phase reactions of formation of active elements and oxygen and, thereby, improve its emission properties. The new technology of manufacturing MPC is aimed at solving the problem of increasing the durability of electro vacuum devices - more than 100,000 hours. The obtained results are intended for use in technologies for manufacturing of electron sources for electro vacuum devices used in space communication and navigation systems. In addition, they can be useful for other areas of electronics that use a metal-porous thermal cathode as sources of electron emission. There are manufactured models with the use of Ugleron and Astralens in a sponge and emission substance. A layout using Ugleron in the emission substance is tested for durability and currently has an operating time of 40,000 hours. A model with the use of Astralens and Ugleron in a sponge and emission substance respectively is tested for maximum current density. To date, it shows results comparable to the standard cathode. However, there is a suggestion that cathodes with Astralens and Ugleron have a lower evaporation rate of the active substance. There is predicted longer durability than for the standard cathode at the same emissivity.

  5. Silver and copper nanoclusters in the lustre decoration of Italian Renaissance pottery: an EXAFS study

    Science.gov (United States)

    Padovani, S.; Borgia, I.; Brunetti, B.; Sgamellotti, A.; Giulivi, A.; D'Acapito, F.; Mazzoldi, P.; Sada, C.; Battaglin, G.

    Lustre is one of the most important decorative techniques of the Medieval and Renaissance pottery of the Mediterranean basin, capable of producing brilliant metallic reflections and iridescence. Following the recent finding that the colour of lustre decorations is mainly determined by copper and silver nanoclusters dispersed in the glaze layer, the local environment of copper and silver atoms has been studied by extended X-ray absorption fine structure (EXAFS) spectroscopy on original samples of gold and red lustre. It has been found that, in gold lustre, whose colour is attributed mainly to the silver nanocluster dispersion, silver is only partially present in the metallic form and copper is almost completely oxidised. In the red lustre, whose colour is attributed mainly to the copper nanocluster dispersion, only a fraction of copper is present in the metallic form. EXAFS measurements on red lustre, carried out in the total electron yield mode to probe only the first 150 nm of the glaze layer, indicated that in some cases lustre nanoclusters may be confined in a very thin layer close to the surface.

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

    Science.gov (United States)

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

    2012-09-12

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

  7. Morphological Evolution of Nanocluster Aggregates and Single Crystals in Alkaline Zinc Electrodeposition

    Energy Technology Data Exchange (ETDEWEB)

    Desai, D; Turney, DE; Anantharaman, B; Steingart, DA; Banerjee, S

    2014-04-24

    The morphology of Zn electrodeposits is studied on carbon-coated transmission electron microscopy grids. At low over-potentials (eta = -50 mV), the morphology develops by aggregation at two distinct length scales: similar to 5 nm diameter monocrystalline nanoclusters form similar to 50 nm diameter polycrystalline aggregates, and the aggregates form a branched network. Epitaxial (00 (0) over bar2) growth above an overpotential of vertical bar eta(c)vertical bar > 125 mV leads to the formation of hexagonal single crystals up to 2 mu m in diameter. Potentiostatic current transients were used to calculate the nucleation rate from Scharifker et al.'s model. The exp(eta) dependence of the nucleation rates indicates that atomistic nucleation theory explains the nucleation process better than Volmer-Weber theory. 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.

  8. Formation of nanoclusters of gadolinium atoms in silicon

    International Nuclear Information System (INIS)

    Iliev, Kh.M.; Saparniyazova, Z.M.; Ismajlov, K.A.; Madzhitov, M.Kh.

    2011-01-01

    A technology of stage wise low temperature diffusion of gadolinium into silicon that makes it possible to form nanoclusters of impurity atoms with a significant magnetic moment distributed throughout the volume of the material has been developed. It is shown that, unlike the samples obtained by high temperature diffusion doping, the samples prepared by the new technology do not have surface erosion, and alloys and silicides are not formed in the near surface region. Nanoclusters of impurity atoms of gadolinium in the volume of the crystal lattice of the silicon are studied using an MIK-5 infrared microscope. It is found that, in the stage wise low temperature diffusion, the temperature and time of the diffusion have an effect not only on the depth of penetration of the impurities but also on the sizes of the resulting clusters; these factors can also prevent the formation of clusters. The study of the effect of low temperature treatments on the size and distribution of clusters shows that, upon annealing in the temperature range of 500-700 degrees Celsius, the ordering of the clusters of gadolinium impurity atoms is observed. A further increase in the annealing temperature leads to the destruction of gadolinium clusters in the silicon bulk. (authors)

  9. 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

  10. Plasmon tsunamis on metallic nanoclusters.

    Science.gov (United States)

    Lucas, A A; Sunjic, M

    2012-03-14

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

  11. Conditions for forming composite carbon nanotube-diamond like carbon material that retain the good properties of both materials

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Wei, E-mail: wei.ren@helsinki.fi; Avchaciov, Konstantin; Nordlund, Kai [Department of Physics, University of Helsinki, P.O. Box 43, FIN-00014 Helsinki (Finland); Iyer, Ajai; Koskinen, Jari [Department of Materials Science and Engineering, School of Chemical Technology, Aalto University, P.O. Box 16200, 00076 Espoo (Finland); Kaskela, Antti; Kauppinen, Esko I. [NanoMaterials Group, Department of Applied Physics, Aalto University School of Science, P.O. Box 15100, 00076 Aalto (Finland)

    2015-11-21

    Carbon nanotubes are of wide interest due to their excellent properties such as tensile strength and electrical and thermal conductivity, but are not, when placed alone on a substrate, well resistant to mechanical wear. Diamond-like carbon (DLC), on the other hand, is widely used in applications due to its very good wear resistance. Combining the two materials could provide a very durable pure carbon nanomaterial enabling to benefit from the best properties of both carbon allotropes. However, the synthesis of high-quality diamond-like carbon uses energetic plasmas, which can damage the nanotubes. From previous works it is neither clear whether the quality of the tubes remains good after DLC deposition, nor whether the DLC above the tubes retains the high sp{sup 3} bonding fraction. In this work, we use experiments and classical molecular dynamics simulations to study the mechanisms of DLC formation on various carbon nanotube compositions. The results show that high-sp{sup 3}-content DLC can be formed provided the deposition conditions allow for sidewards pressure to form from a substrate close beneath the tubes. Under optimal DLC formation energies of around 40–70 eV, the top two nanotube atom layers are fully destroyed by the plasma deposition, but layers below this can retain their structural integrity.

  12. Enzymatic reduction of U60 nanoclusters by Shewanella oneidensis MR-1

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Qiang; Fein, Jeremy B. [Notre Dame Univ., IN (United States). Dept. of Civil and Environmental Engineering and Earth Sciences

    2018-04-01

    In this study, a series of reduction experiments were conducted using a representative uranyl peroxide nanocluster, U60 (K{sub 16}Li{sub 44}[UO{sub 2}(O{sub 2})OH]{sub 60}) and a bacterial species, Shewanella oneidensis MR-1, that is capable of enzymatic U(VI) reduction. U60 was reduced by S. oneidensis in the absence of O{sub 2}, but the reduction kinetics for U60 were significantly slower than was observed in this study for aqueous uranyl acetate, and were faster than was reported in previous studies for solid phase U(VI). Our results indicate that U60 aggregates bigger than 0.2 μm formed immediately upon mixing with the bacterial growth medium, and that these aggregates were gradually broken down during the process of reduction. Neither reduction nor dissolution of U60 was observed during 72 h of control experiments open to the atmosphere, indicating that the breakdown and dissolution of U60 aggregates is caused by the reduction of U60, and that S. oneidensis is capable of direct reduction of the U(VI) within the U60 nanoclusters, likely due to the adsorption of U60 aggregates onto bacterial cells. This study is first to show the reduction capacity of bacteria for uranyl peroxide nanoclusters, and the results yield a better understanding of the long term fate of uranium in environmental systems in which uranyl peroxide nanoclusters are present.

  13. Surface mediated assembly of small, metastable gold nanoclusters

    Science.gov (United States)

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

    2013-06-01

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

  14. Fragmentation of neutral carbon clusters formed by high velocity atomic collision; Fragmentation d'agregats de carbone neutres formes par collision atomique a haute vitesse

    Energy Technology Data Exchange (ETDEWEB)

    Martinet, G

    2004-05-01

    The aim of this work is to understand the fragmentation of small neutral carbon clusters formed by high velocity atomic collision on atomic gas. In this experiment, the main way of deexcitation of neutral clusters formed by electron capture with ionic species is the fragmentation. To measure the channels of fragmentation, a new detection tool based on shape analysis of current pulse delivered by semiconductor detectors has been developed. For the first time, all branching ratios of neutral carbon clusters are measured in an unambiguous way for clusters size up to 10 atoms. The measurements have been compared to a statistical model in microcanonical ensemble (Microcanonical Metropolis Monte Carlo). In this model, various structural properties of carbon clusters are required. These data have been calculated with Density Functional Theory (DFT-B3LYP) to find the geometries of the clusters and then with Coupled Clusters (CCSD(T)) formalism to obtain dissociation energies and other quantities needed to compute fragmentation calculations. The experimental branching ratios have been compared to the fragmentation model which has allowed to find an energy distribution deposited in the collision. Finally, specific cluster effect has been found namely a large population of excited states. This behaviour is completely different of the atomic carbon case for which the electron capture in the ground states predominates. (author)

  15. Theoretical Studies of Nanoclusters (Briefing Charts)

    Science.gov (United States)

    2015-07-23

    nanoclusters. However, scanning transmission electron microscopy ( STEM ) measures show cluster inversion occurred to produce MgyCux(!) a) copper atoms b...methane (née CLL -1) as a potential explosive ingredient: a theoretical study”, Propellants, Explosives, Pyrotechnics 38, 9-13 (2013). Jesus Paulo L

  16. Peptide-stabilized, fluorescent silver nanoclusters

    DEFF Research Database (Denmark)

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

    2016-01-01

    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...

  17. Fluorescent Pressure Response of Protein-Nanocluster Polymer Composites

    Science.gov (United States)

    2016-05-01

    composites as pressure sensitive indicators of brain damage. The PNC composites are made up of protein coated gold nanoclusters and a styrene-ethylene...enhancement of the BSA- protected gold nanoclusters and the corresponding conformational changes of protein, J Phys Chem C. 2013;117:639–647...public release; distribution is unlimited. 13. SUPPLEMENTARY NOTES 14. ABSTRACT This research focuses on the uses of polymer gold nanocluster (PNC

  18. Experimental measurements of U60 nanocluster stability in aqueous solution

    Science.gov (United States)

    Flynn, Shannon L.; Szymanowski, Jennifer E. S.; Gao, Yunyi; Liu, Tianbo; Burns, Peter C.; Fein, Jeremy B.

    2015-05-01

    In this study, the aqueous behavior of isolated U60 nanoclusters (K16Li25[UO2(O2)OH]60)-19 was studied under several pH conditions and nanocluster concentrations to determine if the nanoclusters exhibit solid phase buffering behavior or if they exhibit behavior more like aqueous complexes. U60 is a cage cluster consisting of 60 (UO2)(O2)2(OH)2 uranyl polyhedral which share OH and O2 groups with their neighboring uranyl polyhedral, resulting in negatively charged cage clusters whose charge is at least partially offset by K+ and Li+ in the aqueous phase. Batch experiments to monitor nanocluster stability were conducted for 16 days at pH 7.5, 8.0 and 8.5 at nanocluster suspension concentrations of 1.4, 2.8 and 6.0 g/L. The aqueous concentrations of U, Li, and K, determined after 10 kDa molecular weight filtration, achieved steady-state with the nanoclusters within 24 h. The steady-state aqueous U, Li, and K concentrations were independent of solution pH, however they increased with increasing nanocluster concentration, indicating that the nanoclusters do not buffer the aqueous activities as a bulk solid phase would, but exhibit behavior that is more characteristic of dissolved aqueous complexes. The ion activity product (I.A.P.) value was calculated using two approaches: (1) treating the nanoclusters as a solid phase with an activity of one, and (2) treating the nanoclusters as aqueous complexes with a non-unit activity equal to their concentration in solution. The I.A.P. values that were calculated with non-unit activity for the nanoclusters exhibited significantly less variation as a function of nanocluster concentration compared to the I.A.P. values calculated with a nanocluster activity of one. The results yield a calculated log dissociation constant for the U60 nanoclusters of 9.2 + 0.2/-0.3 (1σ). Our findings provide a better understanding of the thermodynamic stability and behavior of U60 nanoclusters in aqueous systems, and can be used to estimate the

  19. Quantifying the linear and nonlinear relations between the urban form fragmentation and the carbon emission distribution

    Science.gov (United States)

    Zuo, S.; Dai, S.; Ren, Y.; Yu, Z.

    2017-12-01

    Scientifically revealing the spatial heterogeneity and the relationship between the fragmentation of urban landscape and the direct carbon emissions are of great significance to land management and urban planning. In fact, the linear and nonlinear effects among the various factors resulted in the carbon emission spatial map. However, there is lack of the studies on the direct and indirect relations between the carbon emission and the city functional spatial form changes, which could not be reflected by the land use change. The linear strength and direction of the single factor could be calculated through the correlation and Geographically Weighted Regression (GWR) analysis, the nonlinear power of one factor and the interaction power of each two factors could be quantified by the Geodetector analysis. Therefore, we compared the landscape fragmentation metrics of the urban land cover and functional district patches to characterize the landscape form and then revealed the relations between the landscape fragmentation level and the direct the carbon emissions based on the three methods. The results showed that fragmentation decreased and the fragmented patches clustered at the coarser resolution. The direct CO2 emission density and the population density increased when the fragmentation level aggregated. The correlation analysis indicated the weak linear relation between them. The spatial variation of GWR output indicated the fragmentation indicator (MESH) had the positive influence on the carbon emission located in the relatively high emission region, and the negative effects regions accounted for the small part of the area. The Geodetector which explores the nonlinear relation identified the DIVISION and MESH as the most powerful direct factor for the land cover patches, NP and PD for the functional district patches, and the interactions between fragmentation indicator (MESH) and urban sprawl metrics (PUA and DIS) had the greatly increased explanation powers on the

  20. Differential effects of ocean acidification on carbon acquisition in two bloom-forming dinoflagellate species

    NARCIS (Netherlands)

    Eberlein, T.; Van de Waal, D.B.; Rost, B.

    2014-01-01

    Dinoflagellates represent a cosmopolitan group of phytoplankton with the ability to form harmful algal blooms. Featuring a Ribulose-1,5-bisphosphate carboxylase/oxygenase (RubisCO) with very low CO2-affinities, photosynthesis of this group may be particularly prone to carbon limitation and thus

  1. Influence of changing carbonate chemistry on morphology and weight of coccoliths formed by Emiliania huxleyi

    Directory of Open Access Journals (Sweden)

    K. G. Schulz

    2012-08-01

    Full Text Available The coccolithophore Emiliania huxleyi is a marine phytoplankton species capable of forming small calcium carbonate scales (coccoliths which cover the organic part of the cell. Calcification rates of E. huxleyi are known to be sensitive to changes in seawater carbonate chemistry. It has, however, not yet been clearly determined how these changes are reflected in size and weight of individual coccoliths and which specific parameter(s of the carbonate system drive morphological modifications. Here, we compare data on coccolith size, weight, and malformation from a set of five experiments with a large diversity of carbonate chemistry conditions. This diversity allows distinguishing the influence of individual carbonate chemistry parameters such as carbon dioxide (CO2, bicarbonate (HCO3−, carbonate ion (CO32−, and protons (H+ on the measured parameters. Measurements of fine-scale morphological structures reveal an increase of coccolith malformation with decreasing pH suggesting that H+ is the major factor causing malformations. Coccolith distal shield area varies from about 5 to 11 μm2. Changes in size seem to be mainly induced by varying [HCO3−] and [H+] although influence of [CO32−] cannot be entirely ruled out. Changes in coccolith weight were proportional to changes in size. Increasing CaCO3 production rates are reflected in an increase in coccolith weight and an increase of the number of coccoliths formed per unit time. The combined investigation of morphological features and coccolith production rates presented in this study may help to interpret data derived from sediment cores, where coccolith morphology is used to reconstruct calcification rates in the water column.

  2. Hydrogen retention in carbon-tungsten co-deposition layer formed by hydrogen RF plasma

    International Nuclear Information System (INIS)

    Katayama, K.; Kawasaki, T.; Manabe, Y.; Nagase, H.; Takeishi, T.; Nishikawa, M.

    2006-01-01

    Carbon-tungsten co-deposition layers (C-W layers) were formed by sputtering method using hydrogen or deuterium RF plasma. The deposition rate of the C-W layer by deuterium plasma was faster than that by hydrogen plasma, where the increase of deposition rate of tungsten was larger than that of carbon. This indicates that the isotope effect on sputtering-depositing process for tungsten is larger than that for carbon. The release curve of hydrogen from the C-W layer showed two peaks at 400 deg. C and 700 deg. C. Comparing the hydrogen release from the carbon deposition layer and the tungsten deposition layer, it is considered that the increase of the release rate at 400 deg. C is affected by tungsten and that at 700 deg. C is affected by carbon. The obtained hydrogen retention in the C-W layers which have over 60 at.% of carbon was in the range between 0.45 and 0.16 as H/(C + W)

  3. High temperature, high heating rate carbonisation - a route to new forms of carbon

    International Nuclear Information System (INIS)

    Wilson, M. A.

    1998-01-01

    Carbonisation (more properly called pyrolysis) of coal has long been an important process for the good of mankind. It is relevant to coke making, the production of briquettes, the formation of specialist carbons such as anodes and other more exotic carbon forms. During heating, volatiles are produced and compounds containing carbon, hydrogen and oxygen are lost. The yield of volatiles and residues (inappropriately called char) depends on the rank of the coal used, the temperature of pyrolysis, and the heating rate. Mathematical models have been devised to account for loss of weight at constant heating rate, gas evolution, plasticity, swelling and changes in density, and other physical properties. Moreover chemical models of pyrolysis have also been devised. When carbon radicals are formed they may polymerize to form, if the correct number of hexagons or pentagons are present, a closed structure, such as the soccerball molecules. An account is given on the work carried out in Australia, at the University of Technology where the scientists were successful in identifying and then preparing buckyballs from coal rather than expensive graphite, first by laser pyrolysis and then by plasma arcing

  4. Primary estimation of forming date for carbonate weathering crust in Guizhou province

    International Nuclear Information System (INIS)

    Liu Chunru; Liu Xiuming; Wang Shijie; Wan Jinglin; Zheng Dewen

    2008-01-01

    The problem of directed dating of carbonate weathering crust in Guizhou Province hasn't been resolved. On the base of our previous study, we tested in detail the ages of antigenic quartz grains by fission track dating method and give a limitation of the forming date to carbonate weathering crust. The results show that the age of Xinpu profile is younger than 8.5 Ma, and the age of Guanba profile is younger than 7.3 Ma, and the age of Daxing profile is younger than 4.6 Ma. (authors)

  5. Interfacial electron transfer dynamics of photosensitized zinc oxide nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Murakoshi, Kei; Yanagida, Shozo [Osaka Univ. (Japan). Graduate School of Engineering; Capel, M. [Brookhaven National Lab., Upton, NY (United States)] [and others

    1997-06-01

    The authors have prepared and characterized photosensitized zinc oxide (ZnO) nanoclusters, dispersed in methanol, using carboxylated coumarin dyes for surface adsorption. Femtosecond time-resolved emission spectroscopy allows the authors to measure the photo-induced charge carrier injection rate constant from the adsorbed photosensitizer to the n-type semiconductor nanocluster. These results are compared with other photosensitized semiconductors.

  6. Synthesis and characterization of mixed ligand chiral nanoclusters

    KAUST Repository

    Guven, Zekiye P.

    2016-06-22

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

  7. Synthesis and characterization of mixed ligand chiral nanoclusters

    KAUST Repository

    Guven, Zekiye P.; Ustbas, Burcin; Harkness, Kellen M.; Coskun, Hikmet; Joshi, Chakra Prasad; Besong, Tabot M.D.; Stellacci, Francesco; Bakr, Osman; Akbulut, Ozge

    2016-01-01

    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. Molecular interactions in particular Van der Waals nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-04-01

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

  9. [Characteristics of organic carbon forms in the sediment of Wuliangsuhai and Daihai Lakes].

    Science.gov (United States)

    Mao, Hai-Fang; He, Jiang; Lü, Chang-Wei; Liang, Ying; Liu, Hua-Lin; Wang, Feng-Jiao

    2011-03-01

    The characteristics and differences of organic carbon forms in the sediments of the Wuliangsuhai and the Daihai Lakes with different eutrophication types were discussed in the present study. The results showed that the range of total organic carbon content (TOC) in Wuliangsuhai Lake was 4.50-22.83 g x kg(-1) with the average of 11.80 g x kg(-1). The range of heavy-fraction organic carbon content was 3.38-21.67 g x kg(-1) with the average of 10.76 g x kg(-1). The range of light-fraction organic carbon content was 0.46-1.80 g x kg(-1) with the average of 1.04 g x kg(-1); The range of ROC content was 0.62-3.64 g x kg(-1) with the average of 2.11 g x kg(-1), while the range of total organic carbon content in Daihai lake was 6.84-23.46 g x kg(-1) with the average of 14.94 g x kg(-1). The range of heavy-fraction organic carbon content was 5.27-22.23 g x kg(-1) with the average of 13.89 g x kg(-1). The range of light-fraction organic carbon content was 0.76-1.57 g x kg(-1). The range of ROC content was 1.54-7.08 g x kg(-1) with the average of 3.62 g x kg(-1). The results indicated that the heavy-fraction organic carbon was the major component of the organic carbon and plays an important role in the accumulation of organic carbon in the sediments of two Lakes. The content of light-fraction organic carbon was similar in the sediments of two lakes, whereas, the contents of total organic carbon and heavy-fraction organic carbon in the sediment of Wuliangsuhai Lake were less than those in the sediment of Daihai Lake, and the value of LFOC/TOC in the Wuliangsuhai Lake was larger than that in the Daihai Lake. The humin was the dominant component of the sediment humus, followed by fulvic acid in the two lakes. The values of HM/HS in the sediments of Wuliangsuhai lake range from 43.06% to 77.25% with the average of 62.15% and values of HM/HS in the sediments of Dahai lake range from 49.23% to 73.85% with the average of 65.30%. The tightly combined humus was the dominant form in

  10. Site of Er ions in silica layers codoped with Si nanoclusters and Er

    International Nuclear Information System (INIS)

    Pellegrino, P.; Garrido, B.; Arbiol, J.; Garcia, C.; Lebour, Y.; Morante, J.R.

    2006-01-01

    Silica layers implanted with Si and Er ions to various doses and annealed at 950 deg. C have been investigated by means of energy-filtered transmission electron microscopy (EFTEM) and high annular angle dark field (HAADF). EFTEM analysis reveals Si nanoclusters (Si-nc) with an average size around 3 nm for high Si content (15 at. %) whereas no clusters can be imaged for the lowest Si excess (5 at. %). Raman scattering supports that amorphous Si precipitates are present in all the samples. Moreover, the filtered images show that Er ions appear preferentially located outside the Si-nc. HAADF analysis confirms that the Er atoms form agglomerations of 5-10 nm size when the Er concentration exceeds 1x10 20 cm -3 . This observation correlates well with the reduction of the Er population excitable by Si nanoclusters, in the best case corresponding to 10% of the total. A suitable tuning of the annealing drastically reduces this deleterious effect

  11. Solventless acid-free synthesis of mesostructured titania: Nanovessels for metal complexes and metal nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Dag, Oe.; Celik, Oe.; Ozin, G.A. [Department of Chemistry, Bilkent University, 06533 Ankara (Turkey); Soten, I.; Polarz, S.; Coombs, N. [Materials Chemistry Research Group, Chemistry Department, University of Toronto, 80 St. George Street, Toronto, Ontario M5S 3H6 (Canada)

    2003-01-01

    A new and highly reproducible method to obtain mesostructured titania materials is introduced in this contribution. The mesostructured titania is obtained by employing self-assembled structures of non-ionic alkyl-poly(ethylene oxide) surfactants as templates. The materials are produced without additional solvents such as alcohols, or even water. Only the titanium(IV) ethoxide and the surfactant (C{sub 12}EO{sub 10}) are needed. Water, in the form of that attached to the surfactant and from the atmosphere, induces growth of titania nanoclusters in the synthesis sol. It is indicated that these nanoclusters interact with the surfactant EO-head groups to form a new titanotropic amphiphile. The new amphiphiles self-assemble into titanium nanocluster-surfactant hybrid lyotropic phases, which are transformed to the final mesostructured materials by further condensation of the titania network. The titania materials can be obtained also with noble-metal particles immobilized in the mesostructured framework. It is seen that when different metal salts are used as the metal precursors, different interactions with the titania walls are found. The materials are characterized by X-ray diffraction (XRD), polarization optical microscopy (POM), transmission electron microscopy (TEM), UV-vis spectroscopy, and micro-Raman analysis. (Abstract Copyright [2003], Wiley Periodicals, Inc.)

  12. Fragmentation of neutral carbon clusters formed by high velocity atomic collision

    International Nuclear Information System (INIS)

    Martinet, G.

    2004-05-01

    The aim of this work is to understand the fragmentation of small neutral carbon clusters formed by high velocity atomic collision on atomic gas. In this experiment, the main way of deexcitation of neutral clusters formed by electron capture with ionic species is the fragmentation. To measure the channels of fragmentation, a new detection tool based on shape analysis of current pulse delivered by semiconductor detectors has been developed. For the first time, all branching ratios of neutral carbon clusters are measured in an unambiguous way for clusters size up to 10 atoms. The measurements have been compared to a statistical model in microcanonical ensemble (Microcanonical Metropolis Monte Carlo). In this model, various structural properties of carbon clusters are required. These data have been calculated with Density Functional Theory (DFT-B3LYP) to find the geometries of the clusters and then with Coupled Clusters (CCSD(T)) formalism to obtain dissociation energies and other quantities needed to compute fragmentation calculations. The experimental branching ratios have been compared to the fragmentation model which has allowed to find an energy distribution deposited in the collision. Finally, specific cluster effect has been found namely a large population of excited states. This behaviour is completely different of the atomic carbon case for which the electron capture in the ground states predominates. (author)

  13. Face-centered-cubic lithium crystals formed in mesopores of carbon nanofiber electrodes.

    Science.gov (United States)

    Lee, Byoung-Sun; Seo, Jong-Hyun; Son, Seoung-Bum; Kim, Seul Cham; Choi, In-Suk; Ahn, Jae-Pyoung; Oh, Kyu Hwan; Lee, Se-Hee; Yu, Woong-Ryeol

    2013-07-23

    In the foreseeable future, there will be a sharp increase in the demand for flexible Li-ion batteries. One of the most important components of such batteries will be a freestanding electrode, because the traditional electrodes are easily damaged by repeated deformations. The mechanical sustainability of carbon-based freestanding electrodes subjected to repeated electrochemical reactions with Li ions is investigated via nanotensile tests of individual hollow carbon nanofibers (HCNFs). Surprisingly, the mechanical properties of such electrodes are improved by repeated electrochemical reactions with Li ions, which is contrary to the conventional wisdom that the mechanical sustainability of carbon-based electrodes should be degraded by repeated electrochemical reactions. Microscopic studies reveal a reinforcing mechanism behind this improvement, namely, that inserted Li ions form irreversible face-centered-cubic (FCC) crystals within HCNF cavities, which can reinforce the carbonaceous matrix as strong second-phase particles. These FCC Li crystals formed within the carbon matrix create tremendous potential for HCNFs as freestanding electrodes for flexible batteries, but they also contribute to the irreversible (and thus low) capacity of HCNFs.

  14. SU-F-T-144: Analytical Closed Form Approximation for Carbon Ion Bragg Curves in Water

    Energy Technology Data Exchange (ETDEWEB)

    Tuomanen, S; Moskvin, V; Farr, J [St. Jude Children’s Research Hospital, Memphis, TN (United States)

    2016-06-15

    Purpose: Semi-empirical modeling is a powerful computational method in radiation dosimetry. A set of approximations exist for proton ion depth dose distribution (DDD) in water. However, the modeling is more complicated for carbon ions due to fragmentation. This study addresses this by providing and evaluating a new methodology for DDD modeling of carbon ions in water. Methods: The FLUKA, Monte Carlo (MC) general-purpose transport code was used for simulation of carbon DDDs for energies of 100–400 MeV in water as reference data model benchmarking. Based on Thomas Bortfeld’s closed form equation approximating proton Bragg Curves as a basis, we derived the critical constants for a beam of Carbon ions by applying models of radiation transport by Lee et. al. and Geiger to our simulated Carbon curves. We hypothesized that including a new exponential (κ) residual distance parameter to Bortfeld’s fluence reduction relation would improve DDD modeling for carbon ions. We are introducing an additional term to be added to Bortfeld’s equation to describe fragmentation tail. This term accounts for the pre-peak dose from nuclear fragments (NF). In the post peak region, the NF transport will be treated as new beams utilizing the Glauber model for interaction cross sections and the Abrasion- Ablation fragmentation model. Results: The carbon beam specific constants in the developed model were determined to be : p= 1.75, β=0.008 cm-1, γ=0.6, α=0.0007 cm MeV, σmono=0.08, and the new exponential parameter κ=0.55. This produced a close match for the plateau part of the curve (max deviation 6.37%). Conclusion: The derived semi-empirical model provides an accurate approximation of the MC simulated clinical carbon DDDs. This is the first direct semi-empirical simulation for the dosimetry of therapeutic carbon ions. The accurate modeling of the NF tail in the carbon DDD will provide key insight into distal edge dose deposition formation.

  15. Properties and potential of formed cokes derived from two Turkish lignites by carbonization of binderless briquettes

    Energy Technology Data Exchange (ETDEWEB)

    Bayraktur, K.N.; Lawson, G.J.

    1984-09-01

    Two high-sulphur Turkish lignites were briquetted at room temperature under pressures of 113 or 212 MPa and the briquettes were carbonized to 1158-1173 K over special heating cycles. The lowerrank lignite gave a formed coke of superior mechanical strength, lower porosity and higher sulphur content than typical blast furnace cokes. The formed coke produced from the higher-rank lignite briquettes had slightly poorer mechanical strength, lower porosity and much higher ash and sulphur content than conventional cokes. The products were considered attractive for use in non-ferrous metallurgy.

  16. Properties and potential of formed cokes derived from two Turkish lignites by carbonization of binderless briquettes

    Energy Technology Data Exchange (ETDEWEB)

    Bayraktar, K.N.; Lawson, G.J.

    1984-09-01

    Two high-sulphur Turkish lignites were briquetted at room temperature under pressures of 113 or 212 MPa and the briquettes were carbonized to 1158-1173 K over special heating cycles. The lower-rank lignite gave a formed coke of superior mechanical strength, lower porosity and higher sulphur content than typical blast furnace cokes. The formed coke produced from the higher-rank lignite briquettes had slightly poorer mechanical strength, lower porosity and much higher ash yield and sulphur content than conventional cokes. The products were considered attractive for use in non-ferrous metallurgy. 38 references.

  17. Multifunctional nanocomposites of carbon nanotubes and nanoparticles formed via vacuum filtration

    Science.gov (United States)

    Hersam, Mark C; Ostojic, Gordana; Liang, Yu Teng

    2013-10-22

    In one aspect, the present invention provides a method of forming a film of nanocomposites of carbon nanotubes (CNTs) and platinum (Pt) nanoparticles. In one embodiment, the method includes the steps of (a) providing a first solution that contains a plurality of CNTs, (b) providing a second solution that contains a plurality of Pt nanoparticles, (c) combining the first solution and the second solution to form a third solution, and (d) filtering the third solution through a nanoporous membrane using vacuum filtration to obtain a film of nanocomposites of CNTs and Pt nanoparticles.

  18. Platinum catalyst formed on carbon nanotube by the in-liquid plasma method for fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Show, Yoshiyuki; Hirai, Akira; Almowarai, Anas; Ueno, Yutaro

    2015-12-01

    In-liquid plasma was generated in the carbon nanotube (CNT) dispersion fluid using platinum electrodes. The generated plasma spattered the surface of the platinum electrodes and dispersed platinum particles into the CNT dispersion. Therefore, the platinum nanoparticles were successfully formed on the CNT surface in the dispersion. The platinum nanoparticles were applied to the proton exchange membrane fuel cell (PEMFC) as a catalyst. The electrical power of 108 mW/cm{sup 2} was observed from the fuel cell which was assembled with the platinum catalyst formed on the CNT by the in-liquid plasma method. - Highlights: • The platinum catalyst was successfully formed on the CNT surface in the dispersion by the in-liquid plasma method. • The electrical power of 108 mW/cm{sup 2} was observed from the fuel cell which was assembled with the platinum catalyst formed on the CNT by the in-liquid plasma method.

  19. Method for producing bio-fuel that integrates heat from carbon-carbon bond-forming reactions to drive biomass gasification reactions

    Science.gov (United States)

    Cortright, Randy D [Madison, WI; Dumesic, James A [Verona, WI

    2011-01-18

    A low-temperature catalytic process for converting biomass (preferably glycerol recovered from the fabrication of bio-diesel) to synthesis gas (i.e., H.sub.2/CO gas mixture) in an endothermic gasification reaction is described. The synthesis gas is used in exothermic carbon-carbon bond-forming reactions, such as Fischer-Tropsch, methanol, or dimethylether syntheses. The heat from the exothermic carbon-carbon bond-forming reaction is integrated with the endothermic gasification reaction, thus providing an energy-efficient route for producing fuels and chemicals from renewable biomass resources.

  20. Electronic Properties of Metallic Nanoclusters on Semiconductor Surfaces: Implications for Nanoelectronic Device Applications

    International Nuclear Information System (INIS)

    Lee, Takhee; Liu Jia; Chen, N.-P.; Andres, R.P.; Janes, D.B.; Reifenberger, R.

    2000-01-01

    We review current research on the electronic properties of nanoscale metallic islands and clusters deposited on semiconductor substrates. Reported results for a number of nanoscale metal-semiconductor systems are summarized in terms of their fabrication and characterization. In addition to the issues faced in large-area metal-semiconductor systems, nano-systems present unique challenges in both the realization of well-controlled interfaces at the nanoscale and the ability to adequately characterize their electrical properties. Imaging by scanning tunneling microscopy as well as electrical characterization by current-voltage spectroscopy enable the study of the electrical properties of nanoclusters/semiconductor systems at the nanoscale. As an example of the low-resistance interfaces that can be realized, low-resistance nanocontacts consisting of metal nanoclusters deposited on specially designed ohmic contact structures are described. To illustrate a possible path to employing metal/semiconductor nanostructures in nanoelectronic applications, we also describe the fabrication and performance of uniform 2-D arrays of such metallic clusters on semiconductor substrates. Using self-assembly techniques involving conjugated organic tether molecules, arrays of nanoclusters have been formed in both unpatterned and patterned regions on semiconductor surfaces. Imaging and electrical characterization via scanning tunneling microscopy/spectroscopy indicate that high quality local ordering has been achieved within the arrays and that the clusters are electronically coupled to the semiconductor substrate via the low-resistance metal/semiconductor interface

  1. 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

  2. Controllable growth and magnetic properties of nickel nanoclusters electrodeposited on the ZnO nanorod template

    International Nuclear Information System (INIS)

    Tang Yang; Zhao Dongxu; Shen Dezhen; Zhang Jiying; Wang Xiaohua

    2009-01-01

    The ZnO nanorods were used as a template to fabricate nickel nanoclusters by electrodeposition. The ZnO nanorod arrays act as a nano-semiconductor electrode for depositing metallic and magnetic nickel nanoclusters. The growth sites of Ni nanoclusters could be controlled by adjusting the applied potential. Under -1.15 V the Ni nanoclusters could be grown on the tips of ZnO nanorods. On increasing the potential to be more negative the ZnO nanorods were covered by Ni nanoclusters. The magnetic properties of the electrodeposited Ni nanoclusters also evolved with the applied potentials.

  3. Controllable growth and magnetic properties of nickel nanoclusters electrodeposited on the ZnO nanorod template

    Energy Technology Data Exchange (ETDEWEB)

    Tang Yang; Zhao Dongxu; Shen Dezhen; Zhang Jiying [Key Laboratory of Excited State Processes, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, 16 East Nan-Hu Road, Open Economic Zone, Changchun 130033 (China); Wang Xiaohua, E-mail: dxzhao2000@yahoo.com.c [National Key Laboratory of High Power Semiconductor Laser, Changchun University of Science and Technology, 7089 WeiXing Road, ChangChun 130022 (China)

    2009-12-09

    The ZnO nanorods were used as a template to fabricate nickel nanoclusters by electrodeposition. The ZnO nanorod arrays act as a nano-semiconductor electrode for depositing metallic and magnetic nickel nanoclusters. The growth sites of Ni nanoclusters could be controlled by adjusting the applied potential. Under -1.15 V the Ni nanoclusters could be grown on the tips of ZnO nanorods. On increasing the potential to be more negative the ZnO nanorods were covered by Ni nanoclusters. The magnetic properties of the electrodeposited Ni nanoclusters also evolved with the applied potentials.

  4. A dual amplified electrochemical immunosensor for ofloxacin: Polypyrrole film-Au nanocluster as the matrix and multi-enzyme-antibody functionalized gold nanorod as the label

    International Nuclear Information System (INIS)

    Zang, Shuai; Liu, Yingju; Lin, Mouhong; Kang, Jianli; Sun, Yuanming; Lei, Hongtao

    2013-01-01

    Graphical abstract: Schematic representation of the OFL electrochemical immunosensor using Au nanoclusters/PPy/GCE as the substrate and multi-HRP-GNR-Ab2 bioconjugates as the label. Highlights: ► Gold nanorod was used to load HRP and Ab 2 to form multi-HRP-GNR-Ab 2 . ► A sensitive immunosensor for ofloxacin was constructed using the homemade antibody. ► A dual signal amplified strategy was based on the PPy-Au and multi-HRP-GNR-Ab 2 . -- Abstract: In this work, an electrochemical immunosensor, basing on a dual signal amplified strategy by employing a biocompatible polypyrrole film-Au nanocluster matrix as a sensor platform and multi-enzyme-antibody functionalized gold nanorod as an electrochemical detection label, is established for sensitive detection of ofloxacin (OFL). Firstly, polypyrrole film and Au nanoclusters were progressively fabricated onto the surface of a glassy carbon electrode via electropolymerization and electrochemical deposition, respectively. Such PPy-Au nanocomposite modified electrode was used to immobilize OFL-OVA, blocked with the blocking reagent, and then associated with the corresponding antibody. Secondly, gold nanorod (GNR) was synthesized to load horseradish peroxidase (HRP) and horseradish peroxidase-secondary antibody (HRP-Ab 2 ), and the resulting nanostructure (multi-HRP-GNR-Ab 2 ) was applied as the detection label. The fabrication process of the ordered multilayer structure and immunosensor were characterized by scanning electron microscopy (SEM) and electrochemical measurements, respectively. Finally, based on a competitive immunoassay, i.e., the association ability with the corresponding antibody between the captured antigen and free OFL in the solution, the fabricated immunosensor exhibited a sensitive response to OFL in the range from 0.08 to 410 ng/mL with a detection limit of 0.03 ng/mL. The current immunosensor exhibited good sensitivity, selectivity and long-term stability. This amplification strategy shows excellent

  5. Electronic structure and orientation relationship of Li nanoclusters embedded in MgO studied by depth-selective positron annihilation two-dimensional angular correlation

    Science.gov (United States)

    Falub, C. V.; Mijnarends, P. E.; Eijt, S. W.; van Huis, M. A.; van Veen, A.; Schut, H.

    2002-08-01

    Quantum-confined positrons are sensitive probes for determining the electronic structure of nanoclusters embedded in materials. In this work, a depth-selective positron annihilation 2D-ACAR (two-dimensional angular correlation of annihilation radiation) method is used to determine the electronic structure of Li nanoclusters formed by implantation of 1016-cm-2 30-keV 6Li ions in MgO (100) and (110) crystals and by subsequent annealing at 950 K. Owing to the difference between the positron affinities of lithium and MgO, the Li nanoclusters act as quantum dots for positrons. 2D-ACAR distributions for different projections reveal a semicoherent fitting of the embedded metallic Li nanoclusters to the host MgO lattice. Ab initio Korringa-Kohn-Rostoker calculations of the momentum density show that the anisotropies of the experimental distributions are consistent with an fcc crystal structure of the Li nanoclusters. The observed reduction of the width of the experimental 2D-ACAR distribution is attributed to positron trapping in vacancies associated with Li clusters. This work proposes a method for studying the electronic structure of metallic quantum dots embedded in an insulating material.

  6. A cuboctahedral platinum (Pt79) nanocluster enclosed by well defined facets favours di-sigma adsorption and improves the reaction kinetics for methanol fuel cells.

    Science.gov (United States)

    Mahata, Arup; Choudhuri, Indrani; Pathak, Biswarup

    2015-08-28

    The methanol dehydrogenation steps are studied very systematically on the (111) facet of a cuboctahedral platinum (Pt79) nanocluster enclosed by well-defined facets. The various intermediates formed during the methanol decompositions are adsorbed at the edge and bridge site of the facet either vertically (through C- and O-centres) or in parallel. The di-sigma adsorption (in parallel) on the (111) facet of the nanocluster is the most stable structure for most of the intermediates and such binding improves the interaction between the substrate and the nanocluster and thus the catalytic activity. The reaction thermodynamics, activation barrier, and temperature dependent reaction rates are calculated for all the successive methanol dehydrogenation steps to understand the methanol decomposition mechanism, and these values are compared with previous studies to understand the catalytic activity of the nanocluster. We find the catalytic activity of the nanocluster is excellent while comparing with any previous reports and the methanol dehydrogenation thermodynamics and kinetics are best when the intermediates are adsorbed in a di-sigma manner.

  7. Building machine learning force fields for nanoclusters

    Science.gov (United States)

    Zeni, Claudio; Rossi, Kevin; Glielmo, Aldo; Fekete, Ádám; Gaston, Nicola; Baletto, Francesca; De Vita, Alessandro

    2018-06-01

    We assess Gaussian process (GP) regression as a technique to model interatomic forces in metal nanoclusters by analyzing the performance of 2-body, 3-body, and many-body kernel functions on a set of 19-atom Ni cluster structures. We find that 2-body GP kernels fail to provide faithful force estimates, despite succeeding in bulk Ni systems. However, both 3- and many-body kernels predict forces within an ˜0.1 eV/Å average error even for small training datasets and achieve high accuracy even on out-of-sample, high temperature structures. While training and testing on the same structure always provide satisfactory accuracy, cross-testing on dissimilar structures leads to higher prediction errors, posing an extrapolation problem. This can be cured using heterogeneous training on databases that contain more than one structure, which results in a good trade-off between versatility and overall accuracy. Starting from a 3-body kernel trained this way, we build an efficient non-parametric 3-body force field that allows accurate prediction of structural properties at finite temperatures, following a newly developed scheme [A. Glielmo et al., Phys. Rev. B 95, 214302 (2017)]. We use this to assess the thermal stability of Ni19 nanoclusters at a fractional cost of full ab initio calculations.

  8. The effect of silicon crystallographic orientation on the formation of silicon nanoclusters during anodic electrochemical etching

    International Nuclear Information System (INIS)

    Timokhov, D. F.; Timokhov, F. P.

    2009-01-01

    Possible ways for increasing the photoluminescence quantum yield of porous silicon layers have been investigated. The effect of the anodization parameters on the photoluminescence properties for porous silicon layers formed on silicon substrates with different crystallographic orientations was studied. The average diameters for silicon nanoclusters are calculated from the photoluminescence spectra of porous silicon. The influence of the substrate crystallographic orientation on the photoluminescence quantum yield of porous silicon is revealed. A model explaining the effect of the substrate orientation on the photoluminescence properties for the porous silicon layers formed by anode electrochemical etching is proposed.

  9. Metal nanoparticles as a conductive catalyst

    Science.gov (United States)

    Coker, Eric N [Albuquerque, NM

    2010-08-03

    A metal nanocluster composite material for use as a conductive catalyst. The metal nanocluster composite material has metal nanoclusters on a carbon substrate formed within a porous zeolitic material, forming stable metal nanoclusters with a size distribution between 0.6-10 nm and, more particularly, nanoclusters with a size distribution in a range as low as 0.6-0.9 nm.

  10. 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...... source in which the helium carrier gas was mixed with hydrogen. RBS revealed that oxidation of the Co nanoclusters is considerably reduced by the presence of hydrogen during cluster formation. The capping did not modify the influence of the passivation. The hydrogen passivation method is especially...... effective in cases when capping of the films is not desirable, for example for magnetic studies. Clear differences in the magnetic domain structures between hydrogen passivated and non-passivated Co nanocluster films were demonstrated by MFM and are attributed to a difference in inter-cluster magnetic...

  11. Adsorption of small gas molecules on B36 nanocluster

    Indian Academy of Sciences (India)

    Supplementary Information. Journal of Chemical Sciences. Adsorption of small gas molecules on B36 nanocluster. YOUNES VALADBEIGI. *. , HOSSEIN FARROKHPOUR and MAHMOUD TABRIZCHI. Department of chemistry, Isfahan University of Technology, Isfahan, 84156-83111, Iran. *. Corresponding Author: Younes ...

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

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa; Joshi, Chakra Prasad; Alhilaly, Mohammad J.; Bakr, Osman

    2016-01-01

    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

  13. Biological Apatite Formed from Polyphosphate and Alkaline Phosphatase May Exchange Oxygen Isotopes from Water through Carbonate

    Science.gov (United States)

    Omelon, S. J.; Stanley, S. Y.; Gorelikov, I.; Matsuura, N.

    2011-12-01

    The oxygen isotopic composition in bone mineral phosphate is known to reflect the local water composition, environmental humidity, and diet1. Once ingested, biochemical processes presumably equilibrate PO43- with "body water" by the many biochemical reactions involving PO43- 2. Blake et al. demonstrated that enzymatic release of PO43- from organophosphorus compounds, and microbial metabolism of dissolved orthophosphate, significantly exchange the oxygen in precipitated apatite within environmental water3,4, which otherwise does not exchange with water at low temperatures. One of the enzymes that can cleave phosphates from organic substrates is alkaline phosphastase5, the enzyme also associated with bone mineralization. The literature often states that the mineral in bone in hydroxylapatite, however the mineral in bone is carbonated apatite that also contains some fluoride6. Deprotonation of HPO32- occurs at pH 12, which is impossibly high for biological system, and the predominate carbonate species in solution at neutral pH is HCO3-. To produce an apatite mineral without a significant hydroxyl content, it is possible that apatite biomineralization occurs through a polyphosphate pathway, where the oxygen atom required to transform polyphosphate into individual phosphate ions is from carbonate: [PO3-]n + CO32- -> [PO3-]n-1 + PO43- + CO2. Alkaline phosphatase can depolymerise polyphosphate into orthophosphate5. If alkaline phosphatase cleaves an oxygen atom from a calcium-carbonate complex, then there is no requirement for removing a hydrogen atom from the HCO3- or HPO43- ions of body water to form bioapatite. A mix of 1 mL of 1 M calcium polyphosphate hydogel, or nano-particles of calcium polyphosphate, and amorphous calcium carbonate were reacted with alkaline phosphatase, and maintained at neutral to basic pH. After two weeks, carbonated apatite and other calcium phosphate minerals were identified by powder x-ray diffraction. Orthophosphate and unreacted

  14. Self-selection in size and structure in argon clusters formed on amorphous carbon

    Energy Technology Data Exchange (ETDEWEB)

    Krainyukova, Nina V.; Waal, Benjamin W. van de

    2004-07-01

    Argon clusters formed on an amorphous carbon substrate as deposited from the vapor phase were studied by means of transmission high energy electron diffraction using the liquid helium cryostat. Electron diffractograms were analysed on the basis of assumption that there exist a cluster size distribution in samples formed on substrate and multi-shell structures such as icosahedra, decahedra, fcc and hcp were probed for different sizes up to {approx}15 000 atoms. The experimental data were considered as a result of a superposition of diffracted intensities from clusters of different sizes and structures. The comparative analysis was based on the R-factor minimization that was found to be equal to 0.014 for the best fit between experiment and modelling. The total size and structure distribution function shows the presence of 'non-crystallographic' structures such as icosahedra and decahedra with five-fold symmetry that was found to prevail and a smaller amount of fcc and hcp structures. Possible growth mechanisms as well as observed general tendency to self-selection in sizes and structures are presumably governed by confined pore-like geometry in an amorphous carbon substrate.

  15. Positron annihilation 2D-ACAR study of semi-coherent Li nanoclusters in MgO(1 0 0) and MgO(1 1 0)

    International Nuclear Information System (INIS)

    Falub, C.V.; Mijnarends, P.E.; Eijt, S.W.H.; Huis, M.A. van; Veen, A. van; Schut, H.

    2002-01-01

    Depth selective positron annihilation two-dimensional angular correlation of annihilation radiation (2D-ACAR) is used to determine the electronic structure of Li nanoclusters formed by implantation of 10 16 cm -2 6 Li ions (with an energy of 30 keV) in MgO(1 0 0) and (1 1 0) crystals, and subsequently annealed at 950 K. The 2D-ACAR spectra of Li-implanted MgO obtained with 4 keV positrons reveal the semi-coherent ordering state of the embedded metallic Li nanoclusters. The results agree with ab initio Korringa-Kohn-Rostoker calculations

  16. Positron annihilation 2D-ACAR study of semi-coherent Li nanoclusters in MgO(1 0 0) and MgO(1 1 0)

    Energy Technology Data Exchange (ETDEWEB)

    Falub, C.V. E-mail: c.falub@iri.tudelft.nl; Mijnarends, P.E.; Eijt, S.W.H.; Huis, M.A. van; Veen, A. van; Schut, H

    2002-05-01

    Depth selective positron annihilation two-dimensional angular correlation of annihilation radiation (2D-ACAR) is used to determine the electronic structure of Li nanoclusters formed by implantation of 10{sup 16} cm{sup -2} {sup 6}Li ions (with an energy of 30 keV) in MgO(1 0 0) and (1 1 0) crystals, and subsequently annealed at 950 K. The 2D-ACAR spectra of Li-implanted MgO obtained with 4 keV positrons reveal the semi-coherent ordering state of the embedded metallic Li nanoclusters. The results agree with ab initio Korringa-Kohn-Rostoker calculations.

  17. Positron annihilation 2D-ACAR study of semi-coherent Li nanoclusters in MgO( 1 0 0 ) and MgO( 1 1 0 )

    Science.gov (United States)

    Falub, C. V.; Mijnarends, P. E.; Eijt, S. W. H.; van Huis, M. A.; van Veen, A.; Schut, H.

    2002-05-01

    Depth selective positron annihilation two-dimensional angular correlation of annihilation radiation (2D-ACAR) is used to determine the electronic structure of Li nanoclusters formed by implantation of 10 16 cm -26Li ions (with an energy of 30 keV) in MgO(1 0 0) and (1 1 0) crystals, and subsequently annealed at 950 K. The 2D-ACAR spectra of Li-implanted MgO obtained with 4 keV positrons reveal the semi-coherent ordering state of the embedded metallic Li nanoclusters. The results agree with ab initio Korringa-Kohn-Rostoker calculations.

  18. Computational modeling of electrically conductive networks formed by graphene nanoplatelet-carbon nanotube hybrid particles

    KAUST Repository

    Mora Cordova, Angel

    2018-01-30

    One strategy to ensure that nanofiller networks in a polymer composite percolate at low volume fractions is to promote segregation. In a segregated structure, the concentration of nanofillers is kept low in some regions of the sample. In turn, the concentration in remaining regions is much higher than the average concentration of the sample. This selective placement of the nanofillers ensures percolation at low average concentration. One original strategy to promote segregation is by tuning the shape of the nanofillers. We use a computational approach to study the conductive networks formed by hybrid particles obtained by growing carbon nanotubes (CNTs) on graphene nanoplatelets (GNPs). The objective of this study is (1) to show that the higher electrical conductivity of these composites is due to the hybrid particles forming a segregated structure and (2) to understand which parameters defining the hybrid particles determine the efficiency of the segregation. We construct a microstructure to observe the conducting paths and determine whether a segregated structure has indeed been formed inside the composite. A measure of efficiency is presented based on the fraction of nanofillers that contribute to the conductive network. Then, the efficiency of the hybrid-particle networks is compared to those of three other networks of carbon-based nanofillers in which no hybrid particles are used: only CNTs, only GNPs, and a mix of CNTs and GNPs. Finally, some parameters of the hybrid particle are studied: the CNT density on the GNPs, and the CNT and GNP geometries. We also present recommendations for the further improvement of a composite\\'s conductivity based on these parameters.

  19. Computational modeling of electrically conductive networks formed by graphene nanoplatelet-carbon nanotube hybrid particles

    Science.gov (United States)

    Mora, A.; Han, F.; Lubineau, G.

    2018-04-01

    One strategy to ensure that nanofiller networks in a polymer composite percolate at low volume fractions is to promote segregation. In a segregated structure, the concentration of nanofillers is kept low in some regions of the sample. In turn, the concentration in the remaining regions is much higher than the average concentration of the sample. This selective placement of the nanofillers ensures percolation at low average concentration. One original strategy to promote segregation is by tuning the shape of the nanofillers. We use a computational approach to study the conductive networks formed by hybrid particles obtained by growing carbon nanotubes (CNTs) on graphene nanoplatelets (GNPs). The objective of this study is (1) to show that the higher electrical conductivity of these composites is due to the hybrid particles forming a segregated structure and (2) to understand which parameters defining the hybrid particles determine the efficiency of the segregation. We construct a microstructure to observe the conducting paths and determine whether a segregated structure has indeed been formed inside the composite. A measure of efficiency is presented based on the fraction of nanofillers that contribute to the conductive network. Then, the efficiency of the hybrid-particle networks is compared to those of three other networks of carbon-based nanofillers in which no hybrid particles are used: only CNTs, only GNPs, and a mix of CNTs and GNPs. Finally, some parameters of the hybrid particle are studied: the CNT density on the GNPs, and the CNT and GNP geometries. We also present recommendations for the further improvement of a composite’s conductivity based on these parameters.

  20. Forming mechanism of the Ordovician karst carbonate reservoirs on the northern slope of central Tarim Basin

    Directory of Open Access Journals (Sweden)

    Heng Fu

    2017-07-01

    Full Text Available The Ordovician karst carbonate reservoirs on the northern slope of central Tarim Basin are important oil and gas exploration targets in the basin, but their dissolution mechanisms are in controversy. In this paper, based on the integrated study of sedimentation, sequence and reservoir, together with microscopic analysis and macroscopic seismic data analysis, the carbonate karst reservoirs in the study area were divided into three types: dissolved pore-cavity limestone reservoir, pore-cavity dolomite reservoir and fracture-cavity siliceous reservoir, and their forming mechanisms were discussed respectively. Some findings were obtained. First, dissolved pore-cavity limestone reservoirs are distributed in the upper Yingshan Fm and Yijianfang Fm of the Ordovician vertically, while pore-cavity dolomite reservoirs are mainly developed in the Penglai Fm and lower Yingshan Fm of the Ordovician with great thickness. Second, dissolved pore-cavity limestone reservoirs were formed by karstification on the third-order sequence boundary (lowstand tract, while pore-cavity dolomite reservoirs were formed by deep burial dolomitization controlled by karstification on the third-order sequence boundary, both of which are distributed in the highstand tract below the third-order sequence boundary. Third, siliceous reservoirs are developed under the control of faulting, as a result of reworking of deep hydrothermal fluids along faults to the limestone, and the siliceous reservoirs and their hydrothermal solution fracture-cavity systems are distributed near faults. It is further predicted that, in addition to the three types of reservoir above, platform-margin reef-flat reservoirs are developed in the Ordovician on the northern slope of central Tarim Basin.

  1. Computational modeling of electrically conductive networks formed by graphene nanoplatelet-carbon nanotube hybrid particles

    KAUST Repository

    Mora Cordova, Angel; Han, Fei; Lubineau, Gilles

    2018-01-01

    One strategy to ensure that nanofiller networks in a polymer composite percolate at low volume fractions is to promote segregation. In a segregated structure, the concentration of nanofillers is kept low in some regions of the sample. In turn, the concentration in remaining regions is much higher than the average concentration of the sample. This selective placement of the nanofillers ensures percolation at low average concentration. One original strategy to promote segregation is by tuning the shape of the nanofillers. We use a computational approach to study the conductive networks formed by hybrid particles obtained by growing carbon nanotubes (CNTs) on graphene nanoplatelets (GNPs). The objective of this study is (1) to show that the higher electrical conductivity of these composites is due to the hybrid particles forming a segregated structure and (2) to understand which parameters defining the hybrid particles determine the efficiency of the segregation. We construct a microstructure to observe the conducting paths and determine whether a segregated structure has indeed been formed inside the composite. A measure of efficiency is presented based on the fraction of nanofillers that contribute to the conductive network. Then, the efficiency of the hybrid-particle networks is compared to those of three other networks of carbon-based nanofillers in which no hybrid particles are used: only CNTs, only GNPs, and a mix of CNTs and GNPs. Finally, some parameters of the hybrid particle are studied: the CNT density on the GNPs, and the CNT and GNP geometries. We also present recommendations for the further improvement of a composite's conductivity based on these parameters.

  2. Comparison between two forms of granular activated carbon for the removal of pharmaceuticals from different waters.

    Science.gov (United States)

    Lima, Lisandra; Baêta, Bruno E L; Lima, Diego R S; Afonso, Robson J C F; de Aquino, Sérgio F; Libânio, Marcelo

    2016-01-01

    The aim of this study was to evaluate the performance of two forms of basic granular activated carbon (GAC), mineral (pH = 10.5) and vegetal (pH = 9), for the removal of three pharmaceuticals, as sulphamethoxazole (SMX), diclofenac (DCF) and 17β-estradiol (E2), from two different matrices: fortified distilled (2.4-3.0 mg L(-1) and pH from 5.5 to 6.5) and natural (∼1.0 mg L(-1) and pH from 7.1 to 7.2) water in a bench scale. The Rapid Small-Scale Column Test used to assess the ability of mineral and vegetal GAC on removal of such pharmaceuticals led to removal capacities varying from 14.9 to 23.5 mg g(-1) for E2, from 23.7 to 24.2 mg g(-1) for DCF and from 20.5 to 20.6 mg g(-1) for SMX. Removal efficiencies of 71%, 88% and 74% for DCF, SMX and E2, respectively, were obtained at breakthrough point when using mineral GAC, whereas for the vegetal GAC the figures were 76%, 77% and 65%, respectively. The carbon usage rate at the breakthrough point varied from 11.9 to 14.5 L g(-1) for mineral GAC and from 8.8 to 14.8 L g(-1) for vegetal GAC. Mineral CAG also exhibited the best performance when treating fortified natural water, since nearly complete removal was observed for all contaminants in the column operated for 22 h at a carbon usage rate of 2.9 L g(-1).

  3. 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...

  4. Open site tests on corrosion of carbon steel containers for radioactive waste forms

    International Nuclear Information System (INIS)

    Barinov, A.S.; Ojovan, M.I.; Ojovan, N.V.; Startceva, I.V.; Chujkova, G.N.

    1999-01-01

    Testing of waste containers under open field conditions is a component part of the research program that is being carried out at SIA Radon for more than 20 years to understand the long-term behavior of radioactive waste forms and waste packages. This paper presents the preliminary results of these ongoing studies. The authors used a typical NPP operational waste, containing 137 Cs, 134 Cs, and 60 Co as the dominant radioactive constituents. Bituminized and vitrified waste samples with 30--50 wt.% waste loading were prepared. Combined effects of climatic factors on corrosion behavior of carbon steel containers were estimated using gravimetric and chemical analyses. The observations suggest that uniform corrosion of containers prevails under open field conditions. The upper limits for the lifetime of containers were derived from calculations based on the model of atmospheric steel corrosion. Estimated lifetime values range from 300 to 600 years for carbon steel containers with the wall thickness of 2 mm containing vitrified waste, and from 450 to 500 years for containers with the wall thickness of 2.5 mm that were used for bituminized waste. However, following the most conservative method, pitting corrosion may cause container integrity failure after 60 to 90 years of exposure

  5. The bacterial carbon-fixing organelle is formed by shell envelopment of preassembled cargo.

    Directory of Open Access Journals (Sweden)

    Anna H Chen

    Full Text Available Cyanobacteria play a significant role in the global carbon cycle. In Synechococcuselongatus, the carbon-fixing enzyme ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO is concentrated into polyhedral, proteinaceous compartments called carboxysomes.Using live cell fluorescence microscopy, we show that carboxysomes are first detected as small seeds of RuBisCO that colocalize with existing carboxysomes. These seeds contain little or no shell protein, but increase in RuBisCO content over several hours, during which time they are exposed to the solvent. The maturing seed is then enclosed by shell proteins, a rapid process that seals RuBisCO from the cytosol to establish a distinct, solvent-protected microenvironment that is oxidizing relative to the cytosol. These closure events can be spatially and temporally coincident with the appearance of a nascent daughter RuBisCO seed.Carboxysomes assemble in a stepwise fashion, inside-to-outside, revealing that cargo is the principle organizer of this compartment's biogenesis. Our observations of the spatial relationship of seeds to previously formed carboxysomes lead us to propose a model for carboxysome replication via sequential fission, polymerization, and encapsulation of their internal cargo.

  6. 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.

  7. Dynamics of Oxidation of Aluminum Nanoclusters using Variable Charge Molecular-Dynamics Simulations on Parallel Computers

    Science.gov (United States)

    Campbell, Timothy; Kalia, Rajiv K.; Nakano, Aiichiro; Vashishta, Priya; Ogata, Shuji; Rodgers, Stephen

    1999-06-01

    Oxidation of aluminum nanoclusters is investigated with a parallel molecular-dynamics approach based on dynamic charge transfer among atoms. Structural and dynamic correlations reveal that significant charge transfer gives rise to large negative pressure in the oxide which dominates the positive pressure due to steric forces. As a result, aluminum moves outward and oxygen moves towards the interior of the cluster with the aluminum diffusivity 60% higher than that of oxygen. A stable 40 Å thick amorphous oxide is formed; this is in excellent agreement with experiments.

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

    International Nuclear Information System (INIS)

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

    2011-01-01

    Human transferrin has been biolabelled with gold nanoclusters (Au NCs) using a simple, fast and non-toxic method. These nanocrystals ( 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 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.

  9. Study of the effect of magnesium concentration on the deposit of allotropic forms of calcium carbonate and related carbon steel interface behavior

    International Nuclear Information System (INIS)

    Ben Amor, Y.; Bousselmi, L.; Tribollet, B.; Triki, E.

    2010-01-01

    Different allotropic forms of calcium carbonate scales were electrochemically deposited on a carbon steel surface in artificial underground Tunisian water at -0.95 V SCE and various Mg 2+ concentrations. Because of the importance of the diffusion process, the rotating disk electrode was used. The deposition kinetics were analyzed by chronoamperometry measurements and the calcareous layers were characterized by electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM). The physical model proposed by Gabrielli was used to analyze the EIS measurements. Independent of the deposited allotropic form of calcium carbonate, the measurements showed that the oxygen reduction occurs in the pores formed between the CaCO 3 crystals and the metallic surface.

  10. 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

  11. Study of nanocluster-assembled ZnO thin films by nanocluster-beam deposition

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Zhiwei; Lei, Wei; Zhang, Xiaobing [School of Electronic Science and Engieering, Southeast University, Nanjing (China); Tay, Beng Kang [School of Electronical and Electronic Engineering, Nanyang Technological University, Nanyang (Singapore)

    2012-01-15

    Nanocluster-assembled ZnO thin films were obtained by nanocluster-beam deposition, in which nanoclusters were produced by a magnetron sputtering gas aggregation source. Two kinds of ZnO thin films were obtained using this method with the one grown under the on-line heating temperature of 700 C, and the other grown without on-line heating. Film microstructure and optical properties are investigated by various diagnostic techniques. It was found that both of film microstructure of ZnO thin films keep wurtzite structure as that of ZnO bulk materials. The averaged particle size for the film grown without on-line heating is around 6 nm, which is a little lower than that grown with the on-line heating. It was also found that as increasing the wavelength, both of the absorbance spectra for the films decrease sharply near ultra-visible to extend slowly to the visible and infrared wavelength range. For the film grown without on-line heating, the bandgap energy was estimated to 3.77 eV, while for the film grown with on-line heating, the bandgap energy was redshift to 3.71 eV. Similar behavior was also found for PL spectra analysis, where PL spectrum exhibited a peak centered at 3.31 eV without on-line heating, while it redshift to 3.20 eV with on-line heating. The mechanisms behind these behaviors were presented in this article. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  12. Cluster perturbation theory for calculation of electronic properties of ensembles of metal nanoclusters

    Science.gov (United States)

    Zhumagulov, Yaroslav V.; Krasavin, Andrey V.; Kashurnikov, Vladimir A.

    2018-05-01

    The method is developed for calculation of electronic properties of an ensemble of metal nanoclusters with the use of cluster perturbation theory. This method is applied to the system of gold nanoclusters. The Greens function of single nanocluster is obtained by ab initio calculations within the framework of the density functional theory, and then is used in Dyson equation to group nanoclusters together and to compute the Greens function as well as the electron density of states of the whole ensemble. The transition from insulator state of a single nanocluster to metallic state of bulk gold is observed.

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

    Science.gov (United States)

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

    2012-06-01

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

  14. Filterability of corrosion products formed between carbon steel and water. Influence of temperature and oxygen content

    International Nuclear Information System (INIS)

    Kelen, T.; Falk, I.

    1975-09-01

    A laboratory investigation has been made for the purpose of studying the influence of temperature and oxygen content on the filterability of corrosion products formed between carbon-steel and water. The experiments were performed in a high temperature loop where the water is initially heated in a pre-heater, then cooled and finally filtered. The corrosion products were transferred to thewater from a carbon-steel surface that had previously been neutron activated and the amount of iron present was determined from measurements of the γ-radiation emitted by Fe-59. Filterability was then computed as the ratio between the total amount of iron in the water phase and the amount of iron retained on the filter. The investigation covers a series of experiments at filtering temperatures of 20, 90 and 160 dec G, pre-heater temperatures up to 300 deg C and oxygen contents of 10 and 300 ppb O 2 . In addition the extent of iron deposition in the pre-heater and heat regulator has been determined after each series of experiments. Filterability exhibited a pronounced dependence upon both the filter and pre-heater temperatures and also upon the oxygen content. Among the conclusions to which the results lead is the observation that a strict comparison of filterability values for the fraction of corrosion products in cooled water samples is impossible when these are taken from 1) different sections of a high temperature system 2) a single sampling point while the system is being run up 3) two separate systems (e.g. steam boilers) operated at different temperatures 4) two separate systems operated at different oxygen contents. It accordingly appears advizable to restrict the use of cold-filtered samples from conventional steam-raising plants to the comparison of values relating to a single sampling point under constant operating conditions. (author)

  15. Observations concerning the particle-size of the oxidation products of uranium formed in air or in carbon dioxide

    International Nuclear Information System (INIS)

    Baque, P.; Leclercq, D.

    1964-01-01

    This report brings together the particle-size analysis results obtained on products formed by the oxidation or the ignition of uranium in moist air or dry carbon dioxide. The results bring out the importance of the nature of the oxidising atmosphere, the combustion in moist air giving rise to the formation of a larger proportion of fine particles than combustion in carbon dioxide under pressure. (authors) [fr

  16. Nanocluster irradiation evolution in Fe-9%Cr ODS and ferritic-martensitic alloys

    Science.gov (United States)

    Swenson, M. J.; Wharry, J. P.

    2017-12-01

    The objective of this study is to evaluate the influence of dose rate and cascade morphology on nanocluster evolution in a model Fe-9%Cr oxide dispersion strengthened steel and the commercial ferritic/martensitic (F/M) alloys HCM12A and HT9. We present a large, systematic data set spanning the three alloys, three irradiating particle types, four orders of magnitude in dose rate, and doses ranging 1-100 displacements per atom over 400-500 °C. Nanoclusters are characterized using atom probe tomography. ODS oxide nanoclusters experience partial dissolution after irradiation due to inverse Ostwald ripening, while F/M nanoclusters undergo Ostwald ripening. Damage cascade morphology is indicative of nanocluster number density evolution. Finally, the effects of dose rate on nanocluster morphology provide evidence for a temperature dilation theory, which purports that a negative temperature shift is necessary for higher dose rate irradiations to emulate nanocluster evolution in lower dose rate irradiations.

  17. 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.

  18. Physical contact and carbon transfer between a lichen-forming Trebouxia alga and a novel Alphaproteobacterium.

    Science.gov (United States)

    Kono, Mieko; Tanabe, Hideyuki; Ohmura, Yoshihito; Satta, Yoko; Terai, Yohey

    2017-05-01

    Recent progress in molecular techniques has begun to alter traditional recognition of lichens as symbiotic organisms comprised of a fungus and photosynthetic partners (green algae and/or cyanobacteria). Diverse organisms, especially various non-photosynthetic bacteria, are now indicated to be integral components of lichen symbiosis. Although lichen-associated bacteria are inferred to have functions that could support the symbiosis, little is known about their physical and nutritional interaction with fungi and algae. In the present study, we identified specific interaction between a lichen-forming alga and a novel bacterium. Trebouxia alga was isolated from a lichen, Usnea hakonensis, and kept as a strain for 8 years. Although no visible bacterial colonies were observed in this culture, high-throughput sequencing of DNA isolated from the culture revealed that the strain is composed of a Trebouxia alga and an Alphaproteobacterium species. In situ hybridization showed that bacterial cells were localized on the surface of the algal cells. Physiological assays revealed that the bacterium was able to use ribitol, glucose and mannitol, all of which are known to exist abundantly in lichens. It was resistant to three antibiotics. Bacteria closely related to this species were also identified in lichen specimens, indicating that U. hakonensis may commonly associate with this group of bacteria. These features of the novel bacterium suggest that it may be involved in carbon cycling of U. hakonensis as a member of lichen symbiosis and less likely to have become associated with the alga after isolation from a lichen.

  19. Alternative waste form development: low-temperature pyrolytic-carbon coatings

    International Nuclear Information System (INIS)

    Oma, K.H.; Rusin, J.M.; Kidd, R.W.; Browning, M.F.

    1981-01-01

    Large simulted waste-forms can be coated with PyC in screw-agitated coater (SAC) at low temperatures. Higher coating rates are obtained using Ni(CO) 4 as a catalyst rather than Fe(CO) 5 or Co(AcAc) 2 ; coating quality and deposition rates are improved when C 2 H 2 is used as carbon-source gas rather than methane, propane, heptane and toluene; H 2 is a better carrier gas than Ar or N 2 . Improved coating quality and deposition rates are obtained with H 2 ; deposition rates increase with Ni(CO) 4 concentration, C 2 H 2 concentration and reaction temperature. Increasing the Ni(CO) 4 and C 2 H 2 concentrations reduces the quality of the coatings; however, better adhesion of the coating to the substrate is obtained as temperature is increased; highest quality catalyzed PyC coatings have been obtained using 0.001 and 0.01 mole % Ni(CO) 4 , 1.5 to 3.0 mole % C 2 H 2 , and the balance H 2 at 425 and 525 0 C; and deposition rates are higher in the fluidized bed coater than the SAC

  20. Enhanced pulsed magneto-motive ultrasound imaging using superparamagnetic nanoclusters

    International Nuclear Information System (INIS)

    Mehrmohammadi, M; Qu, M; Emelianov, S Y; Yoon, K Y; Johnston, K P

    2011-01-01

    Recently, pulsed magneto-motive ultrasound (pMMUS) imaging augmented with ultra-small magnetic nanoparticles has been introduced as a tool capable of imaging events at molecular and cellular levels. The sensitivity of a pMMUS system depends on several parameters, including the size, geometry and magnetic properties of the nanoparticles. Under the same magnetic field, larger magnetic nanostructures experience a stronger magnetic force and produce larger displacement, thus improving the sensitivity and signal-to-noise ratio (SNR) of pMMUS imaging. Unfortunately, large magnetic iron-oxide nanoparticles are typically ferromagnetic and thus are very difficult to stabilize against colloidal aggregation. In the current study we demonstrate improvement of pMMUS image quality by using large size superparamagnetic nanoclusters characterized by strong magnetization per particle. Water-soluble magnetic nanoclusters of two sizes (15 and 55 nm average size) were synthesized from 3 nm iron precursors in the presence of citrate capping ligand. The size distribution of synthesized nanoclusters and individual nanoparticles was characterized using dynamic light scattering (DLS) analysis and transmission electron microscopy (TEM). Tissue mimicking phantoms containing single nanoparticles and two sizes of nanoclusters were imaged using a custom-built pMMUS imaging system. While the magnetic properties of citrate-coated nanoclusters are identical to those of superparamagnetic nanoparticles, the magneto-motive signal detected from nanoclusters is larger, i.e. the same magnetic field produced larger magnetically induced displacement. Therefore, our study demonstrates that clusters of superparamagnetic nanoparticles result in pMMUS images with higher contrast and SNR.

  1. Luminescent Metal Nanoclusters for Potential Chemosensor Applications

    Directory of Open Access Journals (Sweden)

    Muthaiah Shellaiah

    2017-12-01

    Full Text Available Studies of metal nanocluster (M-NCs-based sensors for specific analyte detection have achieved significant progress in recent decades. Ultra-small-size (<2 nm M-NCs consist of several to a few hundred metal atoms and exhibit extraordinary physical and chemical properties. Similar to organic molecules, M-NCs display absorption and emission properties via electronic transitions between energy levels upon interaction with light. As such, researchers tend to apply M-NCs in diverse fields, such as in chemosensors, biological imaging, catalysis, and environmental and electronic devices. Chemo- and bio-sensory uses have been extensively explored with luminescent NCs of Au, Ag, Cu, and Pt as potential sensory materials. Luminescent bi-metallic NCs, such as Au-Ag, Au-Cu, Au-Pd, and Au-Pt have also been used as probes in chemosensory investigations. Both metallic and bi-metallic NCs have been utilized to detect various analytes, such as metal ions, anions, biomolecules, proteins, acidity or alkalinity of a solution (pH, and nucleic acids, at diverse detection ranges and limits. In this review, we have summarized the chemosensory applications of luminescent M-NCs and bi-metallic NCs.

  2. 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.

  3. Characterization of submonolayer film composed of soft-landed copper nanoclusters on HOPG

    Energy Technology Data Exchange (ETDEWEB)

    Mondal, Shyamal, E-mail: shyamal.mondal@saha.ac.in; Das, Pabitra; Chowdhury, Debasree; Bhattacharyya, S. R. [Saha Institute of Nuclear Physics, 1/AF Bidhan Nagar, Kolkata-700 064 (India)

    2015-06-24

    Preformed Copper nanoclusters are deposited on highly oriented pyrolytic graphite (HOPG) at very low energy. For the study of chemical composition X-ray Photoelectron Spectroscopy (XPS) is performed for a wide range of binding energy without exposing the sample in the ambient. Morphological aspects of the supported clusters are characterized employing high resolution scanning electron microscope (SEM). Different types of morphology are observed depending on the nature of the substrate surface. Big fractal islands are formed on terraces while at the step edges small islands are found to form. Ex-situ cathodoluminescence (CL) measurement shows peak at 558 nm wavelength which corresponds to the band gap of 2.22 eV which is due to Cu{sub 2}O nanocrystals formed due to oxidation of the deposited film in ambient.

  4. Glucose oxidase-functionalized fluorescent gold nanoclusters as probes for glucose

    International Nuclear Information System (INIS)

    Xia, Xiaodong; Long, Yunfei; Wang, Jianxiu

    2013-01-01

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

  5. Recyclable fluorescent gold nanocluster membrane for visual sensing of copper(II) ion in aqueous solution.

    Science.gov (United States)

    Lin, Zhijin; Luo, Fenqiang; Dong, Tongqing; Zheng, Liyan; Wang, Yaxian; Chi, Yuwu; Chen, Guonan

    2012-05-21

    Recently, metal-selective fluorescent chemosensors have attracted intense attention for their simple and real-time tracking of metal ions in environmental samples. However, most of the existing fluorescent sensors are one-off sensors and thus suffer from large amount of reagent consumption, significant experimental cost and raising the risk of environmental pollution. In this paper, we developed a green (low reagent consumption, low-toxicity reagent use), recyclable, and visual sensor for Cu(2+) in aqueous solution by using a fluorescent gold nanoclusters membrane (FGM) as the sensing unit, basing on our findings on gold nanoclusters (Au NCs) that the bovine serum albumin (BSA)-coated Au NCs exhibit excellent membrane-forming ability under the isoelectric point of BSA, and thus enable us to obtain a new type of sensing membrane (i.e. FGM) by denaturing Au NCs; the fluorescence of FGM can be significantly quenched by Cu(2+) ion, and the quenched fluorescence can be totally recovered by histidine; the as-prepared FGM is very stable and recyclable, which makes it an ideal sensing material.

  6. In vivo self-bio-imaging of tumors through in situ biosynthesized fluorescent gold nanoclusters

    Science.gov (United States)

    Wang, Jianling; Zhang, Gen; Li, Qiwei; Jiang, Hui; Liu, Chongyang; Amatore, Christian; Wang, Xuemei

    2013-01-01

    Fluorescence imaging in vivo allows non-invasive tumor diagnostic thus permitting a direct monitoring of cancer therapies progresses. It is established herein that fluorescent gold nanoclusters are spontaneously biosynthesized by cancerous cell (i.e., HepG2, human hepatocarcinoma cell line; K562, leukemia cell line) incubated with micromolar chloroauric acid solutions, a biocompatible molecular Au(III) species. Gold nanoparticles form by Au(III) reduction inside cells cytoplasms and ultimately concentrate around their nucleoli, thus affording precise cell imaging. Importantly, this does not occur in non-cancerous cells, as evidenced with human embryo liver cells (L02) used as controls. This dichotomy is exploited for a new strategy for in vivo self-bio-imaging of tumors. Subcutaneous injections of millimolar chloroauric acid solution near xenograft tumors of the nude mouse model of hepatocellular carcinoma or chronic myeloid leukemia led to efficient biosynthesis of fluorescent gold nanoclusters without significant dissemination to the surrounding normal tissues, hence allowing specific fluorescent self-bio-marking of the tumors.

  7. 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.

  8. 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.

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

    KAUST Repository

    Hu, Lianzhe; Deng, Lin; Alsaiari, Shahad K.; Zhang, Dingyuan; Khashab, Niveen M.

    2014-01-01

    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

  10. Distinct metal-exchange pathways of doped Ag25 nanoclusters

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa; Sinatra, Lutfan; Bakr, Osman

    2016-01-01

    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

  11. In-vitro Synthesis of Gold Nanoclusters in Neurons

    Science.gov (United States)

    2016-04-01

    ARL-TN-0753 ● APR 2016 US Army Research Laboratory In-vitro Synthesis of Gold Nanoclusters in Neurons by Maggie Gillan and...longer needed. Do not return it to the originator. ARL-TN-0753 ● APR 2016 US Army Research Laboratory In-vitro Synthesis of...

  12. Enhanced electrochemical water oxidation: the impact of nanoclusters and nanocavities

    NARCIS (Netherlands)

    Zhang, X.; Cao, C.; Bieberle, A.

    2017-01-01

    The structures of transition metal surfaces and metal oxides are commonly believed to have a significant effect on the catalytic reactions. Density functional theory calculations are therefore used in this study to investigate the oxygen evolution reaction (OER) over nanostructured, i.e. nanocluster

  13. Nanoclustering as a dominant feature of plasma membrane organization

    NARCIS (Netherlands)

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

    2014-01-01

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

  14. Chemical forms of the fluorine and carbon in fly ashes recovered from electrostatic precipitators of pulverized coal-fired plants

    Energy Technology Data Exchange (ETDEWEB)

    Naoto Tsubouchi; Hidekazu Hayashi; Akiyuki Kawashima; Masahide Sato; Noboru Suzuki; Yasuo Ohtsuka [Tohoku University, Sendai (Japan). Institute of Multidisciplinary Research for Advanced Materials

    2011-01-15

    The functionalities of the fluorine and carbon present in fly ashes formed in pulverized coal combustion have been studied with X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD) techniques. The ash samples include 20-130 {mu}g/g-dry and 0.4-4.1 mass%-dry of fluorine and carbon elements, respectively, and these components are enriched at the outermost layer of the ash surface. The F consists of both inorganic and organic functionalities, and the proportion of the latter is as high as 84-98 mol%. The C has different types of surface oxygen species, such as carboxyl, lactone/acid anhydride and phenolic groups, and most of these groups decompose to CO{sub 2} or CO up to 700{sup o}C to yield carbon active sites. When the amount of the O-functional forms increases, the content of organic C-F forms tends to increase almost linearly. On the basis of the above results, it may be speculated as one possibility that the formation of covalent C-F bonds takes place mainly through secondary reactions between gaseous F-containing compounds (HF and/or F{sub 2}) in flue gas and carbon active sites produced below 700{sup o}C downstream of coal-fired boilers. 30 refs., 8 figs., 4 tabs.

  15. Microscopical examination of carbon deposits formed in the Windscale advanced gas cooled reactor

    International Nuclear Information System (INIS)

    Livesey, D.J.; Chatwin, W.H.; Pearce, J.H.

    1980-12-01

    Methods are described of sampling and examining carbon deposits on fuel cladding in the Windscale advanced gas-cooled reactor. Deposition is observed on fuel cladding in both the reactor core and experimental loops in carbon dioxide coolants containing various amounts of carbon monoxide and methane. Deposit distribution over the cladding surface indicated that nucleation is dependent on local surface conditions. Microscopical examination showed that deposit thickness increases by carbon filament growth into the coolant gas stream and that the process can be markedly influenced by metallic impurities. There is evidence that nickel can play a particularly significant role in deposition in loop experiments but similar effects have not been observed in the reactor core. (author)

  16. Oxidation Protection Systems for Carbon-Carbon Composites Formed by Chemical Vapor Deposition and Plasma Assisted Chemical Vapor Deposition Techniques

    Science.gov (United States)

    1992-04-22

    Illinois University at Carbondale, 1991, in printing. I 42. E. Tatarzycki, ABS Report-4538216:#3, 10, 1990. 43. C. Ju, et. al., Proc. of 6th Materials...transducer, ie. a more positive scaleI I 34 thickness of fairly continuous conversion layer carbon 10 , •O.0000 resina 0 0 Fiber O0c00.a 0 Bundlea • 06...at 13000C, 0.1 atm. 1 93 IZ- ... an rI pia irgaho tea-ccv~ ab .. au .re ;--24- Oo. C:caI micrograpt~h ofcin th e csr ossivc sczrbc2 ccirzza Fck

  17. Explosive Forming of Low Carbon Steel Sheet into a Stepped Disc Shape

    OpenAIRE

    S. Balasubramanian; S. Sarvat Ali; E.S. Bhagiradha Rao

    1984-01-01

    This paper deals with the explosive forming of deep drawing quality steel into a two stepped disc type shape. An attempt has been made to predict the forming parameters from theoretical considerations by equating the disc shape with an equivalent dome. Results of forming this shape in a single stage vis-a-vis forming in two stages are compared.

  18. The actin cytoskeleton modulates the activation of iNKT cells by segregating CD1d nanoclusters on antigen-presenting cells

    Science.gov (United States)

    Torreno-Pina, Juan A.; Manzo, Carlo; Salio, Mariolina; Aichinger, Michael C.; Oddone, Anna; Lakadamyali, Melike; Shepherd, Dawn; Besra, Gurdyal S.; Cerundolo, Vincenzo

    2016-01-01

    Invariant natural killer T (iNKT) cells recognize endogenous and exogenous lipid antigens presented in the context of CD1d molecules. The ability of iNKT cells to recognize endogenous antigens represents a distinct immune recognition strategy, which underscores the constitutive memory phenotype of iNKT cells and their activation during inflammatory conditions. However, the mechanisms regulating such “tonic” activation of iNKT cells remain unclear. Here, we show that the spatiotemporal distribution of CD1d molecules on the surface of antigen-presenting cells (APCs) modulates activation of iNKT cells. By using superresolution microscopy, we show that CD1d molecules form nanoclusters at the cell surface of APCs, and their size and density are constrained by the actin cytoskeleton. Dual-color single-particle tracking revealed that diffusing CD1d nanoclusters are actively arrested by the actin cytoskeleton, preventing their further coalescence. Formation of larger nanoclusters occurs in the absence of interactions between CD1d cytosolic tail and the actin cytoskeleton and correlates with enhanced iNKT cell activation. Importantly and consistently with iNKT cell activation during inflammatory conditions, exposure of APCs to the Toll-like receptor 7/8 agonist R848 increases nanocluster density and iNKT cell activation. Overall, these results define a previously unidentified mechanism that modulates iNKT cell autoreactivity based on the tight control by the APC cytoskeleton of the sizes and densities of endogenous antigen-loaded CD1d nanoclusters. PMID:26798067

  19. The new carbon forms in the scientific instrumentation; Las nuevas formas del carbono en la instrumentacion cientifica

    Energy Technology Data Exchange (ETDEWEB)

    Saniger B, J.M. [Area de Materiales y Sensores, Centro de Instrumentos, Universidad Nacional Autonoma de Mexico, Apartado Postal 70-186, 04510 Mexico D.F. (Mexico)

    1999-11-01

    Applications in the development of scientific instrumentation of some of the new forms of carbon are discussed in this work. A short revision is presented of the remaining technical problems of the applications of diamond thin films as active semiconductor elements; heat sinks; X-ray, UV and particle detectors; surface acoustic wave devices, etc. Some advances in the improvement of the surface quality and textural design of diamond films are also presented. On the other hand, the possible implications of carbon nano tubes in scientific instrumentation are also discussed mainly for the development of electronic nano devices. Finally, other promising applications of carbon nano tubes as nano tips for atomic force and scanning tunneling microscopes, as well as nano-host structures for the synthesis of metallic carbide and nitride nano wires are also presented. (Author)

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

    International Nuclear Information System (INIS)

    Meerod, Siraprapa; Rutnakornpituk, Boonjira; Wichai, Uthai; Rutnakornpituk, Metha

    2015-01-01

    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

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

    OpenAIRE

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

    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. The...

  2. Dual emission fluorescent silver nanoclusters for sensitive detection of the biological coenzyme NAD+/NADH.

    Science.gov (United States)

    Yuan, Yufeng; Huang, Kehan; Chang, Mengfang; Qin, Cuifang; Zhang, Sanjun; Pan, Haifeng; Chen, Yan; Xu, Jianhua

    2016-02-01

    Fluorescent silver nanoclusters (Ag NCs) displaying dual-excitation and dual-emission properties have been developed for the specific detection of NAD(+) (nicotinamide adenine dinucleotide, oxidized form). With the increase of NAD(+) concentrations, the longer wavelength emission (with the peak at 550 nm) was gradually quenched due to the strong interactions between the NAD(+) and Ag NCs, whereas the shorter wavelength emission (peaking at 395 nm) was linearly enhanced. More important, the dual-emission intensity ratio (I395/I550), fitting by a single-exponential decay function, can efficiently detect various NAD(+) levels from 100 to 4000 μM, as well as label NAD(+)/NADH (reduced form of NAD) ratios in the range of 1-50. Copyright © 2015 Elsevier Inc. All rights reserved.

  3. Analysis of the Interphase on Carbon Black Formed in High Voltage Batteries

    DEFF Research Database (Denmark)

    Younesi, Reza; Christiansen, Ane Sælland; Scipioni, Roberto

    2015-01-01

    Carbon black (CB) additives commonly used to increase the electrical conductivity of electrodes in Li-ion batteries are generally believed to be electrochemically inert additives in cathodes. Decomposition of electrolyte in the surface region of CB in Li-ion cells at high voltages up to 4.9 V...... is here studied using electrochemical measurements as well as structural and surface characterizations. LiPF6 and LiClO4 dissolved in ethylene carbonate:diethylene carbonate (1:1) were used as the electrolyte to study irreversible charge capacity of CB cathodes when cycled between 4.9 V and 2.5 V....... Synchrotron-based soft X-ray photoelectron spectroscopy (SOXPES) results revealed spontaneous partial decomposition of the electrolytes on the CB electrode, without applying external current or voltage. Depth profile analysis of the electrolyte/cathode interphase indicated that the concentration of decomposed...

  4. Mass spectrometric identification of Au68(SR)34 molecular gold nanoclusters with 34-electron shell closing.

    Science.gov (United States)

    Dass, Amala

    2009-08-26

    The molecular formula Au(68)(SCH(2)CH(2)Ph)(34) has been assigned to the 14 kDa nanocluster using MALDI-TOF mass spectrometry. The 34-electron shell closing in a macroscopically obtained thiolated gold nanocluster is demonstrated. The Au(68) nanocluster is predicted to have a 49 atom Marks decahedral core with 19 inner core atoms and 30 outer atoms chelating with the staple motifs. The nanoclusters' predicted formulation is [Au](19+30) [Au(SR)(2)](11) [Au(2)(SR)(3)](4).

  5. Electrostatic Interactions Positively Regulate K-Ras Nanocluster Formation and Function▿

    Science.gov (United States)

    Plowman, Sarah J.; Ariotti, Nicholas; Goodall, Andrew; Parton, Robert G.; Hancock, John F.

    2008-01-01

    The organization of Ras proteins into plasma membrane nanoclusters is essential for high-fidelity signal transmission, but whether the nanoscale enviroments of different Ras nanoclusters regulate effector interactions is unknown. We show using high-resolution spatial mapping that Raf-1 is recruited to and retained in K-Ras-GTP nanoclusters. In contrast, Raf-1 recruited to the plasma membrane by H-Ras is not retained in H-Ras-GTP nanoclusters. Similarly, upon epidermal growth factor receptor activation, Raf-1 is preferentially recruited to K-Ras-GTP and not H-Ras-GTP nanoclusters. The formation of K-Ras-GTP nanoclusters is inhibited by phosphorylation of S181 in the C-terminal polybasic domain or enhanced by blocking S181 phosphorylation, with a concomitant reduction or increase in Raf-1 plasma membrane recruitment, respectively. Phosphorylation of S181 does not, however, regulate in vivo interactions with the nanocluster scaffold galectin-3 (Gal3), indicating separate roles for the polybasic domain and Gal3 in driving K-Ras nanocluster formation. Together, these data illustrate that Ras nanocluster composition regulates effector recruitment and highlight the importance of lipid/protein nanoscale environments to the activation of signaling cascades. PMID:18458061

  6. ELASTO-PLASTIC DEFORMATION OF COMPOSITE POWDERS WITH LAYERED CARBON AND CARBIDE-FORMING ELEMENT COATING

    Directory of Open Access Journals (Sweden)

    V. N. Kovalevsky

    2012-01-01

    Full Text Available Coating structure formation under magnetron spraying of titanium and carbon cathodes and combined cathodes, namely cobalt (EP 131 – nickel, tungsten – carbon have been investigated under conditions of carbide separate synthesis within the temperature range of 650–1200 °C. Usage of cobalt and nickel particles as matrix material leads to their rapid thermal expansion under heating during sintering process in the dilatometer. Subsequent plastic deformation of sintered samples provides obtaining a composite powder material that is a composite with framing structure of cobalt, titanium and tungsten carbides in the coatings.

  7. Fumaric acid: an overlooked form of fixed carbon in Arabidopsis and other plant species

    International Nuclear Information System (INIS)

    Chia, D.W.; Yoder, T.J.; Reiter, W.D.; Gibson, S.I.

    2000-01-01

    Photoassimilates are used by plants for production of energy, as carbon skeletons and in transport of fixed carbon between different plant organs. Many studies have been devoted to characterizing the factors that. regulate photoassimilate concentrations in different plant species. Most studies examining photoassimilate concentrations in C(sub 3) plants have focused on analyzing starch and soluble sugars. However, work presented here demonstrates that a number of C(sub 3) plants, including the popular model organism Arabidopsis thaliana (L.) Heynh., and agriculturally important plants, such as soybean[Glycine ma (L.) Merr.], contain significant quantities of furnaric acid. In fact, furnaric acid can accumulate to levels of several mg per g fresh weight in A-abidopsis leaves, often exceeding starch and soluble sugar levels. Furnaric acid is a component of the tricarboxylic acid cycle and, like starch and soluble sugars, can be metabolized to yield energy and carbon skeletons for production of other compounds. Fumaric acid concentrations increase with plant age and light intensity in Arabidopsis leaves. Arabidopsis phloem exudates contain significant quantities of fumaric acid, raising the possibility that fumaric acid may function in carbon transport

  8. Adsorption of Carbon Dioxide on Sodium and Potassium Forms of STI Zeolite

    Czech Academy of Sciences Publication Activity Database

    Zukal, Arnošt; Zones, S. I.; Kubů, Martin; Davis, T. M.; Čejka, Jiří

    2012-01-01

    Roč. 77, č. 8 (2012), s. 675-681 ISSN 2192-6506 R&D Projects: GA ČR GA203/08/0604 Institutional support: RVO:61388955 Keywords : adsorption * carbon dioxide * zeolites Subject RIV: CF - Physical ; Theoretical Chemistry

  9. Fumaric acid: an overlooked form of fixed carbon in Arabidopsis and other plant species

    Energy Technology Data Exchange (ETDEWEB)

    Chia, D.W.; Yoder, T.J.; Reiter, W.D.; Gibson, S.I.

    2000-10-01

    Photoassimilates are used by plants for production of energy, as carbon skeletons and in transport of fixed carbon between different plant organs. Many studies have been devoted to characterizing the factors that. regulate photoassimilate concentrations in different plant species. Most studies examining photoassimilate concentrations in C{sub 3} plants have focused on analyzing starch and soluble sugars. However, work presented here demonstrates that a number of C{sub 3} plants, including the popular model organism Arabidopsis thaliana (L.) Heynh., and agriculturally important plants, such as soybean [Glycine ma (L.) Merr.], contain significant quantities of furnaric acid. In fact, furnaric acid can accumulate to levels of several mg per g fresh weight in A-abidopsis leaves, often exceeding starch and soluble sugar levels. Furnaric acid is a component of the tricarboxylic acid cycle and, like starch and soluble sugars, can be metabolized to yield energy and carbon skeletons for production of other compounds. Fumaric acid concentrations increase with plant age and light intensity in Arabidopsis leaves. Arabidopsis phloem exudates contain significant quantities of fumaric acid, raising the possibility that fumaric acid may function in carbon transport.

  10. Influence of temperature, chloride ions and chromium element on the electronic property of passive film formed on carbon steel in bicarbonate/carbonate buffer solution

    Energy Technology Data Exchange (ETDEWEB)

    Li, D.G. [School of Materials Science and Engineering, Xi' an Jiaotong University, Xi' an 710049 (China); Tubular Goods Research Center of CNPC, Xi' an 710065 (China)], E-mail: dangguoli78@yahoo.com.cn; Feng, Y.R.; Bai, Z.Q. [Tubular Goods Research Center of CNPC, Xi' an 710065 (China); Zhu, J.W.; Zheng, M.S. [School of Materials Science and Engineering, Xi' an Jiaotong University, Xi' an 710049 (China)

    2007-11-01

    The influences of temperature, chloride ions and chromium element on the electronic property of passive film formed on carbon steel in NaHCO{sub 3}/Na{sub 2}CO{sub 3} buffer solution are investigated by capacitance measurement and electrochemical impedance spectroscopy (EIS). The results show that the passive film appears n-type semiconductive character; with increasing the solution temperature, the addition of chromium into carbon steel and increasing the concentration of chloride ions, the slopes of Mott-Schottky plots decrease, which indicates the increment of the defect density in the passive film. EIS results show that the transfer impedance R{sub 1} and the diffusion impedance W decrease with increasing the solution temperature, with the addition of chromium into carbon steel and with increasing the chloride ions concentration. It can be concluded that the corrosion protection effect of passive film on the substrate decreases with increasing the solution temperature, adding chromium into carbon steel and increasing chloride ions concentration.

  11. Electrodeposition of tantalum on carbon black in non-aqueous solution and its electrocatalytic properties

    International Nuclear Information System (INIS)

    Jo, Ara; Lee, Youngmi; Lee, Chongmok

    2016-01-01

    In this work, we synthesized tantalum (Ta) nanoclusters on carbon black (Ta/CB) via simple electrodeposition in non-aqueous solvent, acetonitrile (ACN) at ambient temperature. Transmission electron microscopy (TEM) images showed that the electrodeposited Ta nanoclusters consisted of tiny Ta nanoparticles. X-ray photoelectron spectroscopy (XPS) result represented that the outermost Ta formed the native oxide on Ta/CB due to its ambient exposure to air. Electrochemical catalytic properties of prepared Ta/CB on glassy carbon electrode (Ta/CB/GC) were investigated toward reductions of oxygen and hydrogen peroxide, and oxidations of ascorbic acid and dopamine. For oxygen reduction reaction (ORR) in acid, Ta/CB/GC represented a decent electrocatalytic performance which was better or comparable to bare Pt. The operational stability in acidic condition was maintained up to 500 repetitive potential cycles presumably due to the protective native Ta oxide layer. Ta/CB/GC also showed high amperometric sensitivity (4.5 (±0.1_6) mA mM"−"1 cm"−"2, n = 5) for reduction of hydrogen peroxide in 0.1 M phosphate buffer solution (PBS, pH 7.4). In addition, Ta/CB/GC was demonstrated for the possibility of simultaneous detection of ascorbic acid and dopamine using differential pulse voltammetry (DPV). - Highlights: • We electrodeposited Ta nanoclusters (Ta/CB/GC) in acetonitrile at room temperature. • The Ta/CB/GC showed better or comparable performance to bare Pt for ORR. • The Ta/CB/GC showed high sensitivity for reduction of hydrogen peroxide at pH 7.4. • The Ta/CB/GC showed possible simultaneous detection of ascorbic acid and dopamine. • We extended the applicability of Ta electrode material for various electrocatalytic reactions.

  12. Electrodeposition of tantalum on carbon black in non-aqueous solution and its electrocatalytic properties

    Energy Technology Data Exchange (ETDEWEB)

    Jo, Ara; Lee, Youngmi, E-mail: youngmilee@ewha.ac.kr; Lee, Chongmok, E-mail: cmlee@ewha.ac.kr

    2016-08-24

    In this work, we synthesized tantalum (Ta) nanoclusters on carbon black (Ta/CB) via simple electrodeposition in non-aqueous solvent, acetonitrile (ACN) at ambient temperature. Transmission electron microscopy (TEM) images showed that the electrodeposited Ta nanoclusters consisted of tiny Ta nanoparticles. X-ray photoelectron spectroscopy (XPS) result represented that the outermost Ta formed the native oxide on Ta/CB due to its ambient exposure to air. Electrochemical catalytic properties of prepared Ta/CB on glassy carbon electrode (Ta/CB/GC) were investigated toward reductions of oxygen and hydrogen peroxide, and oxidations of ascorbic acid and dopamine. For oxygen reduction reaction (ORR) in acid, Ta/CB/GC represented a decent electrocatalytic performance which was better or comparable to bare Pt. The operational stability in acidic condition was maintained up to 500 repetitive potential cycles presumably due to the protective native Ta oxide layer. Ta/CB/GC also showed high amperometric sensitivity (4.5 (±0.1{sub 6}) mA mM{sup −1} cm{sup −2}, n = 5) for reduction of hydrogen peroxide in 0.1 M phosphate buffer solution (PBS, pH 7.4). In addition, Ta/CB/GC was demonstrated for the possibility of simultaneous detection of ascorbic acid and dopamine using differential pulse voltammetry (DPV). - Highlights: • We electrodeposited Ta nanoclusters (Ta/CB/GC) in acetonitrile at room temperature. • The Ta/CB/GC showed better or comparable performance to bare Pt for ORR. • The Ta/CB/GC showed high sensitivity for reduction of hydrogen peroxide at pH 7.4. • The Ta/CB/GC showed possible simultaneous detection of ascorbic acid and dopamine. • We extended the applicability of Ta electrode material for various electrocatalytic reactions.

  13. All-carbon nanotube diode and solar cell statistically formed from macroscopic network

    Institute of Scientific and Technical Information of China (English)

    Albert G. Nasibulin[1,2,3; Adinath M. Funde[3,4; Ilya V. Anoshkin[3; Igor A. Levitskyt[5,6

    2015-01-01

    Schottky diodes and solar cells are statistically created in the contact area between two macroscopic films of single-walled carbon nanotubes (SWNTs) at the junction of semiconducting and quasi-metallic bundles consisting of several high quality tubes. The n-doping of one of the films allows for photovoltaic action, owing to an increase in the built-in potential at the bundle-to-bundle interface. Statistical analysis demonstrates that the Schottky barrier device contributes significantly to the I-V characteristics, compared to the p-n diode. The upper limit of photovoltaic conversion efficiency has been estimated at N20%, demonstrating that the light energy conversion is very efficient for such a unique solar cell. While there have been multiple studies on rectifying SWNT diodes in the nanoscale environment, this is the first report of a macroscopic all-carbon nanotube diode and solar cell.

  14. Size effect on the adsorption and dissociation of CO{sub 2} on Co nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Haiyan; Cao, Dapeng; Fisher, Adrian [International Research Center for Soft Matter, State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 (China); Johnston, Roy L. [School of Chemistry, University of Birmingham, Edgbaston, Birmingham, B15 2TT (United Kingdom); Cheng, Daojian, E-mail: chengdj@mail.buct.edu.cn [International Research Center for Soft Matter, State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 (China)

    2017-02-28

    Highlights: • Co{sub 13}, Co{sub 38} and Co{sub 55} nanoclusters were predicted as the high-symmetry structures. • CO{sub 2} dissociation on the size-selected Co{sub 13}, Co{sub 38} and Co{sub 55} nanoclusters was studied. • Co{sub 55} nanocluster possesses the highest activity relevant to CO{sub 2} dissociation. • A non-monotonous behavior of the dissociation barrier of CO{sub 2} with the size was found. - Abstract: Spin-polarized density functional theory calculations were carried out to study the adsorption and dissociation properties of CO{sub 2} on size-selected Co{sub 13}, Co{sub 38} and Co{sub 55} nanoclusters. Based on genetic algorithm method, Co{sub 13}, Co{sub 38} and Co{sub 55} nanoclusters were predicted as the most stable high-symmetry structures among these Co{sub n} (n = 2–58) nanoclusters from the Gupta potential. For the adsorption of CO{sub 2}, CO and O on size-selected Co{sub 13}, Co{sub 38} and Co{sub 55} nanoclusters, the lowest adsorption strength is found for all the different adsorbates on Co{sub 55} nanocluster. For the dissociation of CO{sub 2} on these size-selected Co nanoclusters, the largest Co{sub 55} nanocluster possesses the greatest catalytic activity for the dissociation of CO{sub 2}, with the smallest reaction barrier of 0.38 eV. Our results reveal a non-monotonous behavior of the catalytic activities of Co nanoclusters on size, which is of fundamental interest for the design of new Co catalysts for the conversion of CO{sub 2}.

  15. Native and denatured forms of proteins can be discriminated at edge plane carbon electrodes

    Czech Academy of Sciences Publication Activity Database

    Ostatná, Veronika; Černocká, Hana; Kurzatkowska, K.; Paleček, Emil

    2012-01-01

    Roč. 735, JUL (2012), s. 31-36 ISSN 0003-2670 R&D Projects: GA AV ČR(CZ) KJB100040901; GA ČR(CZ) GAP301/11/2055; GA MŠk(CZ) ME09038 Institutional research plan: CEZ:AV0Z50040702 Keywords : protein denaturation * carbon electrodes * edge plane pyrolytic graphite Subject RIV: BO - Biophysics Impact factor: 4.387, year: 2012

  16. Silver nanocluster formation in ion-exchanged glasses by annealing, ion beam and laser beam irradiation: An EXAFS study

    International Nuclear Information System (INIS)

    Battaglin, G.; Cattaruzza, E.; Gonella, F.; Polloni, R.; D'Acapito, F.; Colonna, S.; Mattei, G.; Maurizio, C.; Mazzoldi, P.; Padovani, S.; Sada, C.; Quaranta, A.; Longo, A.

    2003-01-01

    Extended X-ray absorption fine structure analysis is used to determine the silver local environment in silicate glasses doped by the Ag-alkali ion-exchange process, followed by different treatments, namely, ion irradiation, thermal annealing in reducing atmosphere, laser irradiation. The obtained results indicate that metal nanocluster composites with different cluster structures may be formed with these multistep methodologies, pointing out the role of the preparation parameters in giving rise to different features. Lattice parameters and cluster diameter were determined by grazing incidence X-ray diffraction

  17. Endohedral confinement of a DNA dodecamer onto pristine carbon nanotubes and the stability of the canonical B form

    International Nuclear Information System (INIS)

    Cruz, Fernando J. A. L.; Pablo, Juan J. de; Mota, José P. B.

    2014-01-01

    Although carbon nanotubes are potential candidates for DNA encapsulation and subsequent delivery of biological payloads to living cells, the thermodynamical spontaneity of DNA encapsulation under physiological conditions is still a matter of debate. Using enhanced sampling techniques, we show for the first time that, given a sufficiently large carbon nanotube, the confinement of a double-stranded DNA segment, 5′-D( * CP * GP * CP * GP * AP * AP * TP * TP * CP * GP * CP * G)-3′, is thermodynamically favourable under physiological environments (134 mM, 310 K, 1 bar), leading to DNA-nanotube hybrids with lower free energy than the unconfined biomolecule. A diameter threshold of 3 nm is established below which encapsulation is inhibited. The confined DNA segment maintains its translational mobility and exhibits the main geometrical features of the canonical B form. To accommodate itself within the nanopore, the DNA's end-to-end length increases from 3.85 nm up to approximately 4.1 nm, due to a ∼0.3 nm elastic expansion of the strand termini. The canonical Watson-Crick H-bond network is essentially conserved throughout encapsulation, showing that the contact between the DNA segment and the hydrophobic carbon walls results in minor rearrangements of the nucleotides H-bonding. The results obtained here are paramount to the usage of carbon nanotubes as encapsulation media for next generation drug delivery technologies

  18. Enhanced electrochemical performance of porous activated carbon by forming composite with graphene as high-performance supercapacitor electrode material

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zhi-Hang; Yang, Jia-Ying [Central South University, College of Chemistry and Chemical Engineering, Hunan Provincial Key Laboratory of Efficient and Clean Utilization of Manganese Resources (China); Wu, Xiong-Wei [Hunan Agricultural University, College of Science (China); Chen, Xiao-Qing; Yu, Jin-Gang, E-mail: yujg@csu.edu.cn [Central South University, College of Chemistry and Chemical Engineering, Hunan Provincial Key Laboratory of Efficient and Clean Utilization of Manganese Resources (China); Wu, Yu-Ping, E-mail: wuyp@fudan.edu.cn [Fudan University, New Energy and Materials Laboratory (NEML), Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials (China)

    2017-02-15

    In this work, a novel activated carbon containing graphene composite was developed using a fast, simple, and green ultrasonic-assisted method. Graphene is more likely a framework which provides support for activated carbon (AC) particles to form hierarchical microstructure of carbon composite. Scanning electron microscope (SEM), transmission electron microscope (TEM), Brunauer–Emmett–Teller (BET) surface area measurement, thermogravimetric analysis (TGA), Raman spectra analysis, XRD, and XPS were used to analyze the morphology and surface structure of the composite. The electrochemical properties of the supercapacitor electrode based on the as-prepared carbon composite were investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), charge/discharge, and cycling performance measurements. It exhibited better electrochemical performance including higher specific capacitance (284 F g{sup −1} at a current density of 0.5 A g{sup −1}), better rate behavior (70.7% retention), and more stable cycling performance (no capacitance fading even after 2000 cycles). It is easier for us to find that the composite produced by our method was superior to pristine AC in terms of electrochemical performance due to the unique conductive network between graphene and AC.

  19. Enhanced electrochemical performance of porous activated carbon by forming composite with graphene as high-performance supercapacitor electrode material

    International Nuclear Information System (INIS)

    Wang, Zhi-Hang; Yang, Jia-Ying; Wu, Xiong-Wei; Chen, Xiao-Qing; Yu, Jin-Gang; Wu, Yu-Ping

    2017-01-01

    In this work, a novel activated carbon containing graphene composite was developed using a fast, simple, and green ultrasonic-assisted method. Graphene is more likely a framework which provides support for activated carbon (AC) particles to form hierarchical microstructure of carbon composite. Scanning electron microscope (SEM), transmission electron microscope (TEM), Brunauer–Emmett–Teller (BET) surface area measurement, thermogravimetric analysis (TGA), Raman spectra analysis, XRD, and XPS were used to analyze the morphology and surface structure of the composite. The electrochemical properties of the supercapacitor electrode based on the as-prepared carbon composite were investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), charge/discharge, and cycling performance measurements. It exhibited better electrochemical performance including higher specific capacitance (284 F g"−"1 at a current density of 0.5 A g"−"1), better rate behavior (70.7% retention), and more stable cycling performance (no capacitance fading even after 2000 cycles). It is easier for us to find that the composite produced by our method was superior to pristine AC in terms of electrochemical performance due to the unique conductive network between graphene and AC.

  20. A nanocluster-based fluorescent sensor for sensitive hemoglobin detection.

    Science.gov (United States)

    Yang, Dongqin; Meng, Huijie; Tu, Yifeng; Yan, Jilin

    2017-08-01

    In this report, a fluorescence sensor for sensitive detection of hemoglobin was developed. Gold nanoclusters were first synthesized with bovine serum albumin. It was found that both hydrogen peroxide and hemoglobin could weakly quench the fluorescence from the gold nanoclusters, but when these two were applied onto the nanolcusters simultaneously, a much improved quenching was resulted. This enhancing effect was proved to come from the catalytic generation of hydroxyl radical by hemoglobin. Under an optimized condition, the quenching linearly related to the concentration of hemoglobin in the range of 1-250nM, and a limit of detection as low as 0.36nM could be obtained. This provided a sensitive means for the quantification of Hb. The sensor was then successfully applied for blood analyses with simple sample pretreatment. Copyright © 2017 Elsevier B.V. All rights reserved.

  1. Chemical forms of the fluorine, chlorine, oxygen and carbon in coal fly ash and their correlations with mercury retention

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Shuang [State Key Laboratory of Environmental Criteria and Risk Assessment (China); Research Academy of Environmental Sciences, Beijing 100012 (China); Shu, Yun [Research Academy of Environmental Sciences, Beijing 100012 (China); Li, Songgeng, E-mail: sgli@ipe.ac.cn [State Key Laboratory of Multi-phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Tian, Gang; Huang, Jiayu [Research Academy of Environmental Sciences, Beijing 100012 (China); Zhang, Fan, E-mail: zhangfan5188@vip.sina.com [Research Academy of Environmental Sciences, Beijing 100012 (China)

    2016-01-15

    Highlights: • Chlorine and fluorine are present mainly in an inorganic form on ash. • Correlations of carbon–oxygen complexes with mercury retention are established. • Concentrations of carbon–oxygen complexes on ash are related to coal type. • No effect of fluorine on mercury retention is observed. • Chlorine, fluorine and carbon in ash are enriched on surface. - Abstract: Fly ashes recovered from the particulate control devices at six pulverized coal boiler unites of China, are studied using an X-ray photoelectron spectroscopy (XPS) with a particular focus on the functionalities of fluorine (F), chlorine (Cl), carbon and oxygen on fly ash. It is found that the inorganic forms of F and Cl are predominant on the ash surface in comparison with their organics, and the proportion of organic Cl is relatively higher than that of organic F. Similar results are also obtained in the bulk by correlating the F and Cl contents with those of the unburnt carbon and other compositions in ash. Strong correlations of mercury retention with surface carbon–oxygen functional groups indicate that the C=O, OH/C−O and (O−C=O)−O on surface are of significant importance for mercury retention in fly ash. Their surface concentrations are related to coal type. The presence of Cl in fly ash helps with mercury retention. No obvious effect of F is observed.

  2. Theory of Nanocluster Size Distributions from Ion Beam Synthesis

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-06-13

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

  3. Chemical- or radiation-assisted selective dealloying in bimetallic nanoclusters

    International Nuclear Information System (INIS)

    Mattei, G.; De Marchi, G.; Maurizio, C.; Mazzoldi, P.; Sada, C.; Bello, V.; Battaglin, G.

    2003-01-01

    A selective dealloying in bimetallic nanoclusters prepared by ion implantation has been found upon thermal annealing in oxidizing atmosphere or irradiation with light ions. In the first process, the incoming oxygen interacts preferentially with copper promoting Cu 2 O formation, therefore extracting copper from the alloy. In the second process the irradiation with Ne ions promotes a preferential extraction of Au from the alloy, resulting in the formation of Au-enriched 'satellite' nanoparticles around the original Au x Cu 1-x cluster

  4. Electrochemical capacitance of nanocomposite films formed by loading carbon nanotubes with ruthenium oxide

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jae-Kyung [Department of Chemical Engineering, University of Seoul, 90 Chonnong-dong, Tongdaemun-gu, Seoul (Korea, Republic of); Pathan, Habib M.; Jung, Kwang-Deog; Joo, Oh-Shim [Eco-Nano Research Center, Korea Institute of Science and Technology (KIST), P.O. Box 131, Cheongryang, Seoul (Korea, Republic of)

    2006-09-22

    This work reports the supercapacitive properties of composite films of multiwalled carbon nanotubes (MWNT) and ruthenium oxide (RuO{sub 2}). Transmission and scanning electron microscopy, cyclic voltammetry, and electrochemical studies revealed that the nanoporous three-dimensional arrangement of RuO{sub 2}-coated MWNT in these films facilitated the improvement of electron and ion transfer relative to MWNT films. The capacitance was measured for films of different RuO{sub 2} loading, revealing specific capacitances per mass as high as 628Fg{sup -1}. The energy storage density of the electrode has increased about three times as compared to MWNT treated with piranha solution. (author)

  5. Stable carbon isotope fractionation of organic cyst-forming dinoflagellates: Evaluating the potential for a CO2 proxy

    Science.gov (United States)

    Hoins, Mirja; Van de Waal, Dedmer B.; Eberlein, Tim; Reichart, Gert-Jan; Rost, Björn; Sluijs, Appy

    2015-07-01

    Over the past decades, significant progress has been made regarding the quantification and mechanistic understanding of stable carbon isotope fractionation (13C fractionation) in photosynthetic unicellular organisms in response to changes in the partial pressure of atmospheric CO2 (pCO2). However, hardly any data is available for organic cyst-forming dinoflagellates while this is an ecologically important group with a unique fossil record. We performed dilute batch experiments with four harmful dinoflagellate species known for their ability to form organic cysts: Alexandrium tamarense, Scrippsiella trochoidea, Gonyaulax spinifera and Protoceratium reticulatum. Cells were grown at a range of dissolved CO2 concentrations characterizing past, modern and projected future values (∼5-50 μmol L-1), representing atmospheric pCO2 of 180, 380, 800 and 1200 μatm. In all tested species, 13C fractionation depends on CO2 with a slope of up to 0.17‰ (μmol L)-1. Even more consistent correlations were found between 13C fractionation and the combined effects of particulate organic carbon quota (POC quota; pg C cell-1) and CO2. Carbon isotope fractionation as well as its response to CO2 is species-specific. These results may be interpreted as a first step towards a proxy for past pCO2 based on carbon isotope ratios of fossil organic dinoflagellate cysts. However, additional culture experiments focusing on environmental variables other than pCO2, physiological underpinning of the recorded response, testing for possible offsets in 13C values between cells and cysts, as well as field calibration studies are required to establish a reliable proxy.

  6. Form of inorganic carbon utilized for photosynthesis in Chlorella vulgaris 11h cells

    International Nuclear Information System (INIS)

    Miyachi, Shigetoh; Shiraiwa, Yoshihiro

    1979-01-01

    The rate of photosynthetic 14 CO 2 fixation in Chlorella vulgaris 11h cells in the presence of 0.55 mM NaH 14 CO 3 at pH 8.0 (20 0 C) was greatly enhanced by the addition of carbonic anhydrase (CA). However, when air containing 400 ppm 14 CO 2 was bubbled through the algal suspension, the rate of 14 CO 2 fixation immediately after the start of the bubbling was suppressed by CA. These effects of CA were observed in cells which had been grown in air containing 2% CO 2 (high-CO 2 cells) as well as those grown in ordinary air (containing 0.04% CO 2 , low-CO 2 cells). We therefore concluded that, irrespective of the CO 2 concentration given to the algal cells during growth, the active species of inorganic carbon absorbed by Chlorella cells is free CO 2 and they cannot utilize bicarbonate. The effects observed in the high-CO 2 cells were much more pronounced than those in the low-CO 2 cells. This difference was accounted for by the difference in the affinity for CO 2 in photosynthesis between the high- and low-CO 2 cells. (author)

  7. A Comparative XAFS Study of Gold-thiolate Nanoparticles and Nanoclusters

    International Nuclear Information System (INIS)

    Chevrier, D M; Chatt, A; Zhang, P; Sham, T K

    2013-01-01

    Tiopronin-capped gold nanoparticles and gold nanoclusters of sizes 3.0 and 1.5 nm, respectively, were investigated with XAFS at the gold L 3 -edge. The specific EXAFS fitting procedure is discussed for obtaining reliable fit parameters for each system. The difficulties and challenges faced when analysing EXAFS data for gold nanoparticles and nanoclusters are also mentioned. Fitting results for gold nanoparticles reveal a small amount of surface Au-thiolate interactions with a large Au-Au metal core. For gold nanoclusters, only a one-shell fit was obtainable. Instead of Au-Au metal core, long-range interactions are expected for gold nanoclusters. Tiopronin-capped gold nanoclusters are proposed to be polymeric in nature, which helps explain the observed red luminescence.

  8. pH-Induced transformation of ligated Au25 to brighter Au23 nanoclusters.

    Science.gov (United States)

    Waszkielewicz, Magdalena; Olesiak-Banska, Joanna; Comby-Zerbino, Clothilde; Bertorelle, Franck; Dagany, Xavier; Bansal, Ashu K; Sajjad, Muhammad T; Samuel, Ifor D W; Sanader, Zeljka; Rozycka, Miroslawa; Wojtas, Magdalena; Matczyszyn, Katarzyna; Bonacic-Koutecky, Vlasta; Antoine, Rodolphe; Ozyhar, Andrzej; Samoc, Marek

    2018-05-01

    Thiolate-protected gold nanoclusters have recently attracted considerable attention due to their size-dependent luminescence characterized by a long lifetime and large Stokes shift. However, the optimization of nanocluster properties such as the luminescence quantum yield is still a challenge. We report here the transformation of Au25Capt18 (Capt labels captopril) nanoclusters occurring at low pH and yielding a product with a much increased luminescence quantum yield which we have identified as Au23Capt17. We applied a simple method of treatment with HCl to accomplish this transformation and we characterized the absorption and emission of the newly created ligated nanoclusters as well as their morphology. Based on DFT calculations we show which Au nanocluster size transformations can lead to highly luminescent species such as Au23Capt17.

  9. 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.

  10. Investigating Molecular Inheritance of Carbon in Star-forming Regions along a Galactic Gradient

    KAUST Repository

    Smith, Rachel L.

    2015-04-01

    Observations of CO isotopologues taken at high spectral resolution toward young stellar objects (YSOs) are valuable tools for investigating protoplanetary chemical reservoirs, and enable robust comparisons between YSOs and solar system material (meteorites and the Sun). Investigating a range of YSO environments also helps parameterize variations in the distribution and evolution of carbon-based molecules, furthering an understanding of prebiotic chemistry. We have begun a wide survey of massive YSOs using Keck-NIRSPEC at high spectral resolution (R=25,000). Fundamental and first-overtone near-IR CO rovibrational absorption spectra have thus far been obtained toward 14 massive, luminous YSOs at Galactocentric radii (RGC) ranging from ~4.5 to 9.7 kpc. From these data we can obtain precise [12CO]/[13CO] gas-phase abundance ratios along a Galactic gradient, and [12CO]/[13CO]Gas can be further evaluated against published [12CO2]/[13CO2]Ice and [12CO]/[13CO]Ice because all observations are in absorption, a robust study of molecular inheritance is possible by virtue of comparing 12C/13C along the same lines-of-sight. Initial results for cold CO gas at RGC ~ 6.1 kpc and 9.4 kpc reveal [12C16O]/[13C16O] of 59+/‑8 and 74+/‑3, respectively, roughly following an expected 12C/13C Galactic gradient. Thus far, we find [12CO]/[13CO] in the cold CO gas to be lower than [12CO2]/[13CO2]Ice, suggesting that CO2 may not originate from CO reservoirs as often assumed. While very high-resolution observations of CO gas toward low-mass YSOs observed with VLT-CRIRES show significant heterogeneity in [12CO]/[13CO] at RGC ~ 8 kpc, this dispersion is not found for the massive YSOs. Both the low-mass and massive YSOs have higher [12CO]/[13CO] in warm vs. cold gas, and both show signatures suggesting possible interplay between CO ice and gas reservoirs. Overall, our results indicate that carbon isotopic evolution in massive YSO environments may follow different paths compared to low-mass YSOs

  11. Investigating Molecular Inheritance of Carbon in Star-forming Regions along a Galactic Gradient

    KAUST Repository

    Smith, Rachel L.; Blake, Geoffrey; Boogert, Adwin; Pontoppidan, Klaus Martin; Lockwood, Alexandra C.

    2015-01-01

    Observations of CO isotopologues taken at high spectral resolution toward young stellar objects (YSOs) are valuable tools for investigating protoplanetary chemical reservoirs, and enable robust comparisons between YSOs and solar system material (meteorites and the Sun). Investigating a range of YSO environments also helps parameterize variations in the distribution and evolution of carbon-based molecules, furthering an understanding of prebiotic chemistry. We have begun a wide survey of massive YSOs using Keck-NIRSPEC at high spectral resolution (R=25,000). Fundamental and first-overtone near-IR CO rovibrational absorption spectra have thus far been obtained toward 14 massive, luminous YSOs at Galactocentric radii (RGC) ranging from ~4.5 to 9.7 kpc. From these data we can obtain precise [12CO]/[13CO] gas-phase abundance ratios along a Galactic gradient, and [12CO]/[13CO]Gas can be further evaluated against published [12CO2]/[13CO2]Ice and [12CO]/[13CO]Ice because all observations are in absorption, a robust study of molecular inheritance is possible by virtue of comparing 12C/13C along the same lines-of-sight. Initial results for cold CO gas at RGC ~ 6.1 kpc and 9.4 kpc reveal [12C16O]/[13C16O] of 59+/‑8 and 74+/‑3, respectively, roughly following an expected 12C/13C Galactic gradient. Thus far, we find [12CO]/[13CO] in the cold CO gas to be lower than [12CO2]/[13CO2]Ice, suggesting that CO2 may not originate from CO reservoirs as often assumed. While very high-resolution observations of CO gas toward low-mass YSOs observed with VLT-CRIRES show significant heterogeneity in [12CO]/[13CO] at RGC ~ 8 kpc, this dispersion is not found for the massive YSOs. Both the low-mass and massive YSOs have higher [12CO]/[13CO] in warm vs. cold gas, and both show signatures suggesting possible interplay between CO ice and gas reservoirs. Overall, our results indicate that carbon isotopic evolution in massive YSO environments may follow different paths compared to low-mass YSOs

  12. Synthesis and Characterization of Atomically Precise Copper Nanoclusters

    Science.gov (United States)

    Nguyen, Thuy-Ai Dang

    The reactivity of MCl3(eta1-TEMPO) (M = Fe, Al; TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) with a variety of lignin models, including 3,4-dimethoxybenzyl alcohol, 1-phenyl-2-phenoxyethanol and 1,2-diphenyl-2-methoxyethanol is investigated. FeCl3(TEMPO) is effective in cleanly converting these substrates to the corresponding aldehyde or ketone. AlCl3(eta1-TEMPO) is also able to oxidize these substrates, however in a few instances the products of over-oxidation are also observed. In contrast, 2-phenoxyethanol is not oxidized by MCl 3(eta1-TEMPO); instead it likely coordinates to the metal center, forming a 2-phenoxyethoxide complex. Oxidation of activated alkanes by MCl3(eta1-TEMPO) suggests that the reactions proceed via an initial 1-electron concerted proton-electron transfer (CPET) event. Finally, reaction of TEMPO with FeBr3 in Et 2O results in oxidation of the solvent. The copper hydride clusters [Cu14H12(phen) 6(PPh3)4][X]2 (X = Cl, OTf) are obtained in good yields by reaction of [(Ph3P)CuH]6 with 1,10-phenanthroline, in the presence of a halide or pseudohalide source. [Cu14H 12(phen)6(PPh3)4][Cl]2 reacts with CO2 in CH2Cl2, in the presence of excess Ph3P, to form the formate complex, [(Ph3P)2Cu(kappa 2-O2CH)], along with [(phen)(Ph3P)CuCl]. [Cu25H22(PPh3)12]Cl and [Cu 18H17(PPh3)10]Cl, are isolated from the reaction of Cu(OAc) and CuCl with Ph2SiH2, in the presence of PPh3. [Cu25H22(PPh3) 12]Cl formally features partial Cu(0) character. Subsequent reaction with Ph2phen resulted in the isolation of [Cu29Cl 4H22(Ph2phen)12]Cl (Ph2phen = 4,7-diphenyl-1,10-phenanthroline), in good yields. A time-resolved kinetic evaluation of the formation of [Cu29Cl4H22(Ph 2phen)12]Cl reveals that the mechanism of cluster growth is initiated by rapid ligand exchange, followed by slower extrusion of CuCl monomer, transport, and subsequent capture by intact clusters. Two Cu26 nanoclusters, tentatively formulated as [Cu 26H17(PPh3)9(OAc)3] and [Cu26H22(PPh3)10(OAc)2], are

  13. Oxygen evolution reaction in nanoconfined carbon nanotubes

    Science.gov (United States)

    Li, Ying; Lu, Xuefeng; Li, Yunfang; Zhang, Xueqing

    2018-05-01

    Improving oxygen electrochemistry through nanoscopic confinement has recently been highlighted as a promising strategy. In-depth understanding the role of confinement is therefore required. In this study, we simulate the oxygen evolution reaction (OER) on iron oxide nanoclusters under confinement of (7,7) and (8,8) armchair carbon nanotubes (CNTs). The free energies of the four proton coupled electron transfer (PCET) steps and the OER overpotentials are calculated. The Fe4O6 nanocluster confined in (7,7) CNT is found to be the most active for OER among the systems considered in this work. This leads to an increase in catalytic efficiency of OER compared to the hematite (110) surface, which was reported recently as an active surface towards OER. The calculated results show that the OER overpotential depends strongly on the magnetic properties of the iron oxide nanocluster. These findings are helpful for experimental design of efficient catalyst for water splitting applications.

  14. Serum albumin forms a lactoferrin-like soluble iron-binding complex in presence of hydrogen carbonate ions.

    Science.gov (United States)

    Ueno, Hiroshi M; Urazono, Hiroshi; Kobayashi, Toshiya

    2014-02-15

    The iron-lactoferrin complex is a common food ingredient because of its iron-solubilizing capability in the presence of hydrogen carbonate ions. However, it is unclear whether the formation of a stable iron-binding complex is limited to lactoferrin. In this study, we investigated the effects of bovine serum albumin (BSA) on iron solubility and iron-catalyzed lipid oxidation in the presence of hydrogen carbonate ions. BSA could solubilize >100-fold molar equivalents of iron at neutral pH, exceeding the specific metal-binding property of BSA. This iron-solubilizing capability of BSA was impaired by thermally denaturing BSA at ≥ 70 °C for 10 min at pH 8.5. The resulting iron-BSA complex inhibited iron-catalyzed oxidation of soybean oil in a water-in-oil emulsion measured using the Rancimat test. Our study is the first to show that BSA, like lactoferrin, forms a soluble iron-binding complex in the presence of hydrogen carbonate ions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. Glucose oxidase-functionalized fluorescent gold nanoclusters as probes for glucose

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-04-15

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

  16. Adsorption of benzene and toluene from aqueous solutions onto activated carbon and its acid and heat treated forms: influence of surface chemistry on adsorption.

    Science.gov (United States)

    Wibowo, N; Setyadhi, L; Wibowo, D; Setiawan, J; Ismadji, S

    2007-07-19

    The influence of surface chemistry and solution pH on the adsorption of benzene and toluene on activated carbon and its acid and heat treated forms were studied. A commercial coal-based activated carbon F-400 was chosen as carbon parent. The carbon samples were obtained by modification of F-400 by means of chemical treatment with HNO3 and thermal treatment under nitrogen flow. The treatment with nitric acid caused the introduction of a significant number of oxygenated acidic surface groups onto the carbon surface, while the heat treatment increases the basicity of carbon. The pore characteristics were not significantly changed after these modifications. The dispersive interactions are the most important factor in this adsorption process. Activated carbon with low oxygenated acidic surface groups (F-400Tox) has the best adsorption capacity.

  17. Endohedral confinement of a DNA dodecamer onto pristine carbon nanotubes and the stability of the canonical B form

    Energy Technology Data Exchange (ETDEWEB)

    Cruz, Fernando J. A. L., E-mail: fj.cruz@fct.unl.pt [Requimte/CQFB, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Caparica 2829-516 (Portugal); Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States); Pablo, Juan J. de [Department of Chemical and Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States); Institute of Molecular Engineering, University of Chicago, Chicago, Illinois 60637 (United States); Mota, José P. B. [Requimte/CQFB, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Caparica 2829-516 (Portugal)

    2014-06-14

    Although carbon nanotubes are potential candidates for DNA encapsulation and subsequent delivery of biological payloads to living cells, the thermodynamical spontaneity of DNA encapsulation under physiological conditions is still a matter of debate. Using enhanced sampling techniques, we show for the first time that, given a sufficiently large carbon nanotube, the confinement of a double-stranded DNA segment, 5′-D({sup *}CP{sup *}GP{sup *}CP{sup *}GP{sup *}AP{sup *}AP{sup *}TP{sup *}TP{sup *}CP{sup *}GP{sup *}CP{sup *}G)-3′, is thermodynamically favourable under physiological environments (134 mM, 310 K, 1 bar), leading to DNA-nanotube hybrids with lower free energy than the unconfined biomolecule. A diameter threshold of 3 nm is established below which encapsulation is inhibited. The confined DNA segment maintains its translational mobility and exhibits the main geometrical features of the canonical B form. To accommodate itself within the nanopore, the DNA's end-to-end length increases from 3.85 nm up to approximately 4.1 nm, due to a ∼0.3 nm elastic expansion of the strand termini. The canonical Watson-Crick H-bond network is essentially conserved throughout encapsulation, showing that the contact between the DNA segment and the hydrophobic carbon walls results in minor rearrangements of the nucleotides H-bonding. The results obtained here are paramount to the usage of carbon nanotubes as encapsulation media for next generation drug delivery technologies.

  18. Platinum Iron Intermetallic Nanoparticles Supported on Carbon Formed In Situ by High-Pressure Pyrolysis for Efficient Oxygen Reduction

    DEFF Research Database (Denmark)

    Hu, Yang; Jensen, Jens Oluf; Zhang, Wei

    2016-01-01

    Carbon-supported PtFe alloy catalysts are synthesized by the one-step, high-temperature pyrolysis of Pt, Fe, and C precursors. As a result of the high temperature, the formed PtFe nanoparticles possess highly ordered, face-centered tetragonal, intermetallic structures with a mean size of ≈11.8 nm....... At 0.9 V versus the reversible hydrogen electrode, the PtFe nanoparticles show a 6.8 times higher specific activity than the reference Pt/C catalyst towards the oxygen reduction reaction (ORR) as well as excellent stability, most likely because of the durable intermetallic structure and the preleaching...... treatment of the catalyst. During these preliminary syntheses, we found that a portion of the PtFe nanoparticles is buried in the in situ formed carbon phase, which limits Pt utilization in the catalyst and results in a mass-specific activity equivalent to the commercial Pt/C catalyst. Moreover...

  19. Transparent Conducting Films with Multilayered Structures Formed by Carbon Nanotubes and Reduced Graphene Oxides

    International Nuclear Information System (INIS)

    Kang, Jie Hun; Jang, Hyun Chul; Choi, Jung Mi; Hyeon, Jae Young; Sok, Jung Hyun

    2014-01-01

    The replacement for indium tin oxide (ITO) in electronic displays should have comparable optical transmittance and electrical conductivity while being easy to source and manufacture. However, novel materials such as single walled carbon nanotubes (SWCNTs) and reduced graphene oxides (RGOs) are incapable of addressing these challenges. We demonstrate a simple method to fabricate good transparent conductive films (TCFs) by combining and leveraging the superior optical transparency of RGOs and the excellent electrical conductivity of SWCNTs. This method affords thin multilayers of SWCNTs and RGOs with excellent optical and electrical properties because these properties are correlated with spraying time and the amount of SWCNTs or RGOs. In general, transmittance is advantageous to RGO as conductance is to CNTs. With a view to finding good TCFs with reduced sheet resistance, but with little sacrifice of transmittance, it is natural to explore the combination of CNT and RGO. The sandwiched multilayer of SWCNTs and RGOs exhibited a low sheet resistance of 214.2 Ω/sq, which was comparable to that of SWCNTs, and a transmittance of 60% at a wavelength of 550 nm. To further reduce the sheet resistance and improve the transparency of the multilayer TCFs, Au doping was carried out. The doping, in combination with controlled spraying of the amount of SWCNTs and RGOs, led to multilayers with resistance/transmittance combinations of 141.3 Ω/sq and 70% and 371.5 Ω/sq and 83%. These properties meet the requisite criteria for an ITO replacement.

  20. Microstructure evolution in carbon-ion implanted sapphire

    International Nuclear Information System (INIS)

    Orwa, J. O.; McCallum, J. C.; Jamieson, D. N.; Prawer, S.; Peng, J. L.; Rubanov, S.

    2010-01-01

    Carbon ions of MeV energy were implanted into sapphire to fluences of 1x10 17 or 2x10 17 cm -2 and thermally annealed in forming gas (4% H in Ar) for 1 h. Secondary ion mass spectroscopy results obtained from the lower dose implant showed retention of implanted carbon and accumulation of H near the end of range in the C implanted and annealed sample. Three distinct regions were identified by transmission electron microscopy of the implanted region in the higher dose implant. First, in the near surface region, was a low damage region (L 1 ) composed of crystalline sapphire and a high density of plateletlike defects. Underneath this was a thin, highly damaged and amorphized region (L 2 ) near the end of range in which a mixture of i-carbon and nanodiamond phases are present. Finally, there was a pristine, undamaged sapphire region (L 3 ) beyond the end of range. In the annealed sample some evidence of the presence of diamond nanoclusters was found deep within the implanted layer near the projected range of the C ions. These results are compared with our previous work on carbon implanted quartz in which nanodiamond phases were formed only a few tens of nanometers from the surface, a considerable distance from the projected range of the ions, suggesting that significant out diffusion of the implanted carbon had occurred.

  1. Structural, electronic and vibrational properties of GexCy (x+y=2-5) nanoclusters: A B3LYP-DFT study

    Science.gov (United States)

    Goswami, Sohini; Saha, Sushmita; Yadav, R. K.

    2015-11-01

    An ab-initio study of the stability, structural and electronic properties has been made for 84 germanium carbide nanoclusters, GexCy (x+y=2-5). The configuration possessing the maximum value of final binding energy (FBE), among the various configurations corresponding to a fixed x+y=n value, is named as the most stable structure. The vibrational and optical properties have been investigated only for the most stable structures. A B3LYP-DFT/6-311G(3df) method has been employed to optimize fully the geometries of the nanoclusters. The binding energies (BE), highest-occupied and lowest-unoccupied molecular orbital (HOMO-LUMO) gaps have been obtained for all the clusters and the bond lengths have been reported for the most stable clusters. We have considered the zero point energy (ZPE) corrections. The adiabatic and vertical ionization potentials (IPs) and electron affinities (EAs), charge on atoms, dipole moments, vibrational frequencies, infrared intensities (IR Int.), relative infrared intensities (Rel. IR Int.) and Raman scattering activities have also been investigated for the most stable structures. The configurations containing the carbon atoms in majority are seen to be the most stable structures. The strong C-C bond has important role in stabilizing the clusters. For the clusters containing one germanium atom and all the other as carbon atoms, the BE increases monotonically with the number of the carbon atoms. The HOMO-LUMO gap, IPs and EAs fluctuates with increase in the number of atoms. The nanoclusters containing even number of carbon atoms have large HOMO-LUMO gaps and IPs, whereas the nanoclusters containing even number of carbon atoms have small EAs. In general, the adiabatic IP (EA) is smaller (greater) than the vertical IP (EA). The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every cluster, and may be used to characterize a specific cluster. All the predicted physical quantities are in good agreement with the

  2. Enhancement of cemented waste forms by supercritical CO2 carbonation of standard portland cements

    International Nuclear Information System (INIS)

    Rubin, J.B.; Carey, J.; Taylor, C.M.V.

    1997-01-01

    We are conducting experiments on an innovative transformation concept, using a traditional immobilization technique, that may significantly reduce the volume of hazardous or radioactive waste requiring transport and long-term storage. The standard practice for the stabilization of radioactive salts and residues is to mix them with cements, which may include additives to enhance immobilization. Many of these wastes do not qualify for underground disposition, however, because they do not meet disposal requirements for free liquids, decay heat, head-space gas analysis, and/or leachability. The treatment method alters the bulk properties of a cemented waste form by greatly accelerating the natural cement-aging reactions, producing a chemically stable form having reduced free liquids, as well as reduced porosity, permeability and pH. These structural and chemical changes should allow for greater actinide loading, as well as the reduced mobility of the anions, cations, and radionuclides in aboveground and underground repositories. Simultaneously, the treatment process removes a majority of the hydrogenous material from the cement. The treatment method allows for on-line process monitoring of leachates and can be transported into the field. We will describe the general features of supercritical fluids, as well as the application of these fluids to the treatment of solid and semi-solid waste forms. some of the issues concerning the economic feasibility of industrial scale-up will be addressed, with particular attention to the engineering requirements for the establishment of on-site processing facilities. Finally, the initial results of physical property measurements made on portland cements before and after supercritical fluid processing will be presented

  3. The carbonate mineralogy and distribution of habitat-forming deep-sea corals in the southwest pacific region

    Science.gov (United States)

    Bostock, Helen C.; Tracey, Dianne M.; Currie, Kim I.; Dunbar, Gavin B.; Handler, Monica R.; Mikaloff Fletcher, Sara E.; Smith, Abigail M.; Williams, Michael J. M.

    2015-06-01

    Habitat-forming deep-sea scleractinian and alcyonacean corals from around the southwest Pacific were analysed for their calcium carbonate mineralogy. Scleractinian coral species Solenosmilia variabilis, Enallopsammia rostrata, Goniocorella dumosa, Madrepora oculata and Oculina virgosa were all found to be 100% aragonitic, while some members of the alcyonacean taxa Keratoisis spp., Lepidisis spp., and Paragorgia spp. were determined to be high magnesium (Mg) calcite (with 8-11 mol% MgCO3) and Primnoa sp. is bimineralic with both aragonite and Mg calcite. The majority of these habitat-forming deep-sea corals are found at intermediate depths (800-1200 m) in the Antarctic Intermediate Waters (AAIW) with low salinities (~34.5), temperatures of 4-8 °C and high oxygen concentrations (>180 μmol/kg) and currently sitting above the aragonite saturation horizon (ASH). However, habitat-forming corals have been recorded from greater depths, in cooler waters (2-4 °C) that are undersaturated with respect to aragonite (Ωaragonite160 μmol/kg. To address the sampling depth bias the coral records were normalised by the number of benthic stations (sampling effort) in the same depth range. This shows that the highest number of corals per sampling effort is between 1000 and 1400 m with corals present in over 5% of the stations at these depths. The normalised records and Boot Strap analyses suggests that scleractinian corals, especially S. variabilis should be present in >1% of stations down to 1800 m water depth, with E. rostrata, M. oculata and G. dumosa slightly shallower. While alcyonacean corals are found in >1% down to 2600 m, with Keratoisis spp. the deepest down to 2600 m, while Lepidisis spp. and Paragorgia spp. found down to 1800 m. This suggests that most species can probably tolerate some undersaturation of aragonite (Ωaragonite=0.8-0.9), with several species/genera (S. variabilis; Keratoisis spp.) even more tolerant of lower carbonate concentrations ([CO3 2 -]), down

  4. 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

  5. Modeling of metal nanocluster growth on patterned substrates and surface pattern formation under ion bombardment

    Energy Technology Data Exchange (ETDEWEB)

    Numazawa, Satoshi

    2012-11-01

    This work addresses the metal nanocluster growth process on prepatterned substrates, the development of atomistic simulation method with respect to an acceleration of the atomistic transition states, and the continuum model of the ion-beam inducing semiconductor surface pattern formation mechanism. Experimentally, highly ordered Ag nanocluster structures have been grown on pre-patterned amorphous SiO{sub 2} surfaces by oblique angle physical vapor deposition at room temperature. Despite the small undulation of the rippled surface, the stripe-like Ag nanoclusters are very pronounced, reproducible and well-separated. The first topic is the investigation of this growth process with a continuum theoretical approach to the surface gas condensation as well as an atomistic cluster growth model. The atomistic simulation model is a lattice-based kinetic Monte-Carlo (KMC) method using a combination of a simplified inter-atomic potential and experimental transition barriers taken from the literature. An effective transition event classification method is introduced which allows a boost factor of several thousand compared to a traditional KMC approach, thus allowing experimental time scales to be modeled. The simulation predicts a low sticking probability for the arriving atoms, millisecond order lifetimes for single Ag monomers and {approx}1 nm square surface migration ranges of Ag monomers. The simulations give excellent reproduction of the experimentally observed nanocluster growth patterns. The second topic specifies the acceleration scheme utilized in the metallic cluster growth model. Concerning the atomistic movements, a classical harmonic transition state theory is considered and applied in discrete lattice cells with hierarchical transition levels. The model results in an effective reduction of KMC simulation steps by utilizing a classification scheme of transition levels for thermally activated atomistic diffusion processes. Thermally activated atomistic movements

  6. In vitro receptivity of carbonate rocks to endolithic lichen-forming aposymbionts.

    Science.gov (United States)

    Favero-Longo, Sergio E; Borghi, Alessandro; Tretiach, Mauro; Piervittori, Rosanna

    2009-10-01

    Sterile cultured isolates of lichen-forming aposymbionts have not yet been used to investigate lichen-rock interactions under controlled conditions. In this study mycobionts and photobiont of the endolithic lichens Bagliettoa baldensis and Bagliettoa marmorea were isolated and inoculated with coupons of one limestone and four marbles commonly employed in the Cultural Heritage framework. After one year of incubation, microscopic observations of polished cross-sections were performed to verify if the typical colonization patterns observed in the field may be reproduced in vitro and to evaluate the receptivity of the five lithotypes to endolithic lichens. The mycobionts of the two species developed both on the surface of and within all the lithotypes, showing different penetration pathways which depend on mineralogical and structural features and highlight different receptivity. By contrast, algae inoculated with the coupons did not penetrate them. Observations suggest that the hyphal penetration along intrinsic discontinuities of rocks is a relatively fast phenomenon when these organisms are generally considered as slow-growing. Samples from limestone outcrops and abandoned marble quarries, colonized by the same species or other representatives of Verrucariaceae, showed penetration pathways intriguingly similar to those reproduced in vitro and highlighted that lichen-driven erosion processes only increase the availability of hyphal passageways after a long-term colonization. These results show that in vitro incubation of sterile cultured lichen-forming ascomycetes with rock coupons is a practicable experimental system to investigate the lichen-rock interactions under controlled conditions and, together with analysis in situ, may support decisions on conservative treatments of historical and cultural significant stone substrata.

  7. Study of the corrosion products formed on carbon steels in the tropical atmosphere of Panama

    Directory of Open Access Journals (Sweden)

    Jaén, J. A.

    2003-12-01

    Full Text Available Mössbauer spectroscopy and X-ray powder diffraction (in selected samples have been used to characterize corrosion products on carbon steels after atmospheric exposure to the tropical Panamanian locations of Panama and Colon, classified according to ISO 9223 as C3 and C5, respectively. Goethite (α-FeOOH of intermediate particle size (20-100 nm, lepidocrocite (γ-FeOOH, a spinel phase consisting of non-stoichiometric magnetite (Fe3-xO4 and/or maghemite (γ-Fe2O3 and nano-sized particles were identified in the corrosion products. The spinel phase is related to short term atmospheric exposure transforms in time to other corrosion products. The corrosion resistance increased with fraction of goethite following a saturation-type behavior.

    Se caracterizaron los productos de corrosión de aceros al carbono expuestos a las atmósferas tropicales panameñas localizadas en Panamá y Colón, mediante el uso de la espectroscopia Mössbauer y difracción de rayos-X (en muestras seleccionadas. Las atmósferas se clasifican como C3 y C5, respectivamente, de acuerdo a la norma ISO 9223. Se lograron identificar los compuestos goethita (α-FeOOH de tamaño de partícula intermedio (20-100 nm, lepidocrocita (γ-FeOOH, una fase de espinela consistente en magnetita no estequiométrica (Fe3-xO4 y/o maghemita (γ-Fe2O3, y nanopartículas. La fase de espinela se puede correlacionar con exposiciones cortas a la atmósfera, transformándose en el tiempo en otros productos de corrosión. La resistencia a la corrosión se incrementa con la cantidad de goethita siguiendo una conducta de saturación.

  8. 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.

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

    Science.gov (United States)

    Kabir, L.; Mandal, A. R.; Mandal, S. K.

    2010-04-01

    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 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 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.

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

    International Nuclear Information System (INIS)

    Kabir, L.; Mandal, A.R.; Mandal, S.K.

    2010-01-01

    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 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 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.

  11. Microwave-heating synthesis and sensing applications of bright gold nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    He, Ding-Fei; Xiang, Yang; Wang, Xu [Department of Physics, Key Laboratory of Artificial Micro- and Nano-structures of Ministry of Education and School of Physics and Technology, Wuhan University, Wuhan 430072 (China); Yu, Xue-Feng, E-mail: yxf@whu.edu.cn [Department of Physics, Key Laboratory of Artificial Micro- and Nano-structures of Ministry of Education and School of Physics and Technology, Wuhan University, Wuhan 430072 (China)

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer We establish a microwave-heating method to synthesize protein-stabilized Au nanoclusters. Black-Right-Pointing-Pointer The obtained Au nanoclusters show bright red fluorescence. Black-Right-Pointing-Pointer The Au nanoclusters can be used as efficient fluorescence probe for Cu{sup 2+} ion sensing. -- Abstract: A rapid microwave-heating method has been developed for the synthesis of bright Au nanoclusters by using bull serum albumin as the template in an aqueous environment. The reaction time needed is only 7.0 min, and the weight of the products at one batch can reach 15 g. The Au nanoclusters exhibit bright fluorescence at {approx}613 nm with quantum yield of {approx}6.0%. By adjusting the pH value, the products can be controlled to precipitate or re-disperse in aqueous solution. Furthermore, the Au nanoclusters have exhibited high sensitivity and selectivity in the determination of Cu{sup 2+} ions in water. These results suggest an efficient method for obtaining metal nanoclusters for the detection and sensing applications.

  12. A DFT study for the structural and electronic properties of Zn m Se n nanoclusters

    Science.gov (United States)

    Yadav, Phool Singh; Pandey, Dheeraj Kumar

    2012-09-01

    An ab initio study has been performed for the stability, structural and electronic properties of 19 small zinc selenide Zn m Se n ( m + n = 2-4) nanoclusters. Out of these nanoclusters, one nanocluster is found to be unstable due to its imaginary vibrational frequency. A B3LYP-DFT/6-311G(3df) method is used in the optimization of the geometries of the nanoclusters. We have calculated the zero point energy (ZPE), which is ignored by the other workers. The binding energies (BE), HOMO-LUMO gaps and bond lengths have been obtained for all the optimized nanoclusters. For the same value of ` m' and ` n', we designate the most stable structure the one, which has maximum final binding energy (FBE) per atom. The adiabatic and vertical ionization potentials (IP) and electron affinities (EA), dipole moments and charge on atoms have been investigated for the most stable nanoclusters. For the same value of ` m' and ` n', the nanocluster containing maximum number of Se atoms is found to be most stable.

  13. Nano-scale clusters formed in the early stage of phase decomposition of Al-Mg-Si alloys

    Energy Technology Data Exchange (ETDEWEB)

    Hirosawa, S.; Sato, T. [Dept. of Metallurgy and Ceramics Science, Tokyo Inst. of Tech. (Japan)

    2005-07-01

    The formation of nano-scale clusters (nanoclusters) prior to the precipitation of the strengthening {beta}'' phase significantly influences two-step aging behavior of Al-Mg-Si alloys. In this work, the existence of two kinds of nanoclusters has been verified in the early stage of phase decomposition by differential scanning calorimetry (DSC) and three-dimensional atom probe (3DAP). Pre-aging treatment at 373 K before natural aging was also found to form preferentially one of the two nanoclusters, resulting in the remarkable restoration of age-hardenability at paint-bake temperatures. Such microstructural control by means of optimized heat-treatments; i.e. nanocluster assist processing (NCAP), possesses great potential for enabling Al-Mg-Si alloys to be used more widely as a body-sheet material of automobiles. (orig.)

  14. Morphological and magnetic properties of cobalt nanoclusters electrodeposited onto HOPG

    International Nuclear Information System (INIS)

    Rivera, M.; Rios-Reyes, C.H.; Mendoza-Huizar, L.H.

    2008-01-01

    In this work, the morphological and magnetic properties of cobalt nanoclusters obtained from two different sulphate electrolyte solutions were studied. The aggregates were electrodeposited onto highly oriented pyrolytic graphite electrodes in overpotential conditions, in order to investigate the cationic influence on the final properties of the aggregates. In both cases, scanning electron microscopy and atomic force microscopy showed random isolated clusters on the electrode surface, where size variations were determined by the electrolyte solution. By using magnetic force microscopy, the distribution of the electrodeposited magnetic material was more clearly observed which gave some insights on the growth mechanism of these aggregates.

  15. Ion implantation induced conducting nano-cluster formation in PPO

    International Nuclear Information System (INIS)

    Das, A.; Patnaik, A.; Ghosh, G.; Dhara, S.

    1997-01-01

    Conversion of polymers and non-polymeric organic molecules from insulating to semiconducting materials as an effect of energetic ion implantation is an established fact. Formation of nano-clusters enriched with carbonaceous materials are made responsible for the insulator-semiconductor transition. Conduction in these implanted materials is observed to follow variable range hopping (VRH) mechanism. Poly(2,6-dimethyl phenylene oxide) [PPO] compatible in various proportion with polystyrene is used as a high thermal resistant insulating polymer. PPO has been used for the first time in the ion implantation study

  16. Ultrafast coherence transfer in DNA-templated silver nanoclusters

    DEFF Research Database (Denmark)

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

    2017-01-01

    DNA-templated silver nanoclusters of a few tens of atoms or less have come into prominence over the last several years due to very strong absorption and efficient emission. Applications in microscopy and sensing have already been realized, however little is known about the excited-state structure...... and dynamics in these clusters. Here we report on a multidimensional spectroscopy investigation of the energy-level structure and the early-time relaxation cascade, which eventually results in the population of an emitting state. We find that the ultrafast intramolecular relaxation is strongly coupled...

  17. Late Paleozoic SEDEX deposits in South China formed in a carbonate platform at the northern margin of Gondwana

    Science.gov (United States)

    Qiu, Wenhong Johnson; Zhou, Mei-Fu; Liu, Zerui Ray

    2018-05-01

    SEDEX sulfide deposits hosted in black shale and carbonate are common in the South China Block. The Dajiangping pyrite deposit is the largest of these deposits and is made up of stratiform orebodies hosted in black shales. Sandstone interlayered with stratiform orebodies contains detrital zircon grains with the youngest ages of 429 Ma. Pyrite from the orebodies has a Re-Os isochron age of 389 ± 62 Ma, indicative of formation of the hosting strata and syngenetic pyrite ores in the mid-late Devonian. The hosting strata is a transgression sequence in a passive margin and composed of carbonaceous limestone in the lower part and black shales in the upper part. The ore-hosting black shales have high TOC (total organic carbon), Mo, As, Pb, Zn and Cd, indicating an anoxic-euxinic deep basin origin. The high redox proxies, V/(V + Ni) > 0.6 and V/Cr > 1, and the positive correlations of TOC with Mo and V in black shales are also consistent with an anoxic depositional environment. The Dajiangping deposit is located close to the NE-trending Wuchuan-Sihui fault, which was active during the Devonian. The mid-late Devonian mineralization age and the anoxic-euxinic deep basinal condition of this deposit thus imply that the formation of this deposit was causally linked to hydrothermal fluid exhalation in an anoxic fault-bounded basin that developed in a carbonate platform of the South China Block. The regional distribution of many Devonian, stratiform, carbonaceous sediment-hosted sulfide deposits along the NE-trending fault-bounded basins in South China, similar to the Dajiangping deposit, indicates that these deposits formed at a basin developed in the passive margin setting of the South China Block during the Devonian. This environment was caused by the break-up and northward migration of the South China Block from Gandwana.

  18. Effect of quencher, denaturants, temperature and pH on the fluorescent properties of BSA protected gold nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Chib, Rahul, E-mail: Rahul.chib@live.unthsc.edu [Department of Cell Biology and Immunology, Center for Fluorescence Technologies and Nanomedicine, University of North Texas Health Science Center, Fort Worth, TX 76107 (United States); Butler, Susan [Department of Cell Biology and Immunology, Center for Fluorescence Technologies and Nanomedicine, University of North Texas Health Science Center, Fort Worth, TX 76107 (United States); Raut, Sangram [Department of Cell Biology and Immunology, Center for Fluorescence Technologies and Nanomedicine, University of North Texas Health Science Center, Fort Worth, TX 76107 (United States); Department of Physics and Astronomy, Texas Christian University, Fort Worth, TX 76129 (United States); Shah, Sunil; Borejdo, Julian [Department of Cell Biology and Immunology, Center for Fluorescence Technologies and Nanomedicine, University of North Texas Health Science Center, Fort Worth, TX 76107 (United States); Gryczynski, Zygmunt [Department of Cell Biology and Immunology, Center for Fluorescence Technologies and Nanomedicine, University of North Texas Health Science Center, Fort Worth, TX 76107 (United States); Department of Physics and Astronomy, Texas Christian University, Fort Worth, TX 76129 (United States); Gryczynski, Ignacy, E-mail: ignacy.gryczynski@unthsc.edu [Department of Cell Biology and Immunology, Center for Fluorescence Technologies and Nanomedicine, University of North Texas Health Science Center, Fort Worth, TX 76107 (United States)

    2015-12-15

    In this paper, we have synthesized BSA protected gold nanoclusters (BSA Au nanocluster) and studied the effect of quencher, protein denaturant, pH and temperature on the fluorescence properties of the tryptophan molecule of the BSA Au nanocluster and native BSA. We have also studied their effect on the peak emission of BSA Au nanoclusters (650 nm). The photophysical characterization of a newly developed fluorophore in different environments is absolutely necessary to futher develop their biomedical and analytical applications. It was observed from our experiments that the tryptophan in BSA Au nanoclusters is better shielded from the polar environment. Tryptophan in native BSA showed a red shift in its peak emission wavelength position. Tryptophan is a highly polarity sensitive dye and a minimal change in its microenvironment can be easily observed in its photophysical properties. - Highlights: • Tryptophan is easily accessible in native BSA compared to BSA Au nanoclusters. • Guanidine HCL denatures native BSA more compared to BSA Au nanoclusters. • High temperature decreases the quantum yield of tryptophan and BSA Au nanocluster. • Emission wavelength of BSA Au nanoclusters remains constant with increasing pH. • BSA Au nanoclusters are robust to the changes in their environments.

  19. Effect of quencher, denaturants, temperature and pH on the fluorescent properties of BSA protected gold nanoclusters

    International Nuclear Information System (INIS)

    Chib, Rahul; Butler, Susan; Raut, Sangram; Shah, Sunil; Borejdo, Julian; Gryczynski, Zygmunt; Gryczynski, Ignacy

    2015-01-01

    In this paper, we have synthesized BSA protected gold nanoclusters (BSA Au nanocluster) and studied the effect of quencher, protein denaturant, pH and temperature on the fluorescence properties of the tryptophan molecule of the BSA Au nanocluster and native BSA. We have also studied their effect on the peak emission of BSA Au nanoclusters (650 nm). The photophysical characterization of a newly developed fluorophore in different environments is absolutely necessary to futher develop their biomedical and analytical applications. It was observed from our experiments that the tryptophan in BSA Au nanoclusters is better shielded from the polar environment. Tryptophan in native BSA showed a red shift in its peak emission wavelength position. Tryptophan is a highly polarity sensitive dye and a minimal change in its microenvironment can be easily observed in its photophysical properties. - Highlights: • Tryptophan is easily accessible in native BSA compared to BSA Au nanoclusters. • Guanidine HCL denatures native BSA more compared to BSA Au nanoclusters. • High temperature decreases the quantum yield of tryptophan and BSA Au nanocluster. • Emission wavelength of BSA Au nanoclusters remains constant with increasing pH. • BSA Au nanoclusters are robust to the changes in their environments.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-06-01

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

  1. Size-Dependent Specific Surface Area of Nanoporous Film Assembled by Core-Shell Iron Nanoclusters

    Directory of Open Access Journals (Sweden)

    Jiji Antony

    2006-01-01

    Full Text Available Nanoporous films of core-shell iron nanoclusters have improved possibilities for remediation, chemical reactivity rate, and environmentally favorable reaction pathways. Conventional methods often have difficulties to yield stable monodispersed core-shell nanoparticles. We produced core-shell nanoclusters by a cluster source that utilizes combination of Fe target sputtering along with gas aggregations in an inert atmosphere at 7∘C. Sizes of core-shell iron-iron oxide nanoclusters are observed with transmission electron microscopy (TEM. The specific surface areas of the porous films obtained from Brunauer-Emmett-Teller (BET process are size-dependent and compared with the calculated data.

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

    DEFF Research Database (Denmark)

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

    2008-01-01

    This paper reports the formation of Ge nanoclusters in a multi-layer structure consisting of alternating thin films of Ge-doped silica glass and SiGe, deposited by plasma-enhanced chemical vapor deposition (PECVD) and post annealed at 1100 °C in N2 atmosphere. We studied the annealed samples...... embedded with Ge nanoclusters after annealing. These nanoclusters are crystalline and varied in size. There were no clusters in the Ge-doped glass layer. Raman spectra verified the existence of crystalline Ge clusters. The positional shift of the Ge vibrational peak with the change of the focus depth...

  3. Carbon isotope composition of CO2-rich inclusions in cumulate-forming mantle minerals from Stromboli volcano (Italy)

    Science.gov (United States)

    Gennaro, Mimma Emanuela; Grassa, Fausto; Martelli, Mauro; Renzulli, Alberto; Rizzo, Andrea Luca

    2017-10-01

    We report on measurements of concentration and carbon isotope composition (δ13CCO2) of CO2 trapped in fluid inclusions of olivine and clinopyroxene crystals separated from San Bartolo ultramafic cumulate Xenoliths (SBX) formed at mantle depth (i.e., beneath a shallow Moho supposed to be at 14.8 km). These cumulates, erupted about 2 ka ago at Stromboli volcano (Italy), have been already investigated by Martelli et al. (2014) mainly for Sr-Nd isotopes and for their noble gases geochemistry. The concentration of CO2 varies of one order of magnitude from 3.8·10- 8 mol g- 1 to 4.8·10- 7 mol g- 1, with δ13C values between - 2.8‰ and - 1.5‰ vs V-PDB. These values overlap the range of measurements performed in the crater gases emitted at Stromboli (- 2.5‰ residence within the volcano plumbing system. Such δ13C values are higher than those commonly reported for MORB-like upper mantle (- 8 ÷ - 4‰) and likely reflect the source contamination of the local mantle wedge by CO2 coming from the decarbonation of the sediments carried by the subducting Ionian slab with a contribution of organic carbon up to 7%.

  4. Experimental measurements of U24Py nanocluster behavior in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Flynn, Shannon L.; Szymanowski, Jennifer E.S.; Fein, Jeremy B. [Univ. of Notre Dame, IN (United States). Department of Civil and Environmental Engineering and Earth Sciences; Dembowski, Mateusz [Univ. of Notre Dame, IN (United States). Department of Chemistry and Biochemistry; Burns, Peter C. [Univ. of Notre Dame, IN (United States). Department of Civil and Environmental Engineering and Earth Sciences; Univ. of Notre Dame, IN (United States). Department of Chemistry and Biochemistry

    2016-07-01

    Uranyl peroxide nanoclusters may impact the mobility and partitioning of uranium at contaminated sites and could be used in the isolation of uranium during the reprocessing of nuclear waste. Their behavior in aqueous systems must be better understood to predict the environmental fate of uranyl peroxide nanoclusters and for their use in engineered systems. The aqueous stability of only one uranyl peroxide nanocluster, U60 (K{sub 16}Li{sub 44}[UO{sub 2}(O{sub 2})OH]{sub 60}), has been studied to date [Flynn, S. L., Szymanowski, J. E. S., Gao, Y., Liu, T., Burns, P. C., Fein, J. B.: Experimental measurements of U60 nanocluster stability in aqueous solution. Geochemica et Cosmochimica Acta 156, 94-105 (2015)]. In this study, we measured the aqueous stability of a second uranyl peroxide nanocluster, U24Py (Na{sub 30}[(UO{sub 2}){sub 24}(O{sub 2}){sub 24}(HP{sub 2}O{sub 7}){sub 6}(H{sub 2}P{sub 2}O{sub 7}){sub 6}]), in batch systems as a function of time, pH, and nanocluster concentration, and then compared the aqueous behavior of U24Py to U60 to determine whether the size and morphology differences result in differences in their aqueous behaviors. Systems containing U24Py nanoclusters took over 30 days to achieve steady-state concentrations of monomeric U, Na, and P, illustrating slower reaction kinetics than parallel U60 systems. Furthermore, U24Py exhibited lower stability in solution than U60, with an average of 72% of the total mass in each nanocluster suspension being associated with the U24Py nanocluster, whereas 97% was associated with the U60 nanocluster in parallel experiments [Flynn, S. L., Szymanowski, J. E. S., Gao, Y., Liu, T., Burns, P. C., Fein, J. B.: Experimental measurements of U60 nanocluster stability in aqueous solution. Geochemica et Cosmochimica Acta 156, 94-105 (2015)]. The measurements from the batch experiments were used to calculate ion activity product (IAP) values for the reaction between the U24Py nanocluster and its constituent monomeric

  5. Atomic structure of embedded Fe nanoclusters as a function of host matrix material: a synchrotron radiation study

    International Nuclear Information System (INIS)

    Baker, S H; Roy, M; Gurman, S J; Louch, S; Bleloch, A; Binns, C

    2004-01-01

    The atomic structure of Fe nanoclusters embedded in a range of matrix materials has been studied using synchrotron radiation. In particular, the effect of embedding the clusters in Ag, amorphous carbon (a-C) and a porous C 60 matrix is investigated. The embedded cluster samples were prepared by co-deposition using a gas aggregation cluster source. Samples with both dilute and high-volume-filling fraction of clusters, at 4 and 40% respectively, were prepared. Fe K edge EXAFS measurements were used to probe the structure within the clusters. In a Ag matrix, the Fe clusters retain the b.c.c. structure of bulk Fe while in a-C there is evidence for both b.c.c. and f.c.c. structures in the clusters. These results are independent of cluster volume-filling fraction over the range investigated. When embedded in a porous C 60 matrix, the Fe clusters oxidize to Fe 2 O 3

  6. Coherent radiation by quantum dots and magnetic nanoclusters

    International Nuclear Information System (INIS)

    Yukalov, V. I.; Yukalova, E. P.

    2014-01-01

    The assemblies of either quantum dots or magnetic nanoclusters are studied. It is shown that such assemblies can produce coherent radiation. A method is developed for solving the systems of nonlinear equations describing the dynamics of such assemblies. The method is shown to be general and applicable to systems of different physical nature. Despite mathematical similarities of dynamical equations, the physics of the processes for quantum dots and magnetic nanoclusters is rather different. In a quantum dot assembly, coherence develops due to the Dicke effect of dot interactions through the common radiation field. For a system of magnetic clusters, coherence in the spin motion appears due to the Purcell effect caused by the feedback action of a resonator. Self-organized coherent spin radiation cannot arise without a resonator. This principal difference is connected with the different physical nature of dipole forces between the objects. Effective dipole interactions between the radiating quantum dots, appearing due to photon exchange, collectivize the dot radiation. While the dipolar spin interactions exist from the beginning, yet before radiation, and on the contrary, they dephase spin motion, thus destroying the coherence of moving spins. In addition, quantum dot radiation exhibits turbulent photon filamentation that is absent for radiating spins

  7. 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).

  8. Rust Layer Formed on Low Carbon Weathering Steels with Different Mn, Ni Contents in Environment Containing Chloride Ions

    Directory of Open Access Journals (Sweden)

    Gui-qin FU

    2016-11-01

    Full Text Available The rusting evolution of low carbon weathering steels with different Mn, Ni contents under a simulated environment containing chloride ions has been investigated to clarify the correlation between Mn, Ni and the rust formed on steels. The results show that Mn contents have little impact on corrosion kinetics of experimental steels. Content increase of Ni both enhances the anti-corrosion performance of steel substrate and the rust. Increasing Ni content is beneficial to forming compact rust. Semi-quantitative XRD phase analysis shows that the quantity ratio of α/γ*(α-FeOOH/(γ-FeOOH+Fe3O4 decreases as Mn content increases but it increases as Ni content increases. Ni enhances rust layer stability but Mn content exceeding 1.06 wt.% is disadvantageous for rust layer stability. The content increase of Mn does not significantly alter the parameters of the polarization curve. However, as Ni contents increases, Ecorr has shifted to the positive along with decreased icorr values indicating smaller corrosion rate especially as Ni content increases from 0.42 wt.% to 1.50 wt.%.DOI: http://dx.doi.org/10.5755/j01.ms.22.4.12844

  9. [Case of interval form of carbon monoxide poisoning without increased carboxyhemoglobin level diagnosed by characteristic MR spectroscopy findings].

    Science.gov (United States)

    Kamisawa, Tomoko; Ikawa, Masamichi; Hamano, Tadanori; Nagata, Miwako; Kimura, Hirohiko; Yoneda, Makoto

    2014-01-01

    A 67-year-old man living alone was admitted for acute disturbance of consciousness during winter. He presented with semicoma, a decorticate posture, and exaggerated tendon reflexes of the limbs, but brainstem reflexes were intact. The carboxyhemoglobin (COHb) level was normal in arterial blood gas on admission, and protein in cerebrospinal fluid was increased without pleocytosis. Brain MRI showed diffuse T2 high intensities in the deep white matter bilaterally without a contrast effect and abnormal T1 intensity in the pallidum. (1)H-MR spectroscopy (MRS) of the white matter lesion demonstrated findings suggesting demyelination as an increased choline peak, enhanced anaerobic metabolism as increased lactate and lipids peaks, and reduced neurons as a decreased N-acetylaspartate peak, which corresponded to delayed encephalopathy due to the interval form of carbon monoxide (CO) poisoning. The possibility of CO exposure due to coal briquette use 2 weeks before the symptomatic onset was indicated by his family, so he was diagnosed with CO poisoning. His consciousness slightly improved with corticosteroid therapy and repetitive hyperbaric oxygen therapy, but brain MRI and MRS findings did not improve. Characteristic MRS findings of leukoencephalopathy are helpful for diagnosing the interval form of CO poisoning in the case of a normal COHb level.

  10. Hydrothermal Synthesis of Nanoclusters of ZnS Comprised on Nanowires

    Directory of Open Access Journals (Sweden)

    Magnus Willander

    2013-09-01

    Full Text Available Cetyltrimethyl ammonium bromide cationic (CTAB surfactant was used as template for the synthesis of nanoclusters of ZnS composed of nanowires, by hydrothermal method. The structural and morphological studies were performed by using X-ray diffraction (XRD, scanning electron microscopy (SEM and high resolution transmission electron microscopy (HRTEM techniques. The synthesized ZnS nanoclusters are composed of nanowires and high yield on the substrate was observed. The ZnS nanocrystalline consists of hexagonal phase and polycrystalline in nature. The chemical composition of ZnS nanoclusters composed of nanowires was studied by X-ray photo electron microscopy (XPS. This investigation has shown that the ZnS nanoclusters are composed of Zn and S atoms.

  11. Hydrothermal Synthesis of Nanoclusters of ZnS Comprised on Nanowires.

    Science.gov (United States)

    Ibupoto, Zafar Hussain; Khun, Kimleang; Liu, Xianjie; Willander, Magnus

    2013-09-09

    Cetyltrimethyl ammonium bromide cationic (CTAB) surfactant was used as template for the synthesis of nanoclusters of ZnS composed of nanowires, by hydrothermal method. The structural and morphological studies were performed by using X-ray diffraction (XRD), scanning electron microscopy (SEM) and high resolution transmission electron microscopy (HRTEM) techniques. The synthesized ZnS nanoclusters are composed of nanowires and high yield on the substrate was observed. The ZnS nanocrystalline consists of hexagonal phase and polycrystalline in nature. The chemical composition of ZnS nanoclusters composed of nanowires was studied by X-ray photo electron microscopy (XPS). This investigation has shown that the ZnS nanoclusters are composed of Zn and S atoms.

  12. Mechanical stability of titanium and plasma polymer nanoclusters in nanocomposite coatings

    Energy Technology Data Exchange (ETDEWEB)

    Palesch, E. [Institute of Materials Chemistry, Brno University of Technology, Brno (Czech Republic); Marek, A. [HVM Plasma, spol. s r.o., Prague (Czech Republic); Solar, P.; Kylian, O. [Faculty of Mathematics and Physics, Charles University, Prague (Czech Republic); Vyskocil, J. [HVM Plasma, spol. s r.o., Prague (Czech Republic); Biederman, H. [Faculty of Mathematics and Physics, Charles University, Prague (Czech Republic); Cech, V., E-mail: cech@fch.vutbr.cz [Institute of Materials Chemistry, Brno University of Technology, Brno (Czech Republic)

    2013-10-01

    The mechanical stability of nanoclusters embedded in nanocomposite coatings was investigated by scratch and wear tests supported by atomic force microscopy using surface topography mode. Titanium and plasma polymer nanoclusters were deposited on planar substrates (glass, titanium) using a magnetron-based gas aggregation cluster source. The deposited clusters were overcoated with a thin titanium film of different thicknesses to stabilize the position of the clusters in the nanocomposite coating. Nanotribological measurements were carried out to optimize the thickness of the overcoating film for sufficient interfacial adhesion of the cluster/film system. - Highlights: ► Titanium and plasma polymer nanoclusters were overcoated with thin titanium film. ► The mechanical stability of nanoclusters was characterized by nanotribological tests. ► The film thickness was optimized to stabilize the position of the clusters in coating.

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

    Science.gov (United States)

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

    2015-10-01

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

  14. Pure white-light emitting ultrasmall organic-inorganic hybrid perovskite nanoclusters.

    Science.gov (United States)

    Teunis, Meghan B; Lawrence, Katie N; Dutta, Poulami; Siegel, Amanda P; Sardar, Rajesh

    2016-10-14

    Organic-inorganic hybrid perovskites, direct band-gap semiconductors, have shown tremendous promise for optoelectronic device fabrication. We report the first colloidal synthetic approach to prepare ultrasmall (∼1.5 nm diameter), white-light emitting, organic-inorganic hybrid perovskite nanoclusters. The nearly pure white-light emitting ultrasmall nanoclusters were obtained by selectively manipulating the surface chemistry (passivating ligands and surface trap-states) and controlled substitution of halide ions. The nanoclusters displayed a combination of band-edge and broadband photoluminescence properties, covering a major part of the visible region of the solar spectrum with unprecedentedly large quantum yields of ∼12% and photoluminescence lifetime of ∼20 ns. The intrinsic white-light emission of perovskite nanoclusters makes them ideal and low cost hybrid nanomaterials for solid-state lighting applications.

  15. Synthesis and Optical Properties of a Dithiolate/Phosphine-Protected Au28 Nanocluster

    KAUST Repository

    Aljuhani, Maha A.; Bootharaju, Megalamane Siddaramappa; Sinatra, Lutfan; Basset, Jean-Marie; Mohammed, Omar F.; Bakr, Osman

    2016-01-01

    While monothiols and simple phosphines are commonly exploited for size-controlled synthesis of atomically precise gold nanoclusters (NCs), dithiols or dithiol-phosphine combinations are seldom applied. Herein, we used a dithiol (benzene-1,3-dithiol

  16. Magnetic properties of MnAs nanoclusters embedded in a GaAs semiconductor matrix

    International Nuclear Information System (INIS)

    Hai, Pham Nam; Takahashi, Keisuke; Yokoyama, Masafumi; Ohya, Shinobu; Tanaka, Masaaki

    2007-01-01

    We have clarified fundamental magnetic properties of MnAs nanoclusters (10 nm in diameter) embedded in a thin GaAs matrix (referred to as GaAs:MnAs) through tunneling magnetoresistance (TMR) characteristics of magnetic tunnel junctions (MTJs) consisting of a GaAs:MnAs thin film and a MnAs metal thin film as ferromagnetic electrodes. Although MnAs nanoclusters have coercive forces as small as 150 Oe at 7 K, they show unusually high blocking temperature, which is as large as 300 K. The remanent magnetization of the MnAs nanocluster system linearly decreases with increasing temperature. Those magnetic behaviors cannot be explained by the non-interacting particle model, revealing the important existence of dipolar interactions in MnAs nanocluster system

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

    KAUST Repository

    Aljuhani, Maha A.

    2016-01-01

    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

  18. Stable silver nanoclusters electrochemically deposited on nitrogen-doped graphene as efficient electrocatalyst for oxygen reduction reaction

    Science.gov (United States)

    Jin, Shi; Chen, Man; Dong, Haifeng; He, Bingyu; Lu, Huiting; Su, Lei; Dai, Wenhao; Zhang, Qiaochu; Zhang, Xueji

    2015-01-01

    Metal nanoclusters exhibit unusually high catalytic activity toward oxygen reduction reaction (ORR) due to their small size and unique electronic structures. However, controllable synthesis of stable metal nanoclusters is a challenge, and the durability of metal clusters suffers from the deficiency of dissolution, aggregation, and sintering during catalysis reactions. Herein, silver nanoclusters (AgNCs) (diameter , which is vital in high performance fuel cells, batteries and nanodevices.

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

    Science.gov (United States)

    2016-01-13

    affected by the environment of the stabilizing protein, allowing these hybrid systems to act as sensors in many applications.2,9,14–19 This has led...Biosens Bioelectron. 2012;32:297–299. 8. Joseph D, Geckeler KE. Synthesis of highly fluorescent gold nanoclusters using egg white proteins. Colloids Surf...Chang HW, Chien YC, Hsiao JK, Cheng JT, Chou PT. Insulin -directed synthesis of fluorescent gold nanoclusters: preservation of insulin bioactivity and

  20. Factors of influencing dissolved organic carbon stabilization in two cambic forest soils with contrasting soil-forming processes

    Science.gov (United States)

    Kawasaki, M.; Ohte, N.; Asano, Y.; Uchida, T.; Kabeya, N.; Kim, S.

    2004-05-01

    Stabilization of Dissolved Organic Carbon (DOC) in forest soil is a major process of soil organic carbon formation. However, the factors influencing DOC stabilization are poorly understood. To clarify the factors that affect the stabilization of DOC in forest soil mantle, we measured DOC concentrations and soil properties which were DOC adsorption efficiency at two adjacent cambic forest soils with contrasting forest management histories in Tanakami Mountains, central Japan. Matsuzawa was devastated about 1,200 years ago by excessive timber use and remained denuded for a long period. Hillside restoration and reforestation work have been carried out over the last 100 years and soil loss has been reduced. Fudoji is covered with undisturbed forest (mixed stands of cypress and oaks) with developed forest soils (more than 2,600 years old). There was no apparent seasonal variation in DOC concentration in the soil solution in either catchment. In addition, there were no significant relationships between the DOC concentration, soil temperature, and new water ratio. These results indicate that temporal variation in biological activity and rainfall-runoff process have little effect on temporal variation in DOC. The vertical variation in the DOC adsorption efficiency and DOC concentration differed between Matsuzawa and Fudoji, and the highest DOC removal rate occurred at the lowest DOC adsorption efficiency in the 0 to 10-cm soil layer at Fudoji. These results suggest that DOC removal rate is independent of DOC adsorption efficiency. Below 60 cm soil depth, DOC fluxes were constant and dissolved organic Al concentrations were little or zero in either catchment. These results suggest that abiotic precipitation of DOC is a major mechanism for stabilization of DOC. Therefore, DOC content which is able to form metal complexes may be the most important factor of influencing DOC stabilization in cambic forest soil.

  1. Iron/iron oxide core-shell nanoclusters for biomedical applications

    International Nuclear Information System (INIS)

    Qiang You; Antony, Jiji; Sharma, Amit; Nutting, Joseph; Sikes, Daniel; Meyer, Daniel

    2006-01-01

    Biocompatible magnetic nanoparticles have been found promising in several biomedical applications for tagging, imaging, sensing and separation in recent years. Most magnetic particles or beads currently used in biomedical applications are based on ferromagnetic iron oxides with very low specific magnetic moments of about 20-30 emu/g. Here we report a new approach to synthesize monodispersed core-shell nanostructured clusters with high specific magnetic moments above 200 emu/g. Iron nanoclusters with monodispersive size of diameters from 2 nm to 100 nm are produced by our newly developed nanocluster source and go to a deposition chamber, where a chemical reaction starts, and the nanoclusters are coated with iron oxides. HRTEM Images show the coatings are very uniform and stable. The core-shell nanoclusters are superparamagnetic at room temperature for sizes less than 15 nm, and then become ferromagnetic when the cluster size increases. The specific magnetic moment of core-shell nanoclusters is size dependent, and increases rapidly from about 80 emu/g at the cluster size of around 3 nm to over 200 emu/g up to the size of 100 nm. The use of high magnetic moment nanoclusters for biomedical applications could dramatically enhance the contrast for MRI, reduce the concentration of magnetic particle needs for cell separation, or make drug delivery possible with much lower magnetic field gradients

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

    Science.gov (United States)

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

    2017-02-10

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

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

    Directory of Open Access Journals (Sweden)

    Marija Matulionyte

    2017-02-01

    Full Text Available 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 (MEScapped 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.

  4. ORIGIN OF PALMITIC ACID CARBON IN PALMITATES FORMED FROM HEXADECANE-1-C14 AND TETRADECANE-1-C14 BY MICROCOCCUS CERIFICANS

    Science.gov (United States)

    Finnerty, W. R.; Kallio, R. E.

    1964-01-01

    Finnerty, W. R. (University of Iowa, Iowa City), and R. E. Kallio. Origin of palmitic acid carbon in palmitates formed from hexadecane-1-C14 and tetradecane-1-C14 by Micrococcus cerificans. J. Bacteriol. 87:1261–1265. 1964.—Degradation of the palmitic acid moiety of cetyl palmitate and myristyl palmitate formed from hexadecane-1-C14 and tetradecane-1-C14 by Micrococcus cerificans was carried out. The patterns of C14 labeling in palmitic acid from cetyl palmitate showed that hexadecane is oxidized at the C1 position, and cetyl alcohol and palmitic acid thus formed are directly esterified. Palmitic acid arising from tetradecane and esterified to tetradecanol appeared to have been synthesized by the addition of two carbon atoms to an existing 14-carbon atom skeleton. Considerable mixing of C14 occurred in the C1 and C2 positions of palmitic acid thus synthesized. PMID:14188700

  5. Preparation and Characterization of Chitosan/Soy Protein Isolate Nanocomposite Film Reinforced by Cu Nanoclusters

    Directory of Open Access Journals (Sweden)

    Kuang Li

    2017-06-01

    Full Text Available Soy protein isolate (SPI based films have received considerable attention for use in packaging materials. However, SPI-based films exhibit relatively poor mechanical properties and water resistance ability. To tackle these challenges, chitosan (CS and endogenous Cu nanoclusters (NCs capped with protein were proposed and designed to modify SPI-based films. Attenuated total reflectance-Fourier transform infrared spectroscopy and X-ray diffraction patterns of composite films demonstrated that interactions, such as hydrogen bonds in the film forming process, promoted the cross-linking of composite films. The surface microstructure of CS/SPI films modified with Cu NCs was more uniform and transmission electron microscopy (TEM showed that uniform and discrete clusters were formed. Compared with untreated SPI films, the tensile strength and elongation at break of composite films were simultaneously improved by 118.78% and 74.93%, respectively. Moreover, these composite films also exhibited higher water contact angle and degradation temperature than that of pure SPI film. The water vapor permeation of the modified film also decreased. These improved properties of functional bio-polymers show great potential as food packaging materials.

  6. Role of ligand-ligand vs. core-core interactions in gold nanoclusters.

    Science.gov (United States)

    Milowska, Karolina Z; Stolarczyk, Jacek K

    2016-05-14

    The controlled assembly of ligand-coated gold nanoclusters (NCs) into larger structures paves the way for new applications ranging from electronics to nanomedicine. Here, we demonstrate through rigorous density functional theory (DFT) calculations employing novel functionals accounting for van der Waals forces that the ligand-ligand interactions determine whether stable assemblies can be formed. The study of NCs with different core sizes, symmetry forms, ligand lengths, mutual crystal orientations, and in the presence of a solvent suggests that core-to-core van der Waals interactions play a lesser role in the assembly. The dominant interactions originate from combination of steric effects, augmented by ligand bundling on NC facets, and related to them changes in electronic properties induced by neighbouring NCs. We also show that, in contrast to standard colloidal theory approach, DFT correctly reproduces the surprising experimental trends in the strength of the inter-particle interaction observed when varying the length of the ligands. The results underpin the importance of understanding NC interactions in designing gold NCs for a specific function.

  7. Biotic and abiotic characterization of bioanodes formed on oxidized carbon electrodes as a basis to predict their performance.

    Science.gov (United States)

    Cercado, Bibiana; Cházaro-Ruiz, Luis Felipe; Ruiz, Vianey; López-Prieto, Israel de Jesús; Buitrón, Germán; Razo-Flores, Elías

    2013-12-15

    Bioelectrochemical systems (BESs) are based on the catalytic activity of biofilm on electrodes, or the so-called bioelectrodes, to produce electricity and other valuable products. In order to increase bioanode performance, diverse electrode materials and modification methods have been implemented; however, the factors directly affecting performance are yet unclear. In this work carbon cloth electrodes were modified by thermal, chemical, and electrochemical oxidation to enhance oxygenated surface groups, to modify the electrode texture, and consequently the electron transfer rate and biofilm adhesion. The oxidized electrodes were physically, chemically, and electrochemically characterized, then bioanodes were formed at +0.1 V vs. Ag/AgCl using domestic wastewater amended with acetate. The bioanode performance was evaluated according to the current and charge generated. The efficacy of the treatments were in the order Thermal>Electrochemical>Untreated>Chemical oxidation. The maximum current observed with untreated electrode was 0.152±0.026 mA (380±92 mA m(-2)), and it was increased by 78% and 28% with thermal and electrochemical oxidized electrodes, respectively. Moreover, the volatile solids correlated significantly with the maximum current obtained, and the electrode texture was revealed as a critical factor for increasing the bioanode performance. Copyright © 2013 Elsevier B.V. All rights reserved.

  8. On the Rust Products Formed on Weathering and Carbon Steels Exposed to Chloride in Dry-Wet Cyclical Processes

    International Nuclear Information System (INIS)

    Garcia, K. E.; Morales, A. L.; Barrero, C. A.; Greneche, J. M.

    2005-01-01

    The rust products formed on weathering and carbon steels exposed to dry-wet cyclical processes in different chloride-rich solutions are carefully examined by means of different techniques. Special emphasis is given to the methodology of analysis of the data using 300 K and 77 K Moessbauer spectrometry and X-ray diffraction. The rust that is loosely bound to the metal surface and that it is lost during the corrosion process, for both types of steel, was found to be composed of lepidocrocite, superparamagnetic goethite, hematite, and traces of akaganeite. On the other hand, the adherent rust, which is differentiated as scraped and hit according to the way it is obtained, from both steels was found to be composed of akaganeite, spinel phase, goethite exhibiting broad distribution of particle sizes and lepidocrocite. The relative abundances of rust components for both steels were very similar, suggesting similar corrosion processes. Mass loss measurements show that the corrosion rates increases with increasing the chloride concentration. The presence of large quantities of spinel phase and akaganeite are a consequence of a corrosion process under the influence of very high chloride concentrations. Our results are useful for assessing the behavior of weathering steels where the levels of chlorides are high or in contact with sea water.

  9. Eco-friendly (green) synthesis of magnetically active gold nanoclusters

    Science.gov (United States)

    Kadasala, Naveen Reddy; Lin, Lu; Gilpin, Christopher; Wei, Alexander

    2017-12-01

    Au-FexOy composite nanoparticles (NPs) are of great technological interest due to their combined optical and magnetic properties. However, typical syntheses are neither simple nor ecologically friendly, creating a challenging situation for process scale-up. Here we describe conditions for preparing Au-FexOy NPs in aqueous solutions and at ambient temperatures, without resorting to solvents or amphiphilic surfactants with poor sustainability profiles. These magnetic gold nanoclusters (MGNCs) are prepared in practical yields with average sizes slightly below 100 nm, and surface plasmon resonances that extend to near-infrared wavelengths, and sufficient magnetic moment (up to 6 emu g-1) to permit collection within minutes by handheld magnets. The MGNCs also produce significant photoluminescence when excited at 488 nm. Energy dispersive X-ray (EDX) analysis indicates a relatively even distribution of Fe within the MGNCs, as opposed to a central magnetic core.

  10. Gold Nanocluster-Mediated Cellular Death under Electromagnetic Radiation.

    Science.gov (United States)

    Cifuentes-Rius, Anna; Ivask, Angela; Das, Shreya; Penya-Auladell, Nuria; Fabregas, Laura; Fletcher, Nicholas L; Houston, Zachary H; Thurecht, Kristofer J; Voelcker, Nicolas H

    2017-11-29

    Gold nanoclusters (Au NCs) have become a promising nanomaterial for cancer therapy because of their biocompatibility and fluorescent properties. In this study, the effect of ultrasmall protein-stabilized 2 nm Au NCs on six types of mammalian cells (fibroblasts, B-lymphocytes, glioblastoma, neuroblastoma, and two types of prostate cancer cells) under electromagnetic radiation is investigated. Cellular association of Au NCs in vitro is concentration-dependent, and Au NCs have low intrinsic toxicity. However, when Au NC-incubated cells are exposed to a 1 GHz electromagnetic field (microwave radiation), cell viability significantly decreases, thus demonstrating that Au NCs exhibit specific microwave-dependent cytotoxicity, likely resulting from localized heating. Upon i.v. injection in mice, Au NCs are still present at 24 h post administration. Considering the specific microwave-dependent cytotoxicity and low intrinsic toxicity, our work suggests the potential of Au NCs as effective and safe nanomedicines for cancer therapy.

  11. Exploring Low Internal Reorganization Energies for Silicene Nanoclusters

    Science.gov (United States)

    Pablo-Pedro, Ricardo; Lopez-Rios, Hector; Mendoza-Cortes, Jose-L.; Kong, Jing; Fomine, Serguei; Van Voorhis, Troy; Dresselhaus, Mildred S.

    2018-05-01

    This paper is a contribution to the Physical Review Applied collection in memory of Mildred S. Dresselhaus. High-performance materials rely on small reorganization energies to facilitate both charge separation and charge transport. Here, we perform density-functional-theory calculations to predict small reorganization energies of rectangular silicene nanoclusters with hydrogen-passivated edges denoted by H-SiNC. We observe that across all geometries, H-SiNCs feature large electron affinities and highly stabilized anionic states, indicating their potential as n -type materials. Our findings suggest that fine-tuning the size of H-SiNCs along the "zigzag" and "armchair" directions may permit the design of novel n -type electronic materials and spintronics devices that incorporate both high electron affinities and very low internal reorganization energies.

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

    Energy Technology Data Exchange (ETDEWEB)

    Hao, Jiannan; Shu, Xiaolin, E-mail: shuxlin@buaa.edu.cn; Jin, Shuo; Zhang, Xuesong; Zhang, Ying; Lu, Guang-Hong

    2017-02-15

    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.

  13. Electrically driven light emission from an array of Si nanoclusters

    International Nuclear Information System (INIS)

    Mazzitello, K I; Martin, H O; Aldao, C M; Roman, H E

    2004-01-01

    Charge transport and light emission properties of an array of silicon nanoclusters (NCs), sandwiched between a p-type and an n-type doped silicon crystal, are studied theoretically by assuming that electrons and holes enter from the opposite sides of the array in response to an applied electric field. The size of the NCs considered ranges from 16 nm down to 3.6 nm and their spatial distribution is optimized so that light emission, resulting from radiative recombinations, is peaked in the visible red around 1.8 eV. The light emission efficiency is limited by the carrier hopping times and is found to be in the range 2-0.5%, for fields ranging from 100 kV cm -1 to 500 kV cm -1 , respectively

  14. Melting of Cu nanoclusters by molecular dynamics simulation

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Li; Zhang, Yanning; Bian, Xiufang; Chen, Ying

    2003-04-14

    We present a detailed molecular dynamics study of the melting of copper nanoclusters with up to 8628 atoms within the framework of the embedded-atom method. The finding indicates that there exists an intermediate nanocrystal regime above 456 atoms. The linear relation between the cluster size and its thermodynamics properties is obeyed in this regime. Melting first occurs at the surface of the clusters, leading to T{sub m,N}=T{sub m,Bulk}-{alpha}N{sup -1/3}, dropping from T{sub m,Bulk}=1360 K to T{sub m,456}=990 K. In addition, the size, surface energy as well as the root mean square displacement (RMSD) of the clusters in the intermediate regime have been investigated.

  15. Exploring Low Internal Reorganization Energies for Silicene Nanoclusters

    KAUST Repository

    Pablo-Pedro, Ricardo

    2017-08-17

    High-performance materials rely on small reorganization energies to facilitate both charge separation and charge transport. Here, we performed DFT calculations to predict small reorganization energies of rectangular silicene nanoclusters with hydrogen-passivated edges denoted by H-SiNC. We observe that across all geometries, H-SiNCs feature large electron affinities and highly stabilized anionic states, indicating their potential as n-type materials. Our findings suggest that fine-tuning the size of H-SiNCs along the zigzag and armchair directions may permit the design of novel n-type electronic materials and spinctronics devices that incorporate both high electron affinities and very low internal reorganization energies.

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

    International Nuclear Information System (INIS)

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

    2017-01-01

    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. Connections Between Theory and Experiment for Gold and Silver Nanoclusters

    Science.gov (United States)

    Weerawardene, K. L. Dimuthu M.; Häkkinen, Hannu; Aikens, Christine M.

    2018-04-01

    Ligand-stabilized gold and silver nanoparticles are of tremendous current interest in sensing, catalysis, and energy applications. Experimental and theoretical studies have closely interacted to elucidate properties such as the geometric and electronic structures of these fascinating systems. In this review, the interplay between theory and experiment is described; areas such as optical absorption and doping, where the theory-experiment connections are well established, are discussed in detail; and the current status of these connections in newer fields of study, such as luminescence, transient absorption, and the effects of solvent and the surrounding environment, are highlighted. Close communication between theory and experiment has been extremely valuable for developing an understanding of these nanocluster systems in the past decade and will undoubtedly continue to play a major role in future years.

  18. Critical sizes and critical characteristics of nanoclusters, nanostructures and nanomaterials

    International Nuclear Information System (INIS)

    Suzdalev, I.P.

    2005-01-01

    Full text: Critical sizes and characteristics of nanoclusters and nanostructures are introduced as the parameters of nanosystems and nanomaterials. The next critical characteristics are considered: atomic and electronic 'magic number', critical size of cluster nucleation, critical size of melting-freezing of cluster, critical size of quantum (laser) radiation, critical sizes for the single electron conductivity, critical energy and magnetic field for the magnetic tunneling, critical cluster sizes for the giant magnetic resistance, critical size of the first order magnetic phase transition. The critical characteristics are estimated by thermodynamic approaches, by Moessbauer spectroscopy, AFM, heat capacity, SQUID magnetometry and other technique, The influence of cluster-cluster interactions, cluster-matrix interactions and cluster defects on cluster atomic dynamics, cluster melting, cluster critical sizes, Curie or Neel points and the character of magnetic phase transitions were investigated. The applications of critical size and critical characteristic parameters for the nanomaterial characterization are considered

  19. Modeling the photosensitizing properties of thiolate-protected gold nanoclusters.

    Science.gov (United States)

    Azarias, Cloé; Adamo, Carlo; Perrier, Aurélie

    2016-03-21

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

  20. Electrical transport properties in Co nanocluster-assembled granular film

    Science.gov (United States)

    Zhang, Qin-Fu; Wang, Lai-Sen; Wang, Xiong-Zhi; Zheng, Hong-Fei; Liu, Xiang; Xie, Jia; Qiu, Yu-Long; Chen, Yuanzhi; Peng, Dong-Liang

    2017-03-01

    A Co nanocluster-assembled granular film with three-dimensional cross-connection paralleled conductive paths was fabricated by using the plasma-gas-condensation method in a vacuum environment. The temperature-dependent longitudinal resistivity and anomalous Hall effect of this new type granular film were systematically studied. The longitudinal resistivity of the Co nanocluster-assembled granular film first decreased and then increased with increasing measuring temperature, revealing a minimum value at certain temperature, T min . In a low temperature region ( T governed the electrical transport process, and the temperature coefficient of resistance (TCR) showed an insulator-type behavior. The thermal fluctuation-induced tunneling conduction progressively increased with increasing temperature, which led to a decrease in the longitudinal resistivity. In a high temperature region, the TCR showed a metallic-type behavior, which was primarily attributed to the temperature-dependent scattering. Different from the longitudinal resistivity behavior, the saturated anomalous Hall resistivity increased monotonically with increasing measuring temperature. The value of the anomalous Hall coefficient ( R S ) reached 2.3 × 10-9 (Ω cm)/G at 300 K, which was about three orders of magnitude larger than previously reported in blocky single-crystal Co [E. N. Kondorskii, Sov. Phys. JETP 38, 977 (1974)]. Interestingly, the scaling relation ( ρx y A ∝ ρx x γ ) between saturated anomalous Hall resistivity ( ρx y A ) and longitudinal resistivity ( ρ x x ) was divided into two regions by T min . However, after excluding the contribution of tunneling, the scaling relation followed the same rule. The corresponding physical mechanism was also proposed to explain these phenomena.

  1. Nanoclusters in bcc-Fe containing vacancies, copper and nickel: Structure and energetics

    International Nuclear Information System (INIS)

    Al-Motasem, A.T.; Posselt, M.; Bergner, F.

    2011-01-01

    Highlights: → Fe-Cu-Ni model alloys for RPV steels. → Atomistic simulation, mainly MMC and MD simulations. → Finding the most stable configurations of defect clusters. → Energetics of clusters, formation and binding energies. → Size dependence of monomer binding energy formula as input for OKMC methods. - Abstract: The most stable atomic configuration of coherent nanoclusters in bcc-Fe formed by vacancies, Cu and Ni as well as the corresponding energetics are determined by on-lattice simulated annealing and subsequent off-lattice relaxation. An interatomic potential recently designed for investigations of radiation-induced effects in the ternary Fe-Cu-Ni system is used in the atomistic simulations. Ternary v l Cu m Ni n clusters show a core-shell structure with vacancies in the core coated by a shell of Cu atoms, followed by a shell of Ni atoms. In binary Cu m Ni n clusters the Cu core is covered by a shell of Ni atoms. On the contrary, binary v l Ni n clusters consist of a pure vacancy cluster surrounded by an agglomeration of Ni atoms. The latter is similar to a pure Ni cluster (Ni n ) and consists of Ni atoms at the second nearest neighbor distance. Because of this special arrangement of atoms v l Ni n and Ni n are also called quasi-clusters. In all clusters investigated Ni atoms may be nearest neighbors of Cu atoms but never nearest neighbors of vacancies or other Ni atoms. The atomic configurations found can be understood by the peculiarities of the binding between vacancies, Cu, Ni and Fe atoms. The structure obtained for Cu m Ni n clusters is in agreement with previous theoretical results and with indications from measurements while for the other clusters reference data are not available. It is shown that the presence of Ni atoms promotes the nucleation of clusters containing vacancies and Cu. This is in agreement with experimental observations and with recent results of atomic kinetic Monte Carlo simulations. Based on the specific atomic structure

  2. Fuel Cell Electrodes Based on Carbon Nanotube/Metallic Nanoparticles Hybrids Formed on Porous Stainless Steel Pellets

    Directory of Open Access Journals (Sweden)

    S. M. Khantimerov

    2013-01-01

    Full Text Available The preparation of carbon nanotube/metallic particle hybrids using pressed porous stainless steel pellets as a substrate is described. The catalytic growth of carbon nanotubes was carried out by CVD on a nickel catalyst obtained by impregnation of pellets with a highly dispersive colloidal solution of nickel acetate tetrahydrate in ethanol. Granular polyethylene was used as the carbon source. Metallic particles were deposited by thermal evaporation of Pt and Ag using pellets with grown carbon nanotubes as a base. The use of such composites as fuel cell electrodes is discussed.

  3. Polymer-induced liquid precursor (PILP) phases of calcium carbonate formed in the presence of synthetic acidic polypeptides - relevance to biomineralization

    NARCIS (Netherlands)

    Schenk, A.S.; Zope, H.; Kim, Y.; Kros, A.; Sommerdijk, N.A.J.M.; Meldrum, F.C.

    2012-01-01

    Polymer-induced liquid precursor (PILP) phases of calcium carbonate have attracted significant interest due to possible applications in materials synthesis, and their resemblance to intermediates seen in biogenic mineralisation processes. Further, these PILP phases have been formed in vitro using

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

    KAUST Repository

    AbdulHalim, Lina G.; Ashraf, Sumaira; Katsiev, Khabiboulakh; Kirmani, Ahmad R.; Kothalawala, Nuwan; Anjum, Dalaver H.; Abbas, Sikandar Zameer; Amassian, Aram; Stellacci, Francesco; Dass, Amala; Hussain, Irshad; Bakr, Osman

    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.

  5. β-Cyclodextrin functionalised gold nanoclusters as luminescence probes for the ultrasensitive detection of dopamine.

    Science.gov (United States)

    Ban, Rui; Abdel-Halim, E S; Zhang, Jianrong; Zhu, Jun-Jie

    2015-02-21

    A novel luminescence probe based on mono-6-amino-β-cyclodextrin (NH2-β-CD) functionalised gold nanoclusters (β-CD-AuNC) was designed for dopamine (DA) detection. The NH2-β-CD molecules were conjugated onto the surface of 11-mercaptoundecanoic acid capped AuNCs (11-MUA-AuNC) via a carbodiimide coupling reaction. The integrity of the β-CD cavities was preserved on the surface of AuNCs and they retained their capability for molecular DA host-guest recognition. DA could be captured by the β-CD cavities to form an inclusion complex in which the oxidised DA could quench the fluorescence of the β-CD-AuNC probe by electron transfer. The probe could be used to quantify DA in the range of 5-1000 nM with a detection limit of 2 nM. This sensitivity was 1-2 orders of magnitude higher than that in previously reported methods. Interference by both ascorbic acid (AA) and uric acid (UA) was not observed. Therefore, the β-CD-AuNC probe could be directly used to determine the DA content in biological samples without further separation. This strategy was successfully applied to a DA assay in spiked human serum samples and it exhibited remarkable accuracy, sensitivity and selectivity.

  6. Microscopic parameters of heterostructures containing nanoclusters and thin layers of Ge in Si matrix

    CERN Document Server

    Erenburg, S B; Stepina, N P; Nikiforov, A I; Nenashev, A V; Mazalov, L N

    2001-01-01

    GeK XAFS measurements have been performed using the total electron yield detection mode for pseudomorphous Ge films deposited on Si(0 0 1) substrate via molecular beam epitaxy at 300 deg. C. The samples have been produced by thrice repeating the growing procedure separated by deposition of blocking Si layers at 500 deg. C. The local microstructure parameters (interatomic distances, Ge coordination numbers) are linked to nanostructure morphology and adequate models are suggested and discussed. It was established that pseudomorphous 4-monolayer Ge films contain 50% of Si atoms on the average. Pyramid-like, pure Ge islands formed in the Stranski-Krastanov growth are characterized by the interatomic Ge-Ge distances of 2.41 A (by 0.04 A less than in bulk Ge) and the Ge-Si distances of 2.37 A. It was revealed that the pure Ge nanoclusters are covered by a 1-2-monolayer film with admixture on the average of a 50% Si atom impurity from blocking Si layers.

  7. DNA-hosted copper nanoclusters/graphene oxide based fluorescent biosensor for protein kinase activity detection.

    Science.gov (United States)

    Wang, Mengke; Lin, Zihan; Liu, Qing; Jiang, Shan; Liu, Hua; Su, Xingguang

    2018-07-05

    A novel fluorescent biosensor for protein kinase activity (PKA) detection was designed by applying double-strands DNA-hosted copper nanoclusters (dsDNA-CuNCs) and graphene oxide (GO). One DNA strand of the dsDNA consisted of two domains, one domain can hybridize with another complementary DNA strand to stabilize the fluorescent CuNCs and another domain was adenosine 5'-triphosphate (ATP) aptamer. ATP aptamer of the dsDNA-CuNCs would be spontaneously absorbed onto the GO surface through π-π stacking interactions. Thus GO can efficiently quench the fluorescence (FL) of dsDNA-CuNCs through fluorescence resonance energy transfer (FRET). In the present of ATP, ATP specifically combined with ATP aptamer to form ATP-ATP aptamer binding complexes, which had much less affinity to GO, resulting in the fluorescence recovery of the system. Nevertheless, in the presence of PKA, ATP could be translated into ADP and ADP could not combine with ATP aptamer resulting in the fluorescence quenching of dsDNA-CuNCs again. According to the change of the fluorescence signal, PKA activity could be successfully monitored in the range of 0.1-5.0 U mL -1 with a detection limit (LOD) of 0.039 U mL -1 . Besides, the inhibitory effect of H-89 on PKA activity was studied. The sensor was performed for PKA activity detection in cell lysates with satisfactory results. Copyright © 2018 Elsevier B.V. All rights reserved.

  8. Co-deposition of silver nanoclusters and sputtered alumina for sensor devices

    International Nuclear Information System (INIS)

    Schultes, Guenter; Schmidt, Michael; Truar, Marcel; Goettel, Dirk; Freitag-Weber, Olivia; Werner, Ulf

    2007-01-01

    Heterogeneous thin films may be beneficial for sensoring devices. The electrical conductivity of nanoscale metallic particles being embedded in a matrix of non conducting material should exhibit higher sensitivity to mechanical stress and strain compared to homogeneous films. The production of heterogeneous films may follow different routes. This paper describes the attempt to embed Ag nanoclusters emitted from a gas aggregation cluster source into a growing matrix of alumina originating from sputter sources. The characteristics of the cluster source are first resumed, with their mean masses ranging from approx. 1000 to 100,000 atoms per cluster. The expelled and soft landed clusters are extensively examined by transmission electron microscopy verifying their crystalline form. Yet the use of a radio frequency driven sputter source for the embed material destroys and annihilates the Ag clusters even at very low sputter power. If a reactive direct current sputter process is performed within an oxidising sputter gas instead, the Ag clusters are oxidised to different oxides, but they survive as crystalline entities as verified by X-ray diffraction investigations. A simple subsequent heat treatment reduces the Ag oxides to metallic Ag clusters

  9. Bio-NCs--the marriage of ultrasmall metal nanoclusters with biomolecules.

    Science.gov (United States)

    Goswami, Nirmal; Zheng, Kaiyuan; Xie, Jianping

    2014-11-21

    Ultrasmall metal nanoclusters (NCs) have attracted increasing attention due to their fascinating physicochemical properties. Today, functional metal NCs are finding growing acceptance in biomedical applications. To achieve a better performance in biomedical applications, metal NCs can be interfaced with biomolecules, such as proteins, peptides, and DNA, to form a new class of biomolecule-NC composites (or bio-NCs in short), which typically show synergistic or novel physicochemical and physiological properties. This feature article focuses on the recent studies emerging at the interface of metal NCs and biomolecules, where the interactions could impart unique physicochemical properties to the metal NCs, as well as mutually regulate biological functions of the bio-NCs. In this article, we first provide a broad overview of key concepts and developments in the novel biomolecule-directed synthesis of metal NCs. A special focus is placed on the key roles of biomolecules in metal NC synthesis. In the second part, we describe how the encapsulated metal NCs affect the structure and function of biomolecules. Followed by that, we discuss several unique synergistic effects observed in the bio-NCs, and illustrate them with examples highlighting their potential biomedical applications. Continued interdisciplinary efforts are required to build up in-depth knowledge about the interfacial chemistry and biology of bio-NCs, which could further pave their ways toward biomedical applications.

  10. Bio-NCs - the marriage of ultrasmall metal nanoclusters with biomolecules

    Science.gov (United States)

    Goswami, Nirmal; Zheng, Kaiyuan; Xie, Jianping

    2014-10-01

    Ultrasmall metal nanoclusters (NCs) have attracted increasing attention due to their fascinating physicochemical properties. Today, functional metal NCs are finding growing acceptance in biomedical applications. To achieve a better performance in biomedical applications, metal NCs can be interfaced with biomolecules, such as proteins, peptides, and DNA, to form a new class of biomolecule-NC composites (or bio-NCs in short), which typically show synergistic or novel physicochemical and physiological properties. This feature article focuses on the recent studies emerging at the interface of metal NCs and biomolecules, where the interactions could impart unique physicochemical properties to the metal NCs, as well as mutually regulate biological functions of the bio-NCs. In this article, we first provide a broad overview of key concepts and developments in the novel biomolecule-directed synthesis of metal NCs. A special focus is placed on the key roles of biomolecules in metal NC synthesis. In the second part, we describe how the encapsulated metal NCs affect the structure and function of biomolecules. Followed by that, we discuss several unique synergistic effects observed in the bio-NCs, and illustrate them with examples highlighting their potential biomedical applications. Continued interdisciplinary efforts are required to build up in-depth knowledge about the interfacial chemistry and biology of bio-NCs, which could further pave their ways toward biomedical applications.

  11. 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

  12. A preliminary study of thermo-mechanical stability of carbon S-phase formed in austenitic stainless steel

    Energy Technology Data Exchange (ETDEWEB)

    Li, Wei; Chiu, Yu Long; Dong, Hanshan, E-mail: wsgddf@hotmail.com [School of Metallurgy and Materials, College of Physical and Engineering Sciences, The University of Birmingham, Birmingham (United Kingdom)

    2010-07-01

    Carbon S-phase was generated in the surface of AISI316 austenitic stainless steel by plasma carburising at 500°C for 10h in a gas mixture of 1.5%CH4 and 98.5%H{sub 2}. The thermo-mechanical stability of the carbon S-phase was studied by stressing the 'dog-bone' tensile specimens in the range of 0-200MPa at temperatures ranging from 400 to 500°C for 100-150h. Post-test characterisation was conducted using XRD, SEM, TEM and micro-indentation. The experimental results demonstrate that when tested at a fix temperature the thickness of the carbon S-phase layer increased with the stress applied to the tensile specimens during the thermo-mechanical stability tests. This indicates that tensile stress promotes the diffusion of carbon in the carbon-S-phase. When stressed at 400°C the microstructure of the carbon S-phase was not affected by the stress level; however, when stressed at 450 and 500°C for 100MPa or above, the corrosion resistance of the carbon S-phase slightly deteriorated. The application of a tensile stress during annealing of S-phase layer can retard the deduction of its hardness. This is believed to be related to the early stage precipitation of carbides in the S-phase, which could be facilitated by the applied tensile stress during thermal annealing. (author)

  13. Study of calcium forms and their effect in carbon stabilization in fertile soils by FTIR and XPS

    International Nuclear Information System (INIS)

    Araujo, J.R.; Assis, K.L.S.; Calil, V.L.; Souza, K.R.; Beltrao, M.S.S.; Sena, L.A.; Archanjo, B.S.; Achete, C.A.

    2013-01-01

    Organic matter or black carbon atoms of Terra Preta de Indio (Amazonian Dark Earth) soils are composed of oxidized carbon groups as phenols, epoxide, carbonyl and carboxyl groups in their surface. At the pH of soil, carboxylate groups are deprotonated generating carboxylate anions leaving the surface of these soils with negative charges. Calcium cations can interact with oxidized carbon groups by chemisorption interactions lowering the total system energy. In this work, Terra Preta de Indio was examined by X-ray photoelectron spectroscopy and Infrared spectroscopy in order to correlate its organic fraction rich in calcium with calcium containing samples. (author)

  14. Study of calcium forms and their effect in carbon stabilization in fertile soils by FTIR and XPS

    Energy Technology Data Exchange (ETDEWEB)

    Araujo, J.R.; Assis, K.L.S.; Calil, V.L.; Souza, K.R.; Beltrao, M.S.S.; Sena, L.A.; Archanjo, B.S.; Achete, C.A., E-mail: jraraujo@inmetro.gov.br [Instituto Nacional de Metrologia, Qualidade e Tecnologia (INMETRO), Duque de Caxias, RJ (Brazil). Divisao de Materiais e Metrologia

    2013-07-01

    Organic matter or black carbon atoms of Terra Preta de Indio (Amazonian Dark Earth) soils are composed of oxidized carbon groups as phenols, epoxide, carbonyl and carboxyl groups in their surface. At the pH of soil, carboxylate groups are deprotonated generating carboxylate anions leaving the surface of these soils with negative charges. Calcium cations can interact with oxidized carbon groups by chemisorption interactions lowering the total system energy. In this work, Terra Preta de Indio was examined by X-ray photoelectron spectroscopy and Infrared spectroscopy in order to correlate its organic fraction rich in calcium with calcium containing samples. (author)

  15. 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.

  16. Mobilities in ambipolar field effect transistors based on single-walled carbon nanotube network and formed on a gold nanoparticle template

    Energy Technology Data Exchange (ETDEWEB)

    Wongsaeng, Chalao [Department of Science, Faculty of Sciences and Agricultural Technology, Rajamangala University of Technology Lanna Tak, Tak 63000 (Thailand); Department of Physics and Materials Science, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand); Singjai, Pisith, E-mail: pisith.s@cmu.ac.th [Department of Physics and Materials Science, Faculty of Science, Chiang Mai University, Chiang Mai 50200 (Thailand)

    2014-04-07

    Ambipolar field effect transistors based on a single-walled carbon nanotube (SWNT) network formed on a gold nanoparticle (AuNP) template with polyvinyl alcohol as a gate insulator were studied by measuring the current–gate voltage characteristics. It was found that the mobilities of holes and electrons increased with increasing AuNP number density. The disturbances in the flow pattern of the carbon feedstock in the chemical vapor deposition growth that were produced by the AuNP geometry, resulted in the differences in the crystallinity and the diameter, as well as the changes in the degree of the semiconductor behavior of the SWNTs.

  17. Spherical cauliflower-like carbon dust formed by interaction between deuterium plasma and graphite target and its internal structure

    Energy Technology Data Exchange (ETDEWEB)

    Ohno, N. [Department of Energy Engineering and Science, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan)], E-mail: ohno@ees.nagoya-u.ac.jp; Yoshimi, M. [Department of Energy Engineering and Science, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Tokitani, M. [National Institute for Fusion Science, Oroshi 322-6, Toki 509-5292 (Japan); Takamura, S. [Department of Electronics, Aichi Institute of Technology, Yakusa-cho, Toyota 470-0392 (Japan); Tokunaga, K.; Yoshida, N. [Research Institute for Applied Mechanics, Kyushu University, Kasuga, Fukuoka 816-8580 (Japan)

    2009-06-15

    Simulated experiments to produce carbon dust particles with cauliflower structure have been performed in a liner plasma device, NAGDIS-II by exposing high density deuterium plasma to a graphite sample (IG-430U). Formation of carbon dust depends on the surface temperature and the incident ion energy. At a surface temperature 600-700 K, a lot of isolated spherical dust particles are observed on the graphite target. The internal structure of an isolated dust particle was observed with Focused Ion Beam (FIB) system and Transmission Electron Microscope (TEM) in detail. FIB analysis clearly shows there exist honey-combed cell structure with thin carbon walls in the dust particle and the dust particle grows from the graphite surface. TEM image also shows that the dust particle is made of amorphous carbon with crystallized grains with diameters of 10-50 nm.

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

    Science.gov (United States)

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

    2015-07-01

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

  19. 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.

  20. Effect of thermal treatments on sputtered silver nanocluster/silica composite coatings on soda-lime glasses: ionic exchange and antibacterial activity

    Energy Technology Data Exchange (ETDEWEB)

    Ferraris, M.; Ferraris, S., E-mail: sara.ferraris@polito.it; Miola, M.; Perero, S.; Balagna, C.; Verne, E. [Politecnico di Torino, Department of Applied Science and Technology, Institute of Materials Physics and Engineering (Italy); Gautier, G. [IMAMOTER Institute for Agricultural and Earthmoving Machines (Italy); Manfredotti, Ch.; Battiato, A.; Vittone, E. [University of Torino, Physics Department, NIS Excellence Centre and CNISM (Italy); Speranza, G. [Fondazione Bruno Kessler FBK (Italy); Bogdanovic, I. [Ruder Boskovic Institute, Experimental Physics Department (Croatia)

    2012-12-15

    Silver nanocluster/silica composite coatings were deposited on both soda-lime and silica glasses by radio frequency (RF) co-sputtering. The effect of thermal treatments on the microstructure in the range of 150-450 Degree-Sign C were examined by UV-visible spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Time of Flight-Elastic Recoil Detection Analysis. Sodium/silver ionic exchange was evidenced for coatings sputtered on soda-lime substrates after heating at 450 Degree-Sign C; presence of silver ions and/or silver nanoclusters, nanocluster size and their position inside the sputtered layers will be discussed for as-deposited and heated coatings on both substrates. The antibacterial activity of all coatings was determined against Staphylococcus aureus and Candida albicans by disk diffusion method and colonies forming units count; in agreement with microstructural results, the antibacterial activity present on all coatings was slightly reduced after heating at 450 Degree-Sign C. All coatings have been submitted to humidity plus UV ageing and sterilization by autoclave, gamma ray and ethylene oxide gas. Tape resistance (ASTM D3359-97) tests have been done on each coating before and after ageing and sterilizations, revealing a good adhesion on soda-lime substrates, except for those aged in humidity plus UV and sterilized by autoclave. Scratch tests and nanoindentation tests have been done on each coating, as-deposited and after heating at 450 Degree-Sign C. The coating hardness was improved by heating only when coatings were deposited on silica. The heating of coatings deposited on soda-lime substrates gave opposite effect on their hardness.

  1. Controllable synthesis of hexagonal ZnO–carbon core–shell microrods and the removal of ZnO to form hexagonal carbon microtubes

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Yong, E-mail: xy91007@163.com [Department of Applied Chemistry, South China Agricultural University, Guangzhou 510642 (China); He, Wenqi; Gao, Chuang [Department of Chemistry and Institute of Nanochemistry, Jinan University, Guangzhou 510632 (China); Zheng, Mingtao; Lie, Bingfu; Liu, Xiaotang [Department of Applied Chemistry, South China Agricultural University, Guangzhou 510642 (China); Liu, Yingliang, E-mail: tliuyl@163.com [Department of Applied Chemistry, South China Agricultural University, Guangzhou 510642 (China)

    2013-06-15

    A simple and efficient approach was developed to produce regular and uniform shaped hexagonal ZnO–C core–shell micro-rods and carbon micro-tubes. A single-source raw material, zinc acetate dihydrate, has been used for the in situ generation of the hexagonal ZnO–C micro-rods in a sealed autoclave system at 500 °C for 12 h without a catalyst. The resulting products were characterized by X-ray powder diffraction, scanning and transmission electron microscopy, energy-dispersive X-ray analysis and room-temperature photoluminescence spectroscopy (PL). The partial or complete carbon coating on the ZnO surfaces plays an important role in modifying the PL properties. Impacting factors including thermolysis temperature, time and dose of the reactant on the evolution of the hexagonal shape were investigated. A possible formation diagram for the materials has been proposed and discussed based on the features of the reaction system. - Highlights: • Hexagonal ZnO–C core–shell microrods were synthesized by the lower temperature decomposition of zinc acetate. • The novel hexagonal carbon microtubes can gain by simply handling with dilute acid. • The partial or complete carbon coating on the ZnO surfaces plays an important role in modifying the PL properties. • A possible formation diagram for the materials has been proposed.

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

    KAUST Repository

    Almansaf, Abdulkhaleq

    2017-07-01

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

  3. Formation and growth of embedded indium nanoclusters by In2+ implantation in silica

    International Nuclear Information System (INIS)

    Santhana Raman, P.; Nair, K.G.M.; Kesavamoorthy, R.; Panigrahi, B.K.; Dhara, S.; Ravichandran, V.

    2007-01-01

    Indium nanoclusters are synthesized in an amorphous silica matrix using an ion-implantation technique. Indium ions (In 2+ ) with energy of 890 keV are implanted on silica to fluences in the range of 3 x 10 16 -3 x 10 17 cm -2 . The formation of indium nanoclusters is confirmed by optical absorption spectrometry and glancing incidence X-ray diffraction studies. A low frequency Raman scattering technique is used to study the growth of embedded indium nanoclusters in the silica matrix as a function of fluence and post-implantation annealing duration. Rutherford backscattering spectrometry studies show the surface segregation of implanted indium. Photoluminescence studies indicate the formation of a small quantity of indium oxide phase in the ion-implanted samples. (orig.)

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

    Science.gov (United States)

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

    2018-05-22

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

  5. Fabrication and modification of metal nanocluster composites using ion and laser beams

    International Nuclear Information System (INIS)

    Haglund, R.F. Jr.; Osborne, D.H. Jr.; Magruder, R.H. III; White, C.W.; Zuhr, R.A.; Townsend, P.D.; Hole, D.E.; Leuchtner, R.E.

    1994-12-01

    Metal nanocluster composites have attractive properties for applications in nonlinear optics. However, traditional fabrication techniques -- using melt-glass substrates -- are severely constrained by equilibrium thermodynamics and kinetics. This paper describes the fabrication of metal nanoclusters in both crystalline and glassy hosts by ion implantation and pulsed laser deposition. The size and size distribution of the metal nanoclusters can be modified by controlling substrate temperature during implantation, by subsequent thermal annealing, or by laser irradiation. The authors have characterized the optical response of the composites by absorption and third-order nonlinear-optical spectroscopies; electron and scanning-probe microscopies have been used to benchmark the physical characteristics of the composites. The outlook for controlling the structure and nonlinear optical response properties of these nanophase materials appears increasingly promising

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

    International Nuclear Information System (INIS)

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

    2016-01-01

    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 Au 13 nanoclusters is investigated. We find that a critical step involving the formation of smaller Au 8 -Au 11 metastable intermediate clusters induced by the HCl + HSR etching of the polydisperse Au n precursor clusters occurs firstly. Then these intermediate species undergo a size-growth to Au 13 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. (paper)

  7. Synthesis of hydrophobic gold nanoclusters: growth mechanism study, luminescence property and catalytic application

    International Nuclear Information System (INIS)

    Selvam, Tamil Selvi; Chi, Kai-Ming

    2011-01-01

    One-pot synthesis of well dispersed, size-controlled gold nanoparticles with the average size of 10–15 nm and luminescent gold nanoclusters with average size of 1.7–2.0 nm were successfully achieved by thermal decomposition of gold organometallic precursor CH 3 AuPPh 3 in the presence of thiol surfactants in o-xylene. Only difference between the preparations of two types of Au nanoparticles is the amount of thiol surfactant employed. The mechanistic study of formation of gold nanoparticles was carried out by analyzing the samples at different reaction time intervals and revealed that two-staged growth process was involved. The nanoclusters showed strong red emission with the maximum intensity at about 600 nm. The maximum room temperature photoluminescence quantum yield was measured as 1.2%. The catalytic ability of the Au nanoclusters to promote Suzuki–Miyaura coupling involving the C–C bond formation was also investigated.

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

    International Nuclear Information System (INIS)

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

    2016-01-01

    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.

  9. Advanced fire-resistant forms of activated carbon and methods of adsorbing and separating gases using same

    Science.gov (United States)

    Xiong, Yongliang; Wang, Yifeng

    2015-02-03

    Advanced, fire-resistant activated carbon compositions useful in adsorbing gases; and having vastly improved fire resistance are provided, and methods for synthesizing the compositions are also provided. The advanced compositions have high gas adsorption capacities and rapid adsorption kinetics (comparable to commercially-available activated carbon), without having any intrinsic fire hazard. They also have superior performance to Mordenites in both adsorption capacities and kinetics. In addition, the advanced compositions do not pose the fibrous inhalation hazard that exists with use of Mordenites. The fire-resistant compositions combine activated carbon mixed with one or more hydrated and/or carbonate-containing minerals that release H.sub.2O and/or CO.sub.2 when heated. This effect raises the spontaneous ignition temperature to over 500.degree. C. in most examples, and over 800.degree. C. in some examples. Also provided are methods for removing and/or separating target gases, such as Krypton or Argon, from a gas stream by using such advanced activated carbons.

  10. 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.

  11. Fluorescent silver nanoclusters for ultrasensitive determination of chromium(VI) in aqueous solution

    International Nuclear Information System (INIS)

    Zhang, Jian Rong; Zeng, Ai Lian; Luo, Hong Qun; Li, Nian Bing

    2016-01-01

    Highlights: • Fluorescent Ag nanoclusters were first applied to Cr(VI) detection. • The proposed method is simple, rapid, and environmentally friendly. • The sensor shows a wide linear range, low detection limit, and good selectivity. • The system can also be used for the indirect assay of total chromium and Cr(III). • The analyses in real water samples are satisfactory. - Abstract: In this work, a simple and sensitive Cr(VI) sensor is proposed based on fluorescent polyethyleneimine-stabilized Ag nanoclusters, which allows the determination over a wide concentration range of 0.1 nM–3.0 μM and with a detection limit as low as 0.04 nΜ and a good selectivity. The quenching mechanism was discussed in terms of the absorption and fluorescence spectra, suggesting that Cr(VI) is connected to Ag nanoclusters by hydrogen bond between the oxygen atom at the vertex of tetrahedron structure of Cr(VI) and the amino nitrogen of polyethyleneimine that surrounded Ag nanoclusters and electron transfer from Ag nanoclusters to highly electron-deficient Cr(VI) results in fluorescence quenching. Despite the failure to quench the fluorescence efficiently, Cr(III) can also be measured using the proposed Ag nanoclusters by being oxidized to Cr(VI) in alkaline solution (pH ∼9) containing H 2 O 2 . Therefore, our approach could be used to detect Cr(VI), Cr(III) and the total chromium level in aqueous solution. In addition, Cr(VI) analysis in real water samples were satisfactory, indicating this method could be practically promising for chromium measurements.

  12. Use of Activated Carbon in Packaging to Attenuate Formaldehyde-Induced and Formic Acid-Induced Degradation and Reduce Gelatin Cross-Linking in Solid Dosage Forms.

    Science.gov (United States)

    Colgan, Stephen T; Zelesky, Todd C; Chen, Raymond; Likar, Michael D; MacDonald, Bruce C; Hawkins, Joel M; Carroll, Sophia C; Johnson, Gail M; Space, J Sean; Jensen, James F; DeMatteo, Vincent A

    2016-07-01

    Formaldehyde and formic acid are reactive impurities found in commonly used excipients and can be responsible for limiting drug product shelf-life. Described here is the use of activated carbon in drug product packaging to attenuate formaldehyde-induced and formic acid-induced drug degradation in tablets and cross-linking in hard gelatin capsules. Several pharmaceutical products with known or potential vulnerabilities to formaldehyde-induced or formic acid-induced degradation or gelatin cross-linking were subjected to accelerated stability challenges in the presence and absence of activated carbon. The effects of time and storage conditions were determined. For all of the products studied, activated carbon attenuated drug degradation or gelatin cross-linking. This novel use of activated carbon in pharmaceutical packaging may be useful for enhancing the chemical stability of drug products or the dissolution stability of gelatin-containing dosage forms and may allow for the 1) extension of a drug product's shelf-life when the limiting attribute is a degradation product induced by a reactive impurity, 2) marketing of a drug product in hotter and more humid climatic zones than currently supported without the use of activated carbon, and 3) enhanced dissolution stability of products that are vulnerable to gelatin cross-linking. Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

  13. Significantly enhanced critical current density in nano-MgB2 grains rapidly formed at low temperature with homogeneous carbon doping

    International Nuclear Information System (INIS)

    Liu, Yongchang; Lan, Feng; Ma, Zongqing; Chen, Ning; Li, Huijun; Barua, Shaon; Patel, Dipak; Shahriar, M; Hossain, Al; Kim, Jung Ho; Dou, Shi Xue; Acar, S

    2015-01-01

    High performance MgB 2 bulks using carbon-coated amorphous boron as a boron precursor were fabricated by Cu-activated sintering at low temperature (600 °C, below the Mg melting point). Dense nano-MgB 2 grains with a high level of homogeneous carbon doping were formed in these MgB 2 samples. This type of microstructure can provide a stronger flux pinning force, together with depressed volatility and oxidation of Mg owing to the low-temperature Cu-activated sintering, leading to a significant improvement of critical current density (J c ) in the as-prepared samples. In particular, the value of J c for the carbon-coated (Mg 1.1 B 2 )Cu 0.05 sample prepared here is even above 1 × 10 5 A cm −2 at 20 K, 2 T. The results herein suggest that the combination of low-temperature Cu-activated sintering and employment of carbon-coated amorphous boron as a precursor could be a promising technique for the industrial production of practical MgB 2 bulks or wires with excellent J c , as the carbon-coated amorphous boron powder can be produced commercially at low cost, while the addition of Cu is very convenient and inexpensive. (paper)

  14. Significantly enhanced critical current density in nano-MgB2 grains rapidly formed at low temperature with homogeneous carbon doping

    Science.gov (United States)

    Liu, Yongchang; Lan, Feng; Ma, Zongqing; Chen, Ning; Li, Huijun; Barua, Shaon; Patel, Dipak; Shahriar, M.; Hossain, Al; Acar, S.; Kim, Jung Ho; Xue Dou, Shi

    2015-05-01

    High performance MgB2 bulks using carbon-coated amorphous boron as a boron precursor were fabricated by Cu-activated sintering at low temperature (600 °C, below the Mg melting point). Dense nano-MgB2 grains with a high level of homogeneous carbon doping were formed in these MgB2 samples. This type of microstructure can provide a stronger flux pinning force, together with depressed volatility and oxidation of Mg owing to the low-temperature Cu-activated sintering, leading to a significant improvement of critical current density (Jc) in the as-prepared samples. In particular, the value of Jc for the carbon-coated (Mg1.1B2)Cu0.05 sample prepared here is even above 1 × 105 A cm-2 at 20 K, 2 T. The results herein suggest that the combination of low-temperature Cu-activated sintering and employment of carbon-coated amorphous boron as a precursor could be a promising technique for the industrial production of practical MgB2 bulks or wires with excellent Jc, as the carbon-coated amorphous boron powder can be produced commercially at low cost, while the addition of Cu is very convenient and inexpensive.

  15. Experimental Research on Destruction Mode and Anchoring Performance of Carbon Fiber Phyllostachys pubescens Anchor Rod with Different Forms

    Directory of Open Access Journals (Sweden)

    Wang Yulan

    2018-01-01

    Full Text Available The anchoring technology is extensively applied in reinforcing protection of the earth relics. Now that no specification is available for different new anchor rods in earth relics protection due to diversified destruction modes of earth relics and complexity of engineering technology conditions, it is urgent to guide reinforcing design and construction with a complete detailed anchor rod research document. With the new carbon fiber Phyllostachys pubescens anchor rod as the research object, six lots of in situ tests are designed to, respectively, study the destruction mode and anchoring performance of the carbon fiber Phyllostachys pubescens anchor rod under different anchor length L, anchor rod diameter D, bore diameter H, grouting material S, rib spacing R, and inclination angle A in this paper. By studying load shift curve experiment in drawing of the anchor rod, the destruction mode and ultimate bearing capacity of the carbon fiber Phyllostachys pubescens anchor rod in different experiment lots are obtained, and the concept of permitted application value N in anchor rod design is proposed. By studying strain distribution characteristics of anchor rods in experimental lots along the length direction under action of the permitted application value N and combining the existing destruction mode and ultimate bearing capacity, this paper analyzes influences of L, D, H, S, R, and A on anchoring effect of the carbon fiber Phyllostachys pubescens anchor rod; gives the reasonable value range of L, D, H, and R when the carbon fiber Phyllostachys pubescens anchor rod is used for reinforcing design of the earth relics; and provides favorable experiment basis for reinforcing design of the earth relics based on the carbon fiber Phyllostachys pubescens anchor rod.

  16. Bulky Counterions: Enhancing the Two-Photon Excited Fluorescence of Gold Nanoclusters.

    Science.gov (United States)

    Bertorelle, Franck; Moulin, Christophe; Soleilhac, Antonin; Comby-Zerbino, Clothilde; Dugourd, Philippe; Russier-Antoine, Isabelle; Brevet, Pierre-François; Antoine, Rodolphe

    2018-01-19

    Increasing fluorescence quantum yields of ligand-protected gold nanoclusters has attracted wide research interest. The strategy consisting in using bulky counterions has been found to dramatically enhance the fluorescence. In this Communication, we push forward this concept to the nonlinear optical regime. We show that by an appropriate choice of bulky counterions and of solvent, a 30-fold increase in two-photon excited fluorescence (TPEF) signal at ≈600 nm for gold nanoclusters can be obtained. This would correspond to a TPEF cross-section in the range of 0.1 to 1 GM. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Polarization memory of white luminescence of Ag nanoclusters dispersed in glass host.

    Science.gov (United States)

    Kuznetsov, A S; Tikhomirov, V K; Moshchalkov, V V

    2012-09-10

    A mechanism for white luminescence of Ag nanoclusters dispersed in oxyfluoride glass host has been revealed by studying a temperature dependence of its polarization memory. The spectral dependence of the polarization memory indicates the presence of a variety of Ag nanoclusters, particularly emitting in the blue, green and red. Temperature activated intercluster energy transfer has been found responsible for white luminescence. The means for increasing luminescence quantum yield have been suggested. This efficient white luminescence may be used in highly demanded devices, such as luminescent lamps, displays, color phosphors for LEDs, photovoltaic devices based on down shifting of solar spectrum.

  18. Absorption Spectra of CuGaSe2 and CuInSe2 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.

  19. 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.

  20. Efficient Removal of Arsenic Using Magnetic Multi-Granule Nanoclusters

    International Nuclear Information System (INIS)

    Lee, Seungho; Cha, Jinmyung; Sim, Kyunjong; Lee, Jinkyu

    2014-01-01

    Magnetic multi-granule nanoclusters (MGNCs) were investigated as an inexpensive means to effectively remove arsenic from aqueous environment, particularly groundwater sources consumed by humans. Various size MGNCs were examined to determine both their capacity and efficiency for arsenic adsorption for different initial arsenic concentrations. The MGNCs showed highly efficient arsenic adsorption characteristics, thereby meeting the allowable safety limit of 10 μg/L (ppb), prescribed by the World Health Organization (WHO), and confirming that 0.4 g and 0.6 g of MGNCs were sufficient to remove 0.5 mg/L and 1.0 mg/L of arsenate (AsO 4 3- ) from water, respectively. Adsorption isotherm models for the MGNCs were used to estimate the adsorption parameters. They showed similar parameters for both the Langmuir and Sips models, confirming that the adsorption process in this work was active at a region of low arsenic concentration. The actual efficiency of arsenate removal was then tested against 1 L of artificial arsenic-contaminated groundwater with an arsenic concentration of 0.6 mg/L in the presence of competing ions. In this case, only 1.0 g of 100 nm MGNCs was sufficient to reduce the arsenic concentrations to below the WHO permissible safety limit for drinking water, without adjusting the pH or temperature, which is highly advantageous for practical field applications

  1. 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.

  2. Peculiar features of heat capacity for Cu and Ni nanoclusters

    International Nuclear Information System (INIS)

    Gafner, S. L.; Redel, L. V.; Gafner, Yu. Ya.; Samsonov, V. M.

    2011-01-01

    The heat capacity of copper and nickel clusters (from 2 to 6 nm in diameter) was investigated in the temperature range 200–800 K using molecular dynamics method and a modified tight-binding potential. The simulation results demonstrate a very good agreement with the available experimental data at T = 200 K and a fairy good agreement at higher temperatures. A number of regular trends are revealed in computer experiments which agree with the corresponding theoretical predictions. A conclusion is made that in the case of single free clusters the heat capacity may exceed the capacity of the corresponding bulk material. It is found that at 200 K, the copper nanocluster (D = 6 nm) heat capacity is higher by 10% and for nickel cluster by 13%. The difference diminishes with increasing the nanoparticles size proportionally to the relative number of surface atoms. A conclusion is made that very high values of the nanostructure heat capacity observed in laboratory experiments should not be attributed to free clusters, i.e., the effect in question is caused by other reasons.

  3. Mercury speciation with fluorescent gold nanocluster as a probe.

    Science.gov (United States)

    Yang, Jian-Yu; Yang, Ting; Wang, Xiao-Yan; Chen, Ming-Li; Yu, Yong-Liang; Wang, Jian-Hua

    2018-05-11

    Fluorescent nanoparticles are widely used for sensing biologically significant species. However, it is rarely reported for the discrimination or speciation of metal species. In this work, we report for the first time the speciation of mercury (Hg 2+ ) and methylmercury (CH 3 Hg + ) by taking advantage of the fluorescence feature of folic acid-capped gold nanoclusters (FA-AuNCs). FA-Au NCs exhibit an average size of 2.08±0.15 nm and a maximum emission at λ ex /λ em = 280/440 nm with a quantum yield of 27.3%. It is interesting that Hg 2+ causes a significant quench on the fluorescence of FA-Au NCs, whereas CH 3 Hg + leads to a remarkable fluorescence enhancement. Based on this discriminative fluorescent response between Hg 2+ and CH 3 Hg + , a novel nanosensor for the speciation of CH 3 Hg + and Hg 2+ was developed, providing limits of detection (LOD) of 28 nM for Hg 2+ and 25 nM for CH 3 Hg + within 100-1000 nM. This sensing system is highly selective to mercury. Its practical applications were further demonstrated by the analysis of CH 3 Hg + and the speciation of mercury (CH 3 Hg + and Hg 2+ ) in environmental water and fish samples.

  4. 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.

  5. 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.

  6. A strategy to find minimal energy nanocluster structures.

    Science.gov (United States)

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

    2013-11-05

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

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

    KAUST Repository

    AbdulHalim, Lina G.; Bootharaju, Megalamane Siddaramappa; Tang, Qing; Del Gobbo, Silvano; AbdulHalim, Rasha; Eddaoudi, Mohamed; Jiang, De-en; Bakr, Osman

    2015-01-01

    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.

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

    KAUST Repository

    Hu, Lianzhe

    2014-05-20

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

  9. Efficient Removal of Arsenic Using Magnetic Multi-Granule Nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Seungho; Cha, Jinmyung; Sim, Kyunjong; Lee, Jinkyu [Seoul National Univ., Seoul (Korea, Republic of)

    2014-02-15

    Magnetic multi-granule nanoclusters (MGNCs) were investigated as an inexpensive means to effectively remove arsenic from aqueous environment, particularly groundwater sources consumed by humans. Various size MGNCs were examined to determine both their capacity and efficiency for arsenic adsorption for different initial arsenic concentrations. The MGNCs showed highly efficient arsenic adsorption characteristics, thereby meeting the allowable safety limit of 10 μg/L (ppb), prescribed by the World Health Organization (WHO), and confirming that 0.4 g and 0.6 g of MGNCs were sufficient to remove 0.5 mg/L and 1.0 mg/L of arsenate (AsO{sub 4}{sup 3-}) from water, respectively. Adsorption isotherm models for the MGNCs were used to estimate the adsorption parameters. They showed similar parameters for both the Langmuir and Sips models, confirming that the adsorption process in this work was active at a region of low arsenic concentration. The actual efficiency of arsenate removal was then tested against 1 L of artificial arsenic-contaminated groundwater with an arsenic concentration of 0.6 mg/L in the presence of competing ions. In this case, only 1.0 g of 100 nm MGNCs was sufficient to reduce the arsenic concentrations to below the WHO permissible safety limit for drinking water, without adjusting the pH or temperature, which is highly advantageous for practical field applications.

  10. Towards understanding of poly-guanine activated fluorescent silver nanoclusters

    International Nuclear Information System (INIS)

    Walczak, Sylwia; Morishita, Kiyoshi; Ahmed, Moin; Liu, Juewen

    2014-01-01

    It has been recently reported that the fluorescence of some DNA-templated silver nanoclusters (AgNCs) can be significantly enhanced upon by hybridizing with a partially complementary DNA containing a G-rich overhang near the AgNCs. This discovery has found a number of analytical applications but many fundamental questions remain to be answered. In this work, the photostability of these activated AgNCs is reported. After adding the G-rich DNA activator, the fluorescence intensity peaks in ∼1 h and then starts to decay, where the decaying rate is much faster with light exposure. The lost fluorescence is recovered by adding NaBH 4 , suggesting that the bleaching is an oxidative process. Once activated, the G-rich activator can be removed while the AgNCs still maintain most of their fluorescence intensity. UV–vis spectroscopy suggests that new AgNC species are generated upon hybridization with the activator. The base sequence and length of the template DNA have also been varied, leading to different emission colors and color change after hybridization. G-rich aptamers can also serve as activators. Our results indicate that activation of the fluorescence by G-rich DNA could be a convenient method for biosensor development since the unstable NaBH 4 is not required for the activation step. (paper)

  11. Soluble form of carbonic anhydrase IX (CA IX) in the serum and urine of renal carcinoma patients

    Czech Academy of Sciences Publication Activity Database

    Závada, Jan; Závadová, Zuzana; Zaťovičová, M.; Hyršl, L.; Kawaciuk, I.

    2003-01-01

    Roč. 89, - (2003), s. 1067-1071 ISSN 0007-0920 R&D Projects: GA ČR GA301/99/0356 Institutional research plan: CEZ:AV0Z5052915 Keywords : carbonic anhydrase IX * tumor antigens * cancer diagnostics Subject RIV: EC - Immunology Impact factor: 3.894, year: 2003

  12. Depth-resolution imaging of crystalline nanoclusters attached on and embedded in amorphous films using aberration-corrected TEM

    Energy Technology Data Exchange (ETDEWEB)

    Yamasaki, Jun, E-mail: yamasaki@uhvem.osaka-u.ac.jp [Research Center for Ultra-High Voltage Electron Microscopy, Osaka University, 7-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan); EcoTopia Science Institute, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Mori, Masayuki [Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Hirata, Akihiko [Advanced Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Hirotsu, Yoshihiko [Institute of Scientific and Industrial Research, Osaka University, 8-1 Mihogaoka, Ibaraki, Osaka 567-0047 (Japan); Tanaka, Nobuo [EcoTopia Science Institute, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan)

    2015-04-15

    For observations of crystalline nanoclusters, the features and capabilities of depth-resolution imaging by aberration-corrected transmission electron microscopy (TEM) were investigated using image simulations and experiments for two types of samples. The first sample was gold clusters attached on an amorphous carbon film. The experimental through-focal series indicated that the focal plane for the cluster was shifted 3 nm from that for the supporting film. This difference is due to the depth-resolution imaging of the cluster and film, the mid-planes of which are separated by 3 nm along the depth direction (the electron incident direction). On the basis of this information, the three-dimensional configuration of the sample, such as the film thickness of 2 nm, was successfully illustrated. The second sample was a Zr{sub 66.7}Ni{sub 33.3} metallic glass including a medium-range-order (MRO) structure, which was approximately considered to be a crystalline cluster with a diameter of 1.6 nm. In the experimental through-focal series, the lattice fringe of the MRO cluster was visible at limited focal conditions. Image simulations reproduced well the focal conditions and also indicated a structural condition for the visualization that the embedded cluster must be apart from the mid-plane of the matrix film. Similar to the case of the first sample, this result can be explained by the idea that the “effective focal planes” for the film and cluster are at different heights. This type of depth-resolution phase contrast imaging is possible only in aberration-corrected TEM and when the sample has a simple structure and is sufficiently thin for the kinematical scattering approximation. - Highlights: • Depth-resolution imaging by aberration-corrected TEM was demonstrated. • Thickness of a carbon film supporting gold nano-crystals was successfully estimated. • A crystalline nanocluster embedded in an amorphous matrix was successfully observed. • It was clarified that

  13. Water soluble organic carbon in aerosols (PM1, PM2.5, PM10) and various precipitation forms (rain, snow, mixed) over the southern Baltic Sea station.

    Science.gov (United States)

    Witkowska, Agnieszka; Lewandowska, Anita U

    2016-12-15

    In the urbanized coastal zone of the Southern Baltic, complex measurements of water soluble organic carbon (WSOC) were conducted between 2012 and 2015, involving atmospheric precipitation in its various forms (rain, snow, mixed) and PM1, PM2.5 and PM10 aerosols. WSOC constituted about 60% of the organic carbon mass in aerosols of various sizes. The average concentration of WSOC was equal to 2.6μg∙m -3 in PM1, 3.6μg∙m -3 in PM2.5 and 4.4μg∙m -3 in PM10. The lowest concentration of WSOC was noted in summer as a result of effective removal of this compound with rainfall. The highest WSOC concentrations in PM2.5 and PM10 aerosols were measured in spring, which should be associated with developing vegetation on land and in the sea. On the other hand, the highest WSOC concentrations in PM1 occurred in winter at low air temperatures and greatest atmospheric stability, when there were increased carbon emissions from fuel combustion in the communal-utility sector and from transportation. WSOC concentrations in precipitation were determined by its form. Mixed precipitation turned out to be the richest in soluble organic carbon (5.1mg·dm -3 ), while snow contained the least WSOC (1.7mg·dm -3 ). Snow and rain cleaned carbon compounds from the atmosphere more effectively when precipitation lasted longer than 24h, while in the case of mixed precipitation WSOC was removed most effectively within the first 24h. Copyright © 2016 Elsevier B.V. All rights reserved.

  14. Different sources of reduced carbon contribute to form three classes of terpenoid emitted by Quercus ilex L. leaves

    International Nuclear Information System (INIS)

    Loreto, F.; Ciccioli, P.; Brancaleoni, E.; Cecinato, A.; Frattoni, M.; Sharkey, T.D.

    1996-01-01

    Quercus ilex L. leaves emit terpenes but do not have specialized structures for terpene storage. We exploited this unique feature to investigate terpene biosynthesis in intact leaves of Q. ilex. Light induction allowed us to distinguish three classes of terpenes: (i) a rapidly induced class including alpha-pinene; (ii) a more slowly induced class, including cis-beta-ocimene; and (iii) the most slowly induced class, including 3-methyl-3-buten-1-ol. Using 13C, we found that alpha-pinene and cis-beta-ocimene were labeled quickly and almost completely while there was a delay before label appeared in linalool and 3-methyl-3-buten-1-ol. The acetyl group of 3-methyl-3-buten-1-yl acetate was labeled quickly but label was limited to 20% of the moiety. It is suggested that the ocimene class of monoterpenes is made from one or more terpenes of the alpha-pinene class and that both classes are made entirely from reduced carbon pools inside the chloroplasts. Linalool and 3-methyl-3-buten-1-ol are made from a different pool of reduced carbon, possibly in nonphotosynthetic plastids. The acetyl group of the 3-methyl-3-buten-1-yl acetate is derived mostly from carbon that does not participate in photosynthetic reactions. Low humidity and prolonged exposure to light favored ocimenes emission and induced linalool emission. This may indicate conversion between terpene classes

  15. Should R and D in non-carbon forms of energy be subsidised? The contribution of macro-economic models

    International Nuclear Information System (INIS)

    Taverdet-Popiolek, N.; Lafforgue, G.

    2012-01-01

    This article concentrates on two sorts of distortion that can prevent markets from functioning optimally: the first is pollution (mainly CO) produced by burning fossil fuels; the second is linked to R and D activity given that innovators are generally incapable of capturing completely the rent associated with their innovation. To correct for these externalities, two types of instrument can be used: an environmental tax on carbon emissions on the one hand and subsidies for research on the other. Here, it must be borne in mind that in general equilibrium situations, these instruments have a priori complex interactions. The aim of the article is to recall the economic principles that govern the correction of environmental externalities and of research, then go on to present two top-down models of endogenous growth that bring some answers to the question of interaction of associated public policies. Although they differ according to the way that innovation, climate and damage are integrated, they end up with the following consensual result: the beneficial effect of the carbon tax is reinforced by the simultaneous adoption of a subsidy for R and D int o non-carbon energy and vice-versa. (authors)

  16. Generation and reactivity of putative support systems, Ce-Al neutral binary oxide nanoclusters: CO oxidation and C-H bond activation

    Science.gov (United States)

    Wang, Zhe-Chen; Yin, Shi; Bernstein, Elliot R.

    2013-11-01

    Both ceria (CeO2) and alumina (Al2O3) are very important catalyst support materials. Neutral binary oxide nanoclusters (NBONCs), CexAlyOz, are generated and detected in the gas phase and their reactivity with carbon monoxide (CO) and butane (C4H10) is studied. The very active species CeAlO4• can react with CO and butane via O atom transfer (OAT) and H atom transfer (HAT), respectively. Other CexAlyOz NBONCs do not show reactivities toward CO and C4H10. The structures, as well as the reactivities, of CexAlyOz NBONCs are studied theoretically employing density functional theory (DFT) calculations. The ground state CeAlO4• NBONC possesses a kite-shaped structure with an OtCeObObAlOt configuration (Ot, terminal oxygen; Ob, bridging oxygen). An unpaired electron is localized on the Ot atom of the AlOt moiety rather than the CeOt moiety: this Ot centered radical moiety plays a very important role for the reactivity of the CeAlO4• NBONC. The reactivities of Ce2O4, CeAlO4•, and Al2O4 toward CO are compared, emphasizing the importance of a spin-localized terminal oxygen for these reactions. Intramolecular charge distributions do not appear to play a role in the reactivities of these neutral clusters, but could be important for charged isoelectronic BONCs. DFT studies show that the reaction of CeAlO4• with C4H10 to form the CeAlO4H•C4H9• encounter complex is barrierless. While HAT processes have been previously characterized for cationic and anionic oxide clusters, the reported study is the first observation of a HAT process supported by a ground state neutral oxide cluster. Mechanisms for catalytic oxidation of CO over surfaces of AlxOy/MmOn or MmOn/AlxOy materials are proposed consistent with the presented experimental and theoretical results.

  17. Optical properties and oxidation of carbonized and cross-linked structures formed in polycarbonate by plasma immersion ion implantation

    Energy Technology Data Exchange (ETDEWEB)

    Kosobrodova, E., E-mail: elenak@physics.usyd.edu.au [Department of Applied Plasma and Physics, School of Physics, University of Sydney, NSW 2006 (Australia); Kondyurin, A. [Department of Applied Plasma and Physics, School of Physics, University of Sydney, NSW 2006 (Australia); Chrzanowski, W. [Faculty of Pharmacy, University of Sydney, NSW 2006 (Australia); Department of Nanobiomedical Science and BK21 PLUS NBM Global Research, Center for Regenerative Medicine, Dankook University, Cheonan 330-714 (Korea, Republic of); McCulloch, D.G. [School of Applied Sciences, RMIT University, Melbourne, Victoria 3001 (Australia); McKenzie, D.R.; Bilek, M.M.M. [Department of Applied Plasma and Physics, School of Physics, University of Sydney, NSW 2006 (Australia)

    2014-06-01

    Highlights: • Structure and properties of polycarbonate films spin-coated on silicon are studied. • The films have two thicknesses: thicker and thinner than a depth of ion penetration. • Effect of radio frequency plasma and plasma immersion ion implantation is compared. - Abstract: At ion fluences higher than 5 · 10{sup 15} ions/cm{sup 2}, plasma immersion ion implantation (PIII) of polycarbonate (PC) results in a formation of a carbonized surface layer. The thickness of this layer is close to the depth of ion penetration. A comparison of PIII treated, spin-coated PC films with pre-treatment thicknesses designed to match and exceed the carbonized layer thickness is employed to study the properties of the carbonised layer independently from the less modified underlying structure. At ion fluencies higher than 10{sup 16} ions/cm{sup 2}, the thinner PC film is completely transformed into an amorphous carbon-like material with no traces of the initial PC structure. The thicker films, however, incorporated two layers: a top carbonised layer and a cross-linked layer below. Compared to the two-layered PC film, the completely carbonized layer was found to have a much higher concentration of C=O bonds and much lower concentration of O–H bonds after exposure to atmospheric oxygen. The refractive index of the thicker PC films PIII treated with high ion fluencies is close to the refractive index of diamond-like carbon. Anomalous dispersion of the refractive index of the thicker PC films is observed after formation of the carbonised layer. The refractive index of the thinner PC film has normal dispersion at all ion fluences. At ion fluences of 2 · 10{sup 16} ions/cm{sup 2}, both PC films were found to have the same etching rate as polystyrene. Washing in dichloromethane had no effect on the carbonised layer but affected the underlying material in the case of the thicker PC films leading to a wrinkled structure up to ion fluences of 2 · 10{sup 16} ions/cm{sup 2}. At

  18. Forecasting how residential urban form affects the regional carbon savings and costs of retrofitting and decentralized energy supply

    International Nuclear Information System (INIS)

    Hargreaves, Anthony; Cheng, Vicky; Deshmukh, Sandip; Leach, Matthew; Steemers, Koen

    2017-01-01

    Highlights: • An innovative model for testing combinations of spatial planning and decentralised energy supply. • An improved method of modelling the spatial variability of energy consumption per dwelling type. • Shows how spatial planning would affect the future carbon reduction of decentralised supply. • Forecasts the future carbon reduction and costs of retrofitting and decentralised supply. • A method of forecasting how residential space would affect the suitability of decentralised supply. - Abstract: Low carbon energy supply technologies are increasingly used at the building and community scale and are an important part of the government decarbonisation strategy. However, with their present state of development and costs, many of these decentralised technologies rely on public subsidies to be financially viable. It is questionable whether they are cost effective compared to other ways of reducing carbon emissions, such as decarbonisation of conventional supply and improving the energy efficiency of dwellings. Previous studies have found it difficult to reliably estimate the future potential of decentralised supply because this depends on the available residential space which varies greatly within a city region. To address this problem, we used an integrated modelling framework that converted the residential density forecasts of a regional model into a representation of the building dimensions and land of the future housing stock. This included a method of estimating the variability of the dwellings and residential land. We present the findings of a case study of the wider south east regions of England that forecasted the impacts of energy efficiency and decentralised supply scenarios to year 2031. Our novel and innovative method substantially improves the spatial estimates of energy consumption compared to building energy models that only use standard dwelling typologies. We tested the impact of an alternative spatial planning policy on the future

  19. Reaction of carbon tetrachloride with methane in a non-equilibrium plasma at atmospheric pressure, and characterisation of the polymer thus formed

    Energy Technology Data Exchange (ETDEWEB)

    Gaikwad, Vaibhav [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Kennedy, Eric, E-mail: Eric.Kennedy@newcastle.edu.au [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Mackie, John [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Holdsworth, Clovia [Centre for Organic Electronics, Chemistry Building, School of Environmental and Life Sciences, University of Newcastle, Callaghan, NSW 2308 (Australia); Molloy, Scott; Kundu, Sazal; Stockenhuber, Michael [Process Safety and Environment Protection Research Group, School of Engineering, The University of Newcastle, Callaghan, NSW 2308 (Australia); Dlugogorski, Bogdan [School of Engineering and Information Technology, Murdoch University, Murdoch, WA 6150 (Australia)

    2014-09-15

    Highlights: • CCl{sub 4} remediation using non-equilibrium plasma and non-oxidative conditions is proposed. • The reaction mechanism relies on experimental data and quantum chemical analysis. • Comprehensive mass balance for the reaction is provided. • CCl{sub 4} is converted to an environmentally benign and potentially useful polymer. • Characterisation of the polymer structure based on NMR and FTIR analyses is presented. - Abstract: In this paper we focus on the development of a methodology for treatment of carbon tetrachloride utilising a non-equilibrium plasma operating at atmospheric pressure, which is not singularly aimed at destroying carbon tetrachloride but rather at converting it to a non-hazardous, potentially valuable commodity. This method encompasses the reaction of carbon tetrachloride and methane, with argon as a carrier gas, in a quartz dielectric barrier discharge reactor. The reaction is performed under non-oxidative conditions. Possible pathways for formation of major products based on experimental results and supported by quantum chemical calculations are outlined in the paper. We elucidate important parameters such as carbon tetrachloride conversion, product distribution, mass balance and characterise the chlorinated polymer formed in the process.

  20. Computational investigation of CO adsorbed on Aux, Agx and (AuAg)x nanoclusters (x = 1 - 5, 147) and monometallic Au and Ag low-energy surfaces*

    Science.gov (United States)

    Gould, Anna L.; Catlow, C. Richard A.; Logsdail, Andrew J.

    2018-02-01

    Density functional theory calculations have been performed to investigate the use of CO as a probe molecule for the determination of the structure and composition of Au, Ag and AuAg nanoparticles. For very small nanoclusters (x = 1 - 5), the CO vibrational frequencies can be directly correlated to CO adsorption strength, whereas larger 147-atom nanoparticles show a strong energetic preference for CO adsorption at a vertex position but the highest wavenumbers are for the bridge positions. We also studied CO adsorption on Au and Ag (100) and (111) surfaces, for a 1 monolayer coverage, which proves to be energetically favourable on atop only and bridge positions for Au (100) and atop for Ag (100); vibrational frequencies of the CO molecules red-shift to lower wavenumbers as a result of increased metal coordination. We conclude that CO vibrational frequencies cannot be solely relied upon in order to obtain accurate compositional analysis, but we do propose that elemental rearrangement in the core@shell nanoclusters, from Ag@Au (or Au@Ag) to an alloy, would result in a shift in the CO vibrational frequencies that indicate changes in the surface composition. Contribution to the Topical Issue "Shaping Nanocatalysts", edited by Francesca Baletto, Roy L. Johnston, Jochen Blumberger and Alex Shluger.Supplementary material in the form of one pdf file available from the Journal web page at http://https://doi.org/10.1140/epjb/e2017-80280-7

  1. Trapping of Syntaxin1a in Presynaptic Nanoclusters by a Clinically Relevant General Anesthetic

    Directory of Open Access Journals (Sweden)

    Adekunle T. Bademosi

    2018-01-01

    Full Text Available Summary: Propofol is the most commonly used general anesthetic in humans. Our understanding of its mechanism of action has focused on its capacity to potentiate inhibitory systems in the brain. However, it is unknown whether other neural mechanisms are involved in general anesthesia. Here, we demonstrate that the synaptic release machinery is also a target. Using single-particle tracking photoactivation localization microscopy, we show that clinically relevant concentrations of propofol and etomidate restrict syntaxin1A mobility on the plasma membrane, whereas non-anesthetic analogs produce the opposite effect and increase syntaxin1A mobility. Removing the interaction with the t-SNARE partner SNAP-25 abolishes propofol-induced syntaxin1A confinement, indicating that syntaxin1A and SNAP-25 together form an emergent drug target. Impaired syntaxin1A mobility and exocytosis under propofol are both rescued by co-expressing a truncated syntaxin1A construct that interacts with SNAP-25. Our results suggest that propofol interferes with a step in SNARE complex formation, resulting in non-functional syntaxin1A nanoclusters. : Bademosi et al. use single-molecule imaging microscopy to understand how general anesthetics might affect presynaptic release mechanisms. They find that a clinically relevant concentration of propofol targets the presynaptic release machinery by specifically restricting syntaxin1A mobility on the plasma membrane. This suggests an alternate target process for these drugs. Keywords: super-resolution microscopy, sptPALM, propofol, etomidate, SNARE, Drosophila melanogaster, PC12, syntaxin1A, SNAP-25, neurotransmission

  2. Tailoring the Crystal Structure of Nanoclusters Unveiled High Photoluminescence via Ion Pairing

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa

    2018-03-26

    The lack of structurally distinct nanoclusters (NCs) of identical size and composition prevented the mechanistic understanding of their structural effects on ion pairing and concomitant optical properties. To produce such highly sought NCs, we designed a new monothiolate-for-dithiolate exchange strategy that enabled the selective transformation of the structure of a NC without affecting its metal atomicity or composition. Through this method, a bimetallic [PtAg28(BDT)12(PPh3)4]4– NC (1) was successfully synthesized from [PtAg28(S-Adm)18(PPh3)4]2+ NC (2) (S-Adm, 1-adamantanethiolate; BDT, 1,3-benzenedithiolate; PPh3, triphenylphosphine). The determined X-ray crystal structure of 1 showed a PtAg12 icosahedron core and a partially exposed surface, which are distinct from a face-centered cubic PtAg12 core and a fully covered surface of 2. We reveal through mass spectrometry (MS) that 1 forms ion pairs with counterions attracted by the core charge of the cluster, which is in line with density functional simulations. The MS data for 1, 2, and other NCs suggested that such attraction is facilitated by the exposed surface of 1. The formation of ion pairs increases the photoluminescence (PL) quantum yield of 1 up to 17.6% depending on the bulkiness of the counterion. Unlike small counterions, larger ones are calculated to occupy ≤90% of the volume near the exposed cluster surface and to make the ligand shell of 1 more rigid, which is observed to increase the PL. Thus, the developed synthesis strategy for structurally different NCs of the same size and composition allows us to probe the structure–property relationship for ion pairing and concomitant PL enhancement.

  3. The emergence of nonbulk properties in supported metal clusters: negative thermal expansion and atomic disorder in Pt nanoclusters supported on gamma-Al2O3.

    Science.gov (United States)

    Sanchez, Sergio I; Menard, Laurent D; Bram, Ariella; Kang, Joo H; Small, Matthew W; Nuzzo, Ralph G; Frenkel, Anatoly I

    2009-05-27

    The structural dynamics-cluster size and adsorbate-dependent thermal behaviors of the metal-metal (M-M) bond distances and interatomic order-of Pt nanoclusters supported on a gamma-Al(2)O(3) are described. Data from scanning transmission electron microscopy (STEM) and X-ray absorption spectroscopy (XAS) studies reveal that these materials possess a dramatically nonbulklike nature. Under an inert atmosphere small, subnanometer Pt/gamma-Al(2)O(3) clusters exhibit marked relaxations of the M-M bond distances, negative thermal expansion (NTE) with an average linear thermal expansion coefficient alpha = (-2.4 +/- 0.4) x 10(-5) K(-1), large static disorder and dynamical bond (interatomic) disorder that is poorly modeled within the constraints of classical theory. The data further demonstrate a significant temperature-dependence to the electronic structure of the Pt clusters, thereby suggesting the necessity of an active model to describe the cluster/support interactions mediating the cluster's dynamical structure. The quantitative dependences of these nonbulklike behaviors on cluster size (0.9 to 2.9 nm), ambient atmosphere (He, 4% H(2) in He or 20% O(2) in He) and support identity (gamma-Al(2)O(3) or carbon black) are systematically investigated. We show that the nonbulk structural, electronic and dynamical perturbations are most dramatically evidenced for the smallest clusters. The adsorption of hydrogen on the clusters leads to an increase of the Pt-Pt bondlengths (due to a lifting of the surface relaxation) and significant attenuation of the disorder present in the system. Oxidation of these same clusters has the opposite effect, leading to an increase in Pt-Pt bond strain and subsequent enhancement in nonbulklike thermal properties. The structural and electronic properties of Pt nanoclusters supported on carbon black contrast markedly with those of the Pt/gamma-Al(2)O(3) samples in that neither NTE nor comparable levels of atomic disorder are observed. The Pt

  4. Pinning of size-selected gold and nickel nanoclusters on graphite

    NARCIS (Netherlands)

    Di Vece, M.|info:eu-repo/dai/nl/248753355; Paloma, S.; Palmer, R.E.

    2005-01-01

    Size-selected gold and nickel nanoclusters are of interest from an electronic, catalytic, and biological point of view. These applications require the deposition of the clusters on a surface, and a key challenge is to retain the cluster size. Here controlled energy impact is used to immobilize the

  5. Spectroscopy of metal "superatom" nanoclusters and high-Tc superconducting pairing

    Science.gov (United States)

    Halder, Avik; Kresin, Vitaly V.

    2015-12-01

    A unique property of metal nanoclusters is the "superatom" shell structure of their delocalized electrons. The electronic shell levels are highly degenerate and therefore represent sharp peaks in the density of states. This can enable exceptionally strong electron pairing in certain clusters composed of tens to hundreds of atoms. In a finite system, such as a free nanocluster or a nucleus, pairing is observed most clearly via its effect on the energy spectrum of the constituent fermions. Accordingly, we performed a photoionization spectroscopy study of size-resolved aluminum nanoclusters and observed a rapid rise in the near-threshold density of states of several clusters (A l37 ,44 ,66 ,68 ) with decreasing temperature. The characteristics of this behavior are consistent with compression of the density of states by a pairing transition into a high-temperature superconducting state with Tc≳100 K. This value exceeds that of bulk aluminum by two orders of magnitude. These results highlight the potential of novel pairing effects in size-quantized systems and the possibility to attain even higher critical temperatures by optimizing the particles' size and composition. As a new class of high-temperature superconductors, such metal nanocluster particles are promising building blocks for high-Tc materials, devices, and networks.

  6. Electron microscopy and positron annihilation study of CdSe nanoclusters embedded in MgO

    International Nuclear Information System (INIS)

    Huis, M.A. van; Veen, A. van; Schut, H.; Eijt, S.W.H.; Kooi, B.J.; Hosson, J.Th.M. de

    2004-01-01

    CdSe nanoclusters are created in MgO by means of co-implantation of 280 keV, 1 x 10 16 Cd ions cm -2 and 210 keV, 1 x 10 16 Se ions cm -2 in single crystals of MgO(0 0 1) and subsequent thermal annealing at a temperature of 1300 K. The structural properties and the orientation relationship between the CdSe and the MgO are investigated using cross-sectional transmission electron microscopy (XTEM). The crystal structure of the nanoclusters depends on their size. The smallest nanoclusters with a size below 5 nm have the cubic rocksalt crystal structure. The larger nanoclusters have a different (most likely the cubic sphalerite) crystal structure. The defect evolution in the sample after ion implantation and during thermal annealing is investigated using Doppler broadening positron beam analysis (PBA). The defect evolution in samples co-implanted with Cd and Se is compared to the defect evolution in samples implanted with only Cd or only Se ions

  7. Absorption Spectra of CuGaSe2 and CuInSe2 Semiconducting Nanoclusters

    KAUST Repository

    Mokkath, Junais Habeeb; Singh, Nirpendra; Schwingenschlö gl, Udo

    2015-01-01

    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

  8. Metal Catalysts for Heterogeneous Catalysis: From Single Atoms to Nanoclusters and Nanoparticles.

    Science.gov (United States)

    Liu, Lichen; Corma, Avelino

    2018-05-23

    Metal species with different size (single atoms, nanoclusters, and nanoparticles) show different catalytic behavior for various heterogeneous catalytic reactions. It has been shown in the literature that many factors including the particle size, shape, chemical composition, metal-support interaction, and metal-reactant/solvent interaction can have significant influences on the catalytic properties of metal catalysts. The recent developments of well-controlled synthesis methodologies and advanced characterization tools allow one to correlate the relationships at the molecular level. In this Review, the electronic and geometric structures of single atoms, nanoclusters, and nanoparticles will be discussed. Furthermore, we will summarize the catalytic applications of single atoms, nanoclusters, and nanoparticles for different types of reactions, including CO oxidation, selective oxidation, selective hydrogenation, organic reactions, electrocatalytic, and photocatalytic reactions. We will compare the results obtained from different systems and try to give a picture on how different types of metal species work in different reactions and give perspectives on the future directions toward better understanding of the catalytic behavior of different metal entities (single atoms, nanoclusters, and nanoparticles) in a unifying manner.

  9. Nanomorphology of Polymer Frameworks and Their Role as Templates for Generating Size-Controlled Metal Nanoclusters

    Czech Academy of Sciences Publication Activity Database

    Artuso, F.; D'Archivio, A. A.; Lora, S.; Jeřábek, Karel; Králik, E.; Corain, B.

    2003-01-01

    Roč. 9, č. 21 (2003), s. 5292-5296 ISSN 0947-6539 Grant - others:GA-(IT) 2001038991; VEGA(SK) 1/9142/02 Institutional research plan: CEZ:AV0Z4072921 Keywords : nanoclusters * nano-structures * gel-type resin s Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 4.353, year: 2003

  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...

  11. Electron microscopy and positron annihilation study of CdSe nanoclusters embedded in MgO

    Energy Technology Data Exchange (ETDEWEB)

    Huis, M.A. van E-mail: vanhuis@iri.tudelft.nl; Veen, A. van; Schut, H.; Eijt, S.W.H.; Kooi, B.J.; Hosson, J.Th.M. de

    2004-06-01

    CdSe nanoclusters are created in MgO by means of co-implantation of 280 keV, 1 x 10{sup 16} Cd ions cm{sup -2} and 210 keV, 1 x 10{sup 16} Se ions cm{sup -2} in single crystals of MgO(0 0 1) and subsequent thermal annealing at a temperature of 1300 K. The structural properties and the orientation relationship between the CdSe and the MgO are investigated using cross-sectional transmission electron microscopy (XTEM). The crystal structure of the nanoclusters depends on their size. The smallest nanoclusters with a size below 5 nm have the cubic rocksalt crystal structure. The larger nanoclusters have a different (most likely the cubic sphalerite) crystal structure. The defect evolution in the sample after ion implantation and during thermal annealing is investigated using Doppler broadening positron beam analysis (PBA). The defect evolution in samples co-implanted with Cd and Se is compared to the defect evolution in samples implanted with only Cd or only Se ions.

  12. Electron microscopy and positron annihilation study of CdSe nanoclusters embedded in MgO

    Science.gov (United States)

    van Huis, M. A.; van Veen, A.; Schut, H.; Eijt, S. W. H.; Kooi, B. J.; De Hosson, J. Th. M.

    2004-06-01

    CdSe nanoclusters are created in MgO by means of co-implantation of 280 keV, 1 × 10 16 Cd ions cm -2 and 210 keV, 1 × 10 16 Se ions cm -2 in single crystals of MgO(0 0 1) and subsequent thermal annealing at a temperature of 1300 K. The structural properties and the orientation relationship between the CdSe and the MgO are investigated using cross-sectional transmission electron microscopy (XTEM). The crystal structure of the nanoclusters depends on their size. The smallest nanoclusters with a size below 5 nm have the cubic rocksalt crystal structure. The larger nanoclusters have a different (most likely the cubic sphalerite) crystal structure. The defect evolution in the sample after ion implantation and during thermal annealing is investigated using Doppler broadening positron beam analysis (PBA). The defect evolution in samples co-implanted with Cd and Se is compared to the defect evolution in samples implanted with only Cd or only Se ions.

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

    Directory of Open Access Journals (Sweden)

    Jakob G. Howalt

    2014-01-01

    Full Text Available The presence of water often gives rise to oxygen adsorption on catalyst surfaces through decomposition of water and the adsorbed oxygen or hydroxide species often occupy important surfaces sites, resulting in a decrease or a total hindrance of other chemical reactions taking place at that site. 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 oxygen over nitrogen and hydrogen at neutral bias, but under electrochemical reaction conditions needed for nitrogen reduction, oxygen adsorption is severely weakened and the adsorption energy is comparable to hydrogen and nitrogen adsorption. The potentials required to reduce oxygen off the surface are −0.72 V or lower for all oxygen coverages studied, and it is thus possible to (reactivate (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 and electrochemical ammonia production via the associative mechanism is possible at potentials as low as −0.45 V to −0.7 V.

  14. Phosphatidylserine and GTPase activation control Cdc42 nanoclustering to counter dissipative diffusion.

    Science.gov (United States)

    Sartorel, Elodie; Ünlü, Caner; Jose, Mini; Massoni-Laporte, Aurélie; Meca, Julien; Sibarita, Jean-Baptiste; McCusker, Derek

    2018-04-18

    The anisotropic organization of plasma membrane constituents is indicative of mechanisms that drive the membrane away from equilibrium. However, defining these mechanisms is challenging due to the short spatio-temporal scales at which diffusion operates. Here, we use high-density single protein tracking combined with photoactivation localization microscopy (sptPALM) to monitor Cdc42 in budding yeast, a system in which Cdc42 exhibits anisotropic organization. Cdc42 exhibited reduced mobility at the cell pole, where it was organized in nanoclusters. The Cdc42 nanoclusters were larger at the cell pole than those observed elsewhere in the cell. These features were exacerbated in cells expressing Cdc42-GTP, and were dependent on the scaffold Bem1, which contributed to the range of mobility and nanocluster size exhibited by Cdc42. The lipid environment, in particular phosphatidylserine levels, also played a role in regulating Cdc42 nanoclustering. These studies reveal how the mobility of a Rho GTPase is controlled to counter the depletive effects of diffusion, thus stabilizing Cdc42 on the plasma membrane and sustaining cell polarity. Movie S1 Movie S1 sptPALM imaging of live yeast expressing Pil1-mEOS expressed at the genomic locus. Pil1-mEOS was simultaneously photo-converted with a 405 nm laser and imaged with a 561 nm laser using HiLo illumination. Images were acquired at 20 ms intervals, of which 300 frames are shown at 7 frames per second.

  15. Formation of ring-patterned nanoclusters by laser–plume interaction

    International Nuclear Information System (INIS)

    Sivayoganathan, Mugunthan; Tan Bo; Venkatakrishnan, Krishnan

    2013-01-01

    This article reports for the first time a unique study performed to regulate the ring diameter of nanoclusters fabricated during femtosecond laser ablation of solids and a mechanism is proposed for the formation of those ring clusters. The ring nanoclusters are made out of nanoparticles with a range of 10–30 nm. Our experimental studies showed the synthesis of ring nanoclusters with random diameter distribution on metals, nonmetals, and semiconductors, such as titanium, aluminum, glasses, ceramics, graphite, and silicon. To regulate the ring size, the effects of laser parameters, such as wavelength, pulse duration, pulse energy, and repetition rate on the ring diameter are analyzed. The influence of ablated materials and the background gas on ring size is also elaborated in this article. The motion of plume species under the influence of ponderomotive force on free electrons possibly played a key role in the formation of the ring-patterned nanoclusters. This study could help to understand the fundamentals in laser ablative nanosynthesis as well as to produce nanostructures with organized ring diameter that controls the density and porosity of those 3D nanostructures.

  16. {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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ferraris, M.; Perero, S. [Politecnico di Torino, Department of Applied Science and Technology, Torino, C.so Duca degli Abruzzi 24, I-10129 (Italy); Ferraris, S., E-mail: sara.ferraris@polito.it [Politecnico di Torino, Department of Applied Science and Technology, Torino, C.so Duca degli Abruzzi 24, I-10129 (Italy); Miola, M.; Vernè, E. [Politecnico di Torino, Department of Applied Science and Technology, Torino, C.so Duca degli Abruzzi 24, I-10129 (Italy); Skoglund, S. [KTH Royal Institute of Technology, Div. Surface and Corrosion Science, Dr. Kristinas v. 51, SE-100 44 (Sweden); Blomberg, E. [KTH Royal Institute of Technology, Div. Surface and Corrosion Science, Dr. Kristinas v. 51, SE-100 44 (Sweden); SP Technical Research Institute of Sweden, Chemistry, Materials and Surfaces, P.O. Box 5607, SE-114 86 Stockholm (Sweden); Odnevall Wallinder, I. [KTH Royal Institute of Technology, Div. Surface and Corrosion Science, Dr. Kristinas v. 51, SE-100 44 (Sweden)

    2017-02-28

    Highlights: • A silver nanocluster-silica composite coating sputter-deposited onto stainless steel. • Good adhesion and resistance upon cleaning with NaOH, H{sub 2}SO{sub 4} and detergents. • Low release of silver ions and no release as silver nanoparticles. • Good antibacterial activity against S. aureus even after heating to 450 °C. • Good antibacterial activity shown during cheese production. - Abstract: 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

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

    International Nuclear Information System (INIS)

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

    2017-01-01

    Highlights: • A silver nanocluster-silica composite coating sputter-deposited onto stainless steel. • Good adhesion and resistance upon cleaning with NaOH, H_2SO_4 and detergents. • Low release of silver ions and no release as silver nanoparticles. • Good antibacterial activity against S. aureus even after heating to 450 °C. • Good antibacterial activity shown during cheese production. - Abstract: 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

  19. 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.

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

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa; Burlakov, Victor M.; Besong, Tabot M.D.; Joshi, Chakra Prasad; AbdulHalim, L; Black, David; Whetten, Robert; Goriely, Alain; Bakr, Osman

    2015-01-01

    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.

  1. Application of ionizing radiation for metal nanoclusters synthesis

    International Nuclear Information System (INIS)

    Smietanko-Chmielewska, D.K.; Chmielewski, A.G.; Warsaw University of Technology, Warsaw

    2011-01-01

    Complete text of publication follows. Possibility of ionizing radiation application in nanotechnology has been observed from very beginning when this field of science and technology was named. The lithography is based on electron and ion beam applications, and metal clusters synthesis by radiation induced radicals was reported many years ago. International Atomic Energy Agency was the first organization which has started coordinated programs on radiation applications in nanotechnology which are being continued in the frame of regional cooperation project RER8014. Some of applications led to patented technical solutions. Then review papers and chapters in the books have been published. The main applications beside of lithography deal with metal nanoclusters and nano-composites synthesis. Polymer composites containing metal nanoparticles have attracted a great interest due to their unique chemical and physical properties. 'Green' chemistry promotes application of natural fibers in such structures, among them cellulose is one of the most frequently used. However, cellulose fabric have ability to absorb moisture, so under certain conditions of humidity and temperature they can be subjected to microbial attack. One of the most popular and best known antibacterial agents is silver, which serves as a potential antibacterial material acting against an exceptionally broad spectrum of bacteria including activity against antibiotic-resistant bacteria. Silver nanoparticles (Ag NPs) were grown at the cellulose fibers surface by direct reduction of AgNO 3 with electron beam (EB) application. The big field of development concerns nano composites, possibility of e/X units application enlarge this possibility to industrial scale product manufacturing. Acknowledgement: This work was supported by the IAEA, regional project RER/8/014 and by the Ministry of Science and Higher Education, project DPN/W14/IAEA/2009.

  2. Nuclear graphite waste's behaviour under disposal conditions: Study of the release and repartition of organic and inorganic forms of carbon 14 and tritium in alkaline media

    International Nuclear Information System (INIS)

    Vende, L.

    2012-01-01

    23000 tons of graphite wastes will be generated during dismantling of the first generation of French reactors (9 gas cooled reactors). These wastes are classified as Long Lived Low Level wastes (LLW-LL). As requested by the law, the French National Radioactive Waste Management Agency (Andra) is studying concepts of low-depth disposals.In this work we focus on carbon 14, the main long-lived radionuclide in graphite waste (5730 y), but also on tritium, which is the main contributor to the radioactivity in the short term. Carbon 14 and tritium may be released from graphite waste in many forms in gaseous phase ( 14 CO 2 , HT...) or in solution ( 14 CO 3 2- , HTO...). Their speciation will strongly affect their migration from the disposal site to the environment. Leaching experiments, in alkaline solution (0.1 M NaOH simulating repository conditions) have been performed on irradiated graphite, from Saint-Laurent A2 and G2 reactors, in order to quantify their release and characterize their speciation. The studies show that carbon 14 exists in both gaseous and aqueous phases. In the gaseous phase, release is weak (≤0.1%) and corresponds to oxidizable species. Carbon 14 is mainly released into liquid phase, as both inorganic and organic species. 65% of released fraction is inorganic and 35% organic carbon. Two tritiated species have been identified in gaseous phase: HTO and HT/Organically Bond Tritium. More than 90% of tritium in that phase corresponds to HT/OBT. But release is weak (≤0.1%). HTO is mainly in the liquid phase. (author)

  3. Magnetic behavior of Si-Ge bond in SixGe4-x nano-clusters

    Science.gov (United States)

    Nahali, Masoud; Mehri, Ali

    2018-06-01

    The structure of SixGe4-x nano-clusters were optimized by MPW1B95 level of theory using MG3S and SDB-aug-cc-PVTZ basis set. The agreement of the calculated ionization and dissociation energies with experimental values validates the reported structures of nano-clusters and justifies the use of hybrid meta density functional method. Since the Si-Si bond is stronger than Si-Ge and Ge-Ge bonds, the Si-Si, Si-Ge, and Ge-Ge diagonal bonds determine the precedence of the stability in these nano-clusters. The hybrid meta density functional calculations were carried out to investigate the adsorption of CO on all possible SixGe4-x nano-clusters. It was found that the silicon atom generally makes a stronger bond with CO than germanium and thereby preferentially affects the shape of structures having higher multiplicity. In Si-Ge structures with higher spin more than 95% of spins accumulate on positions with less bonds to other atoms of the cluster. Through CO adsorption on these clusters bridge structures are made that behave as spin bridge which conduct the spin from the nano-cluster surface to the adsorbate atoms. A better understanding of bridged structures was achieved upon introducing the 'spin bridge' concept. Based on exhaustive spin density analysis, it was found that the reason for the extra negative charge on oxygen in the bridged structures is the relocation of spin from the surface through the bridge.

  4. Ultrahigh surface area meso/microporous carbon formed with self-template for high-voltage aqueous supercapacitors

    Science.gov (United States)

    Yang, Jie; Hu, Jiangtao; Zhu, Min; Zhao, Yan; Chen, Haibiao; Pan, Feng

    2017-10-01

    A new hierarchically porous carbon has been synthesized with self-template of silica phase from a commercial silicone resin by pyrolysis and subsequent NaOH activation. The obtained carbon materials achieve an ultrahigh specific surface area (2896 m2 g-1) with abundant mesopores. The C800 sample demonstrates excellent performance in supercapacitors, with a high capacitance of 322 F g-1 at 0.5 A g-1 and outstanding rate capability (182 F g-1 at 100 A g-1) in a three-electrode system using 6.0 mol L-1 KOH electrolyte. The energy density is improved by widening the voltage window using 1.0 mol L-1 alkali metal nitrate solutions (LiNO3, NaNO3, KNO3) in which the strong solvation of alkali metal cations and nitrate anions effectively reduce the activity of water. In a symmetric supercapacitor, the maximum operating voltage is essentially restricted by the potential of positive electrode and the total capacitance is dominated by the capacitance of the anion at the positive electrode. The symmetric supercapacitors based on C800 deliver a high energy density of 22.4 Wh kg-1 at a power density of 0.23 kW kg-1 in 1.0 mol L-1 LiNO3 with a voltage of 1.8 V and long-term stability with a retention of 89.87% after 10000 cycles.

  5. Chemical properties of various organic electrolytes for lithium rechargeable batteries. Pt. 1.. Characterization of passivating layer formed on graphite in alkyl carbonate solutions

    Energy Technology Data Exchange (ETDEWEB)

    Mori, Shoichiro; Asahina, Hitoshi; Suzuki, Hitoshi; Yonei, Ayako; Yokoto, Kiyomi [Tsukuba Research Center, Mitsubishi Chemical Corporation, Ibaraki (Japan)

    1997-09-01

    The characteristics and reaction mechanisms of the passivating film formed on the surface of graphite were investigated in ethylene carbonate-diethyl carbonate solutions containing LiClO{sub 4}, LiPF{sub 6} and LiN(SO{sub 2}CF{sub 3}){sub 2}. The electron consumption resulting on the irreversible capacity of graphite was almost equivalent to that used in the one-electron reduction of Li{sup +} found in the film. The electrochemical reactions in the first discharge process may be divided into the following steps: (i) `initial film formation step` from 1.4 to 0.55 V; (ii) `main film formation step` from 0.55 to 0.2 V, and (iii) `lithium intercalation step from 0.2 to 0.0 V. Most of the passivating film is formed together with the lithium intercalation reaction at step (ii). The passivating film formed at this step contained a significant amount of organic film such as EtOCO{sub 2}Li, (CH{sub 2}OCO{sub 2}Li){sub 2}, etc. Through the consecutive formation of passivating film at steps (i) and (ii), lithium intercalation into graphite proceeds smoothly without further decomposition of organic electrolyte. (orig.)

  6. Exchange bias in reduced dimensions: cobalt nanocluster arrays underthe influence of nanometer thin MnPt capping layers

    Czech Academy of Sciences Publication Activity Database

    Sessi, V.; Hertenberger, S.; Zhang, J.; Schmitz, D.; Gsell, S.; Schreck, M.; Morel, R.; Brenac, A.; Honolka, Jan; Kern, K.

    2014-01-01

    Roč. 113, č. 12 (2014), "123903-1"-"123903-10" ISSN 0021-8979 Institutional support: RVO:68378271 Keywords : antiferromagnetism * cobalt * nanoclusters * quenching * superparamagnetism Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 2.183, year: 2014

  7. Shell model for REO{sub x} nanoclusters in amorphous SiO{sub 2}: charge trapping and electroluminescence quenching

    Energy Technology Data Exchange (ETDEWEB)

    Tiagulskyi, S.; Nazarov, A.; Tyagulskii, I.; Lysenko, V. [Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine, Prospekt Nauki 41, 03028 Kiev (Ukraine); Rebohle, L.; Lehmann, J.; Skorupa, W. [Institute of Ion Beam Physics and Materials Research, Helmholtz-Zentrum Dresden Rossendorf e.V., POB 510119, 01314 Dresden (Germany)

    2012-06-15

    In this work charge trapping and electroluminescence (EL) quenching in rare-earth (RE) implanted SiO{sub 2} on Si as a function of injected charge into the dielectric were studied. The blocking of the luminescent REO{sub X} nanoclusters from the hot exciting electrons by negative charge trapping in a defect region (shell) located in the vicinity of the REO{sub X} nanocluster/SiO{sub 2} interface is considered as the main mechanism of EL quenching for small size (up to 10 nm) REO{sub X} nanoclusters. It is suggested that the increase of the nanoclusters size results in disordering of the SiO{sub 2} matrix but in a decrease of local blocking for excitation of the luminescent centers. (copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  8. Electrochemical, atomic force microscopy and infrared reflection absorption spectroscopy studies of pre-formed mussel adhesive protein films on carbon steel for corrosion protection

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Fan, E-mail: fanzhang@kth.se [KTH Royal Institute of Technology, School of Chemical Science and Engineering, Department of Chemistry, Div. of Surface and Corrosion Science, Drottning Kristinas vaeg.51, SE-100 44 Stockholm (Sweden); Pan, Jinshan [KTH Royal Institute of Technology, School of Chemical Science and Engineering, Department of Chemistry, Div. of Surface and Corrosion Science, Drottning Kristinas vaeg.51, SE-100 44 Stockholm (Sweden); Claesson, Per Martin [KTH Royal Institute of Technology, School of Chemical Science and Engineering, Department of Chemistry, Div. of Surface and Corrosion Science, Drottning Kristinas vaeg.51, SE-100 44 Stockholm (Sweden); Institute for Surface Chemistry, P.O. Box 5607, SE-114 86 Stockholm (Sweden); Brinck, Tore [KTH Royal Institute of Technology, School of Chemical Science and Engineering, Department of Physical Chemistry, Division of Physical Chemistry, Teknikringen 36, SE-10044 Stockholm (Sweden)

    2012-10-01

    Electrochemical measurements, in situ and ex situ atomic force microscopy (AFM) experiments and infrared reflection absorption spectroscopy (IRAS) analysis were performed to investigate the formation and stability as well as corrosion protection properties of mussel adhesive protein (Mefp-1) films on carbon steel, and the influence of cross-linking by NaIO{sub 4} oxidation. The in situ AFM measurements show flake-like adsorbed protein aggregates in the film formed at pH 9. The ex situ AFM images indicate multilayer-like films and that the film becomes more compact and stable in NaCl solution after the cross-linking. The IRAS results reveal the absorption bands of Mefp-1 on carbon steel before and after NaIO{sub 4} induced oxidation of the pre-adsorbed protein. Within a short exposure time, a certain corrosion protection effect was noted for the pre-formed Mefp-1 film in 0.1 M NaCl solution. Cross-linking the pre-adsorbed film by NaIO{sub 4} oxidation significantly enhanced the protection efficiency by up to 80%. - Highlights: Black-Right-Pointing-Pointer Mussel protein was tested as 'green' corrosion protection strategy for steel. Black-Right-Pointing-Pointer At pH 9, the protein adsorbs on carbon steel and forms a multilayer-like film. Black-Right-Pointing-Pointer NaIO{sub 4} leads to structural changes and cross-linking of the protein film. Black-Right-Pointing-Pointer Cross-linking results in a dense and compact film with increased stability. Black-Right-Pointing-Pointer Cross-linking of preformed film significantly enhances the corrosion protection.

  9. Carbonization

    Energy Technology Data Exchange (ETDEWEB)

    Hennebutte, H G; Goutal, E

    1921-07-04

    Materials such as coal, peat, or schist are subjected to a rising temperature in successive stages in apparatus in which the distillation products are withdrawn at each stage. For example in a three-stage process, the acid products of the first or low-temperature stage are fixed in a suitable reagent, the basic products from a second or higher-temperature stage are absorbed in an acid reagent, hydrocarbons being retained by solvents, while the third are subjected to a pyrogenation process carried out in a closed vessel. Wherein the material is subjected in stages to a rising temperature, the gasified products being withdrawn at each stage, and are prevented as far as possible from mixing with the carbonized products.

  10. 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

  11. Spiral patterns of gold nanoclusters in silicon (100) produced by metal vapour vacuum arc implantation of gold ions

    International Nuclear Information System (INIS)

    Venkatachalam, Dinesh Kumar; Sood, Dinesh Kumar; Bhargava, Suresh Kumar

    2008-01-01

    Self-assembled gold nanoclusters are attractive building blocks for future nanoscale sensors and optical devices due to their exciting catalytic properties. In this work, we report direct bottom-up synthesis of spiral patterns of gold nanoclusters in silicon (100) substrates by Au ion implantation followed by thermal annealing. This unique phenomenon is observed only above a critical threshold implantation dose and annealing temperature. Systematic study by electron microscopy, analytical x-ray diffraction and atomic force microscopy shows the temperature- and time-dependent nucleation, growth of Au nanoclusters and evolution of the spiral patterns. The observed patterns of gold nanoclusters bear a resemblance to the spiral growth prevalent in some directionally solidified eutectic alloys. Based on this systematic study of the growth and morphology of nanoclusters, a tentative model has been proposed for the formation mechanism of this unusual self-assembled pattern in an amorphous Si/Au system. This model shows that melting of the implanted layer is essential and without which no spiral patterns are observed. A better understanding of this self-assembly process will open up new ways to fabricate ordered arrays of gold nanoclusters in silicon substrates for seeding selective growth of one-dimensional nanostructures

  12. Covalently linked multimers of gold nanoclusters Au102(p-MBA)44 and Au∼250(p-MBA)n.

    Science.gov (United States)

    Lahtinen, Tanja; Hulkko, Eero; Sokołowska, Karolina; Tero, Tiia-Riikka; Saarnio, Ville; Lindgren, Johan; Pettersson, Mika; Häkkinen, Hannu; Lehtovaara, Lauri

    2016-11-10

    We present the synthesis, separation, and characterization of covalently-bound multimers of para-mercaptobenzoic acid (p-MBA) protected gold nanoclusters. The multimers were synthesized by performing a ligand-exchange reaction of a pre-characterized Au 102 (p-MBA) 44 nanocluster with biphenyl-4,4'-dithiol (BPDT). The reaction products were separated using gel electrophoresis yielding several distinct bands. The bands were analyzed by transmission electron microscopy (TEM) revealing monomer, dimer, and trimer fractions of the nanocluster. TEM analysis of dimers in combination with molecular dynamics simulations suggest that the nanoclusters are covalently bound via a disulfide bridge between BPDT molecules. The linking chemistry is not specific to Au 102 (p-MBA) 44 . The same approach yields multimers also for a larger monodisperse p-MBA-protected cluster of approximately 250 gold atoms, Au ∼250 (p-MBA) n . While the Au 102 (p-MBA) 44 is not plasmonic, the Au ∼250 (p-MBA) n nanocluster supports localized surface plasmon resonance (LSPR) at 530 nm. Multimers of the Au ∼250 (p-MBA) n exhibit additional transitions in their UV-vis spectrum at 630 nm and 810 nm, indicating the presence of hybridized LSPR modes. Well-defined structures and relatively small sizes make these systems excellent candidates for connecting ab initio theoretical studies and experimental quantum plasmonics. Moreover, our work opens new possibilities in the controlled synthesis of advanced monodisperse nanocluster superstructures.

  13. Structure prediction of nanoclusters; a direct or a pre-screened search on the DFT energy landscape?

    Science.gov (United States)

    Farrow, M R; Chow, Y; Woodley, S M

    2014-10-21

    The atomic structure of inorganic nanoclusters obtained via a search for low lying minima on energy landscapes, or hypersurfaces, is reported for inorganic binary compounds: zinc oxide (ZnO)n, magnesium oxide (MgO)n, cadmium selenide (CdSe)n, and potassium fluoride (KF)n, where n = 1-12 formula units. The computational cost of each search is dominated by the effort to evaluate each sample point on the energy landscape and the number of required sample points. The effect of changing the balance between these two factors on the success of the search is investigated. The choice of sample points will also affect the number of required data points and therefore the efficiency of the search. Monte Carlo based global optimisation routines (evolutionary and stochastic quenching algorithms) within a new software package, viz. Knowledge Led Master Code (KLMC), are employed to search both directly and after pre-screening on the DFT energy landscape. Pre-screening includes structural relaxation to minimise a cheaper energy function - based on interatomic potentials - and is found to improve significantly the search efficiency, and typically reduces the number of DFT calculations required to locate the local minima by more than an order of magnitude. Although the choice of functional form is important, the approach is robust to small changes to the interatomic potential parameters. The computational cost of initial DFT calculations of each structure is reduced by employing Gaussian smearing to the electronic energy levels. Larger (KF)n nanoclusters are predicted to form cuboid cuts from the rock-salt phase, but also share many structural motifs with (MgO)n for smaller clusters. The transition from 2D rings to 3D (bubble, or fullerene-like) structures occur at a larger cluster size for (ZnO)n and (CdSe)n. Differences between the HOMO and LUMO energies, for all the compounds apart from KF, are in the visible region of the optical spectrum (2-3 eV); KF lies deep in the UV region

  14. Surface species formed by the adsorption and dissociation of water molecules on Ru(0001) surface containing a small coverage of carbon atoms studied by scanning tunneling microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Dept of Materials Science and Engineering UCB; Dept of Applied Science and Technology, UCB; Institut de Ciencia de Materials de Barcelona, Barcelona, Spain; Instituto de Ciencia de Materiales de Madrid, Madrid, Spain; Department of Mechanical Engineering, Yale University; Salmeron, Miquel; Shimizu, Tomoko K.; Mugarza, Aitor; Cerda, Jorge I.; Heyde, Markus; Qi, Yabing; Schwarz, Udo D.; Ogletree, D. Frank; Salmeron, Miquel

    2008-04-26

    The adsorption and dissociation of water on a Ru(0001) surface containing a small amount ({le} 3 %) of carbon impurities was studied by scanning tunneling microscopy (STM). Various surface species are formed depending on the temperature. These include molecular H{sub 2}O, H{sub 2}O-C complexes, H, O, OH and CH. Clusters of either pure H{sub 2}O or mixed H{sub 2}O-OH species are also formed. Each of these species produces a characteristic contrast in the STM images and can be identified by experiment and by ab initio total energy calculations coupled with STM image simulations. Manipulation of individual species via excitation of vibrational modes with the tunneling electrons has been used as supporting evidence.

  15. Between carbonatite and lamproite—Diamondiferous Torngat ultramafic lamprophyres formed by carbonate-fluxed melting of cratonic MARID-type metasomes

    Science.gov (United States)

    Tappe, Sebastian; Foley, Stephen F.; Kjarsgaard, Bruce A.; Romer, Rolf L.; Heaman, Larry M.; Stracke, Andreas; Jenner, George A.

    2008-07-01

    New U-Pb perovskite ages reveal that diamondiferous ultramafic lamprophyre magmas erupted through the Archean crust of northern Labrador and Quebec (eastern Canada) between ca. 610 and 565 Ma, a period of strong rifting activity throughout contiguous Laurentia and Baltica. The observed Torngat carbonate-rich aillikite/carbonatite and carbonate-poor mela-aillikite dyke varieties show a large spread in Sr-Nd-Hf-Pb isotope ratios with pronounced correlations between isotope systems. An isotopically depleted component is identified solely within aillikites ( 87Sr/ 86Sr i = 0.70323-0.70377; ɛNd i = +1.2-+1.8; ɛHf i = +1.4-+3.5; 206Pb/ 204Pb i = 18.2-18.5), whereas some aillikites and all mela-aillikites range to more enriched isotope signatures ( 87Sr/ 86Sr i = 0.70388-0.70523; ɛNd i = -0.5 to -3.9; ɛHf i = -0.6 to -6.0; 206Pb/ 204Pb i = 17.8-18.2). These contrasting isotopic characteristics of aillikites/carbonatites and mela-aillikites, along with subtle differences in their modal carbonate, SiO 2, Al 2O 3, Na 2O, Cs-Rb, and Zr-Hf contents, are consistent with two distinctive metasomatic assemblages of different age in the mantle magma source region. Integration of petrologic, geochemical, and isotopic information leads us to propose that the isotopically enriched component originated from a reduced phlogopite-richterite-Ti-oxide dominated source assemblage that is reminiscent of MARID suite xenoliths. In contrast, the isotopically depleted component was derived from a more oxidized phlogopite-carbonate dominated source assemblage. We argue that low-degree CO 2-rich potassic silicate melts from the convective upper mantle were preferentially channelled into an older, pre-existing MARID-type vein network at the base of the North Atlantic craton lithosphere, where they froze to form new phlogopite-carbonate dominated veins. Continued stretching and thinning of the cratonic lithosphere during the Late Neoproterozoic remobilized the carbonate-rich vein material and

  16. Projections of Ocean Acidification Under the U.N. Framework Convention of Climate Change Using a Reduced-Form Climate Carbon-Cycle Model

    Science.gov (United States)

    Hartin, C.

    2016-02-01

    Ocean chemistry is quickly changing in response to continued anthropogenic emissions of carbon to the atmosphere. Mean surface ocean pH has already decreased by 0.1 units relative to the preindustrial era. We use an open-source, simple climate and carbon cycle model ("Hector") to investigate future changes in ocean acidification (pH and calcium carbonate saturations) under the climate agreement from the United Nations Convention on Climate Change Conference (UNFCCC) of Parties in Paris 2015 (COP 21). Hector is a reduced-form, very fast-executing model that can emulate the global mean climate of the CMIP5 models, as well as the inorganic carbon cycle in the upper ocean, allowing us to investigate future changes in ocean acidification. We ran Hector under three different emissions trajectories, using a sensitivity analysis approach to quantify model uncertainty and capture a range of possible ocean acidification changes. The first trajectory is a business-as-usual scenario comparable to a Representative Concentration Pathway (RCP) 8.5, the second a scenario with the COP 21 commitments enacted, and the third an idealized scenario keeping global temperature change to 2°C, comparable to a RCP 2.6. Preliminary results suggest that under the COP 21 agreements ocean pH at 2100 will decrease by 0.2 units and surface saturations of aragonite (calcite) will decrease by 0.9 (1.4) units relative to 1850. Under the COP 21 agreement the world's oceans will be committed to a degree of ocean acidification, however, these changes may be within the range of natural variability evident in some paleo records.

  17. Comparison of the quantitative determination of soil organic carbon in coastal wetlands containing reduced forms of Fe and S

    Science.gov (United States)

    Passos, Tassia R. G.; Artur, Adriana G.; Nóbrega, Gabriel N.; Otero, Xosé L.; Ferreira, Tiago O.

    2016-06-01

    The performance of the Walkley-Black wet oxidation chemical method for soil organic carbon (SOC) determination in coastal wetland soils (mangroves, coastal lagoons, and hypersaline tidal flats) was evaluated in the state of Ceará along the semiarid coast of Brazil, assessing pyrite oxidation and its effects on soil C stock (SCS) quantification. SOC determined by the chemical oxidation method (CWB) was compared to that assessed by means of a standard elemental analyzer (CEA) for surficial samples (mangroves, whereas lower values were found in the other settings. CWB values were higher than CEA values. Significant differences in SCS calculations based on CWB and CEA were recorded for the coastal lagoons and hypersaline tidal flats. Nevertheless, the CWB and CEA values were strongly correlated, indicating that the wet oxidation chemical method can be used in such settings. In contrast, the absence of correlation for the mangroves provides evidence of the inadequacy of this method for these soils. Air drying and oxidation decrease the pyrite content, with larger effects rooted in oxidation. Thus, the wet oxidation chemical method is not recommended for mangrove soils, but seems appropriate for SOC/SCS quantification in hypersaline tidal flat and coastal lagoon soils characterized by lower pyrite contents.

  18. Raman light scattering in nanoporous carbon obtained from carbides of silicon and titanium

    International Nuclear Information System (INIS)

    Danishevskij, A.M.; Smorgonskaya, Eh.A.; Gordeev, S.K.; Grechinskaya, A.V.

    2001-01-01

    The Raman spectra in nanoporous carbon obtained through the chemical reaction from the polycrystal α-SiC and TiC are studied. It is shown that the spectra have a multicomponent character differentiating the considered group of materials from graphites and disordered carbon structures. The series of low-frequency modes is registered. The anisotropy and dispersion effects are identified. The results testify to the cluster structure of nanoporous carbon and dimensional quantization of electron and vibrational spectra in the carbon nanoclusters. The fine fragments of curved or fractures graphed sheets are the basic structural elements of nanoclusters in the porous skeleton. The presence of fragments close by structure to the tense cubic or hexagonal diamond is also notes [ru

  19. DNA sequencing, anatomy, and calcification patterns support a monophyletic, subarctic, carbonate reef-forming Clathromorphum (Hapalidiaceae, Corallinales, Rhodophyta).

    Science.gov (United States)

    Adey, Walter H; Hernandez-Kantun, Jazmin J; Johnson, Gabriel; Gabrielson, Paul W

    2015-02-01

    For the first time, morpho-anatomical characters that were congruent with DNA sequence data were used to characterize several genera in Hapalidiaceae-the major eco-engineers of Subarctic carbonate ecosystems. DNA sequencing of three genes (SSU, rbcL, ribulose-1, 5-bisphosphate carboxylase/oxygenase large subunit gene and psbA, photosystem II D1 protein gene), along with patterns of cell division, cell elongation, and calcification supported a monophyletic Clathromorphum. Two characters were diagnostic for this genus: (i) cell division, elongation, and primary calcification occurred only in intercalary meristematic cells and in a narrow vertical band (1-2 μm wide) resulting in a "meristem split" and (ii) a secondary calcification of interfilament crystals was also produced. Neopolyporolithon was resurrected for N. reclinatum, the generitype, and Clathromorphum loculosum was transferred to this genus. Like Clathromorphum, cell division, elongation, and calcification occurred only in intercalary meristematic cells, but in a wider vertical band (over 10-20 μm), and a "meristem split" was absent. Callilithophytum gen. nov. was proposed to accommodate Clathromorphum parcum, the obligate epiphyte of the northeast Pacific endemic geniculate coralline, Calliarthron. Diagnostic for this genus were epithallial cells terminating all cell filaments (no dorsi-ventrality was present), and a distinct "foot" was embedded in the host. Leptophytum, based on its generitype, L. laeve, was shown to be a distinct genus more closely related to Clathromorphum than to Phymatolithon. All names of treated species were applied unequivocally by linking partial rbcL sequences from holotype, isotype, or epitype specimens with field-collected material. Variation in rbcL and psbA sequences suggested that multiple species may be passing under each currently recognized species of Clathromorphum and Neopolyporolithon. © 2014 Phycological Society of America.

  20. Foliar stable carbon and nitrogen isotopes in woody Mediterranean species with different life form and post-fire regeneration.

    Science.gov (United States)

    Saura-Mas, S; Lloret, F

    2010-01-01

    Wildfire is an important ecological disturbance factor in most Mediterranean ecosystems. In the Mediterranean Basin, most shrub species can regenerate after fire by resprouting or seeding. Here, we hypothesize that post-fire regenerative syndromes may potentially co-vary with traits directly related to functional properties involved in resource use. Thus, seeders with a shorter life span and smaller size would have lower water-use efficiency (WUE) than re-sprouting species and would take up nutrients such as nitrogen from more superficial parts of the soil. To test this hypothesis, we compared leaf (13)C and (15)N signatures from 29 co-existing species with different post-fire regeneration strategies. We also considered life form as an additional explanatory variable of the differences between post-fire regenerative groups. Our data support the hypothesis that seeder species (which mostly evolved in the Quaternary under a Mediterranean climate) have lower WUE and less stomatal control than non-seeders (many of which evolved under different climatic conditions in the Tertiary) and consequently greater consumption of water per unit biomass. This would be related to their smaller life forms, which tend to have lower WUE and shorter life and leaf lifespan. Differences in (15)N also support the hypothesis that resprouters have deeper root systems than non-resprouters. The study supports the hypothesis of an overlap between plant functional traits and plant attributes describing post-disturbance resilience.

  1. A sensitive biosensor using double-layer capillary based immunomagnetic separation and invertase-nanocluster based signal amplification for rapid detection of foodborne pathogen.

    Science.gov (United States)

    Huang, Fengchun; Zhang, Huilin; Wang, Lei; Lai, Weihua; Lin, Jianhan

    2018-02-15

    Combining double-layer capillary based high gradient immunomagnetic separation, invertase-nanocluster based signal amplification and glucose meter based signal detection, a novel biosensor was developed for sensitive and rapid detection of E. coli O157:H7 in this study. The streptavidin modified magnetic nanobeads (MNBs) were conjugated with the biotinylated polyclonal antibodies against E. coli O157:H7 to form the immune MNBs, which were captured by the high gradient magnetic field in the double-layer capillary to specifically separate and efficiently concentrate the target bacteria. Calcium chloride was used with the monoclonal antibodies against E. coli O157:H7 and the invertase to form the immune invertase-nanoclusters (INCs), which were used to react with the target bacteria to form the MNB-bacteria-INC complexes in the capillary. The sucrose was then injected into the capillary and catalyzed by the invertase on the complexes into the glucose, which was detected using the glucose meter to obtain the concentration of the glucose for final determination of the E. coli O157:H7 cells in the sample. A linear relationship between the readout of the glucose meter and the concentration of the E. coli O157:H7 cells (from 10 2 to 10 7 CFU/mL) was found and the lower detection limit of this biosensor was 79 CFU/mL. This biosensor might be extended for the detection of other foodborne pathogens by changing the antibodies and has shown the potential for the detection of foodborne pathogens in a large volume of sample to further increase the sensitivity. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Carbon and nitrogen stocks and forms of N in a red dysthropic argisol grown or not with peanut forage

    Directory of Open Access Journals (Sweden)

    Valdinei Tadeu Paulino

    2012-12-01

    Full Text Available The low availability of nitrogen (N is considered one of the most limiting factors for the productivity of pastures, often responsible for their degradation. Overall, due to the high cost of nitrogen fertilizers, it is not applied in sufficient quantities. In this context, the cultivation of legumes is an option for adding nitrogen in the soil and simultaneously is into high-protein food. Forage legume may reduce the emission of greenhouse gases, changing nutrient cycling (C and N and can improve productivity and sustainability of agricultural systems. Most of the N in the soil is in the organic form compounds, that is converted into inorganic fraction, the predominant mineral forms of nitrogen (NH4+ and NO3-, available to plants by mineralization process. The C:N ratios from soil and plant residues affect the decomposition rate and the balance between N mineralization and N immobilization by microbes. The aim of this study was to evaluate the improvements in soil quality by comparing the forage legume Arachis pintoi cv. Belmonte, cultivated for eight years and a bare soil - an adjacent area (AA in a soil Ultissol (Red Dysthrophic argisol. We evaluated the levels and stocks of C, total N and C:N, NH4+ and NO3- in soil from a depth of 0-20 cm. The experimental design was a randomized complete block with ten replications. Variance analysis (ANOVA was used to detect significant differences between the study areas, averages were compared using test for multiple comparisons Student Newman-Keuls - SNK test (p < 0.05. Analyses were performed using SAS (2010. The availability of mineral N in uncultivated area was low, with mean values below 10 mg kg-1 for both nitrate and ammonium, possibly due to the low organic matter content (17.8 g kg-1. However, under the cultivation of the peanut forage there were increases (p < 0.05 of the contents and stocks of C and N, and the levels of ammonium and nitrate. Increases in total N and inorganic N forms are the

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

    Science.gov (United States)

    Li, Lun; Dou, Liguang; Zhang, Hui

    2014-03-01

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

  4. Photo-electrochemical analysis of passive film formed on X80 pipeline steel in bicarbonate/carbonate buffer solution

    Energy Technology Data Exchange (ETDEWEB)

    Li, D.G. [School of Materials Science and Engineering, Xi' an Jiaotong University, Xi' an 710049 (China); Tubular Goods Research Center of CNPC, Xi' an 710065 (China)], E-mail: dangguoli78@yahoo.com.cn; Feng, Y.R.; Bai, Z.Q. [Tubular Goods Research Center of CNPC, Xi' an 710065 (China); Zhu, J.W.; Zheng, M.S. [School of Materials Science and Engineering, Xi' an Jiaotong University, Xi' an 710049 (China)

    2008-02-28

    Photo-electrochemical measurement was used to explore the formation potential, formation time, chloride ions concentration, applied potential and pH value of the solution on the electronic property of passive film formed on X80 pipeline steel in 1 M NaHCO{sub 3}/0.5 M Na{sub 2}CO{sub 3} buffer solution. The results showed that the photocurrent is positive, indicating an n-type semiconductor character of the passive film, the photocurrent increased with increasing the formation potential, prolonging the formation time, decreasing chloride ions concentration, rising applied potential and decreasing the pH value of the solution. Capacitance measurement exhibited a positive slope of Mott-Schottky plot, and the slopes of Mott-Schottky plots increased with the increasing formation potential, showing a decrement of the donor density of the passive film.

  5. Analysis of the Effects of Introduction of an Additional Carbon Tax on the Slovenian Economy Considering Different Forms of Recycling

    Directory of Open Access Journals (Sweden)

    Matjaž Koman

    2014-12-01

    Full Text Available This paper outlines some of the environmental and economic implications of an additional CO2 tax of EUR 15/tCO2 in Slovenia in the period 2012-2030 in order to determine whether it yield a double dividend. Authors analyze (using E3ME model different forms of revenue recycling by reducing the social security contributions of either the employers or the employees or by reducing the public deficit, in order to identify the optimal fiscal instrument for improving the environmental and economic welfare (double dividend. In this policy orientated paper authors argue that a reduction of employee social security contributions has more favourable effect than a reduction in employers' social security contributions.

  6. Ab initio structural and electronic properties of hydrogenated silicon nanoclusters in the ground and excited state

    International Nuclear Information System (INIS)

    Degoli, Elena; Bisi, O.; Ossicini, Stefano; Cantele, G.; Ninno, D.; Luppi, Eleonora; Magri, Rita

    2004-01-01

    Electronic and structural properties of small hydrogenated silicon nanoclusters as a function of dimension are calculated from ab initio technique. The effects induced by the creation of an electron-hole pair are discussed in detail, showing the strong interplay between the structural and optical properties of the system. The distortion induced on the structure after an electronic excitation of the cluster is analyzed together with the role of the symmetry constraint during the relaxation. We point out how the overall effect is that of significantly changing the electronic spectrum if no symmetry constraint is imposed to the system. Such distortion can account for the Stokes shift and provides a possible structural model to be linked to the four-level scheme invoked in the literature to explain recent results for the optical gain in silicon nanoclusters. Finally, formation energies for clusters with increasing dimension are calculated and their relative stability discussed

  7. First-principles investigation of strain effects on the energy gaps in silicon nanoclusters

    International Nuclear Information System (INIS)

    Peng, X-H; Alizadeh, A; Bhate, N; Varanasi, K K; Kumar, S K; Nayak, S K

    2007-01-01

    First-principles density functional calculations were performed to study strain effects on the energy gaps in silicon nanoclusters with diameter ranging from 0.6 to 2 nm. Hydrostatic and non-hydrostatic strains have been found to affect the energy gaps differently. For the same strain energy density, non-hydrostatic strain leads to a significantly larger change in the energy gap of silicon clusters compared to that of the hydrostatic strain case. In contrast, hydrostatic and non-hydrostatic strain effects on the energy gaps of bulk Si or larger size Si quantum dots are comparable. Non-hydrostatic strains break the tetrahedral bonding symmetry in silicon, resulting in significant variation in the energy gaps due to the splitting of the degenerate orbitals in the clusters. Our results suggest that the combination of energy gaps and strains permits the engineering of photoluminescence in silicon nanoclusters and offers the possibility of designing novel optical devices and chemical sensors

  8. Interaction between rare-earth ions and amorphous silicon nanoclusters produced at low processing temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Meldrum, A. [Department of Physics, University of Alberta, Edmonton, T6G2J1 (Canada)]. E-mail: ameldrum@ualberta.ca; Hryciw, A. [Department of Physics, University of Alberta, Edmonton, T6G2J1 (Canada); MacDonald, A.N. [Department of Physics, University of Alberta, Edmonton, T6G2J1 (Canada); Blois, C. [Department of Physics, University of Alberta, Edmonton, T6G2J1 (Canada); Clement, T. [Department of Electrical and Computer Engineering, University of Alberta, Edmonton, T6G2V4 (Canada); De Corby, R. [Department of Electrical and Computer Engineering, University of Alberta, Edmonton, T6G2V4 (Canada); Wang, J. [Department of Physics, Chinese University of Hong Kong, Shatin, Hong Kong (China); Li Quan [Department of Physics, Chinese University of Hong Kong, Shatin, Hong Kong (China)

    2006-12-15

    Temperatures of 1000 deg. C and higher are a significant problem for the incorporation of erbium-doped silicon nanocrystal devices into standard silicon technology, and make the fabrication of contacts and reflectors in light emitting devices difficult. In the present work, we use energy-filtered TEM imaging techniques to show the formation of size-controlled amorphous silicon nanoclusters in SiO films annealed between 400 and 500 deg. C. The PL properties of such films are characteristic of amorphous silicon, and the spectrum can be controlled via a statistical size effect-as opposed to quantum confinement-that has previously been proposed for porous amorphous silicon. Finally, we show that amorphous nanoclusters sensitize the luminescence from the rare-earth ions Er, Nd, Yb, and Tm with excitation cross-sections similar in magnitude to erbium-doped silicon nanocrystal composites, and with a similar nonresonant energy transfer mechanism.

  9. 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

    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...... and electrochemical ammonia production via the associative mechanism is possible at potentials as low as -0.45 V to -0.7 V. © 2014 Howalt and Vegge........ 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...

  10. Ab initio study of structural, electronic, optical, and vibrational properties of ZnxSy (x + y = 2 to 5) nanoclusters

    International Nuclear Information System (INIS)

    Yadav, P. S.; Pandey, D. K.; Agrawal, S.; Agrawal, B. K.

    2010-01-01

    An ab initio study of the stability, structural, electronic. and optical properties has been performed for 46 zinc sulfide nanoclusters Zn x S y (x + y = n = 2 to 5). Five out of them are seen to be unstable as their vibrational frequencies are found to be imaginary. A B3LYP-DFT/6-311G(3df) method is employed to optimize the geometries and a TDDFT method is used for the study of the optical properties. The binding energies (BE), HOMO-LUMO gaps and the bond lengths have been obtained for all the clusters. For the ZnS 2 , ZnS 3 , and ZnS 4 nanoclusters, our stable structures are seen to be different from those obtained earlier by using the effective core potentials. We have also considered the zero point energy (ZPE) corrections ignored by the earlier workers. For a fixed value of n, we designate the most stable structure the one, which has maximum final binding energy per atom. The adiabatic and vertical ionization potentials (IP) and electron affinities (EA), charges on the atoms, dipole moments, optical properties, vibrational frequencies, infrared intensities, relative infrared intensities, and Raman scattering activities have been investigated for the most stable structures. The nanoclusters containing large number of S atoms for each n is found to be most stable. The HOMO-LUMO gap decreases from n = 2-3 and then increases above n = 3. The IP and EA both fluctuate with the cluster size n. The optical absorption is quite weak in visible region but strong in the ultraviolet region in most of the nanoclusters except a few. The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every nanocluster and may be used to characterize a specific nanocluster. The growth of most stable nanoclusters may be possible in the experiments.

  11. Electron microscopy and positron annihilation study of CdSe nanoclusters embedded in MgO

    NARCIS (Netherlands)

    van Huis, M.A.; van Veen, A.; Schut, H.; Eijt, S.W.H.; Kooi, B.J.; de Hosson, J.T.M.

    CdSe nanoclusters are created in MgO by means of co-implantation of 280 keV, 1 x 10(16) Cd ions cm(-2) and 210 keV, 1 x 10(16) Se ions cm(-2) in single crystals of MgO(001) and subsequent thermal annealing at a temperature of 1300 K, The structural properties and the orientation relationship between

  12. 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...... 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....

  13. Solvent Effect on Redox Properties of Hexanethiolate Monolayer-Protected Gold Nanoclusters

    OpenAIRE

    Su, B; Zhang, M; Shao, Y; Girault, HH

    2006-01-01

    The capacitance of monolayer-protected gold nanoclusters (MPCs), CMPC, in solution has been theoretically reconsidered from an electrostatic viewpoint, in which an MPC is considered as an isolated charged sphere within two dielectric layers, the intrinsic coating monolayer, and the bulk solvent. The model predicts that the bulk solvent provides an important contribution to CMPC and influences the redox properties of MPCs. This theoretical prediction is then examined experimentally by comparin...

  14. Au Nanoclusters Sensitized Black TiO2-x Nanotubes for Enhanced Photodynamic Therapy Driven by Near-Infrared Light.

    Science.gov (United States)

    Yang, Dan; Gulzar, Arif; Yang, Guixin; Gai, Shili; He, Fei; Dai, Yunlu; Zhong, Chongna; Yang, Piaoping

    2017-12-01

    The low reactive oxygen species production capability and the shallow tissue penetration of excited light (UV) are still two barriers in photodynamic therapy (PDT). Here, Au cluster anchored black anatase TiO 2- x nanotubes (abbreviated as Au 25 /B-TiO 2- x NTs) are synthesized by gaseous reduction of anatase TiO 2 NTs and subsequent deposition of noble metal. The Au 25 /B-TiO 2- x NTs with thickness of about 2 nm exhibit excellent PDT performance. The reduction process increased the density of Ti 3+ on the surface of TiO 2 , which effectively depresses the recombination of electron and hole. Furthermore, after modification of Au 25 nanoclusters, the PDT efficiency is further enhanced owing to the changed electrical distribution in the composite, which forms a shallow potential well on the metal-TiO 2 interface to further hamper the recombination of electron and hole. Especially, the reduction of anatase TiO 2 can expend the light response range (UV) of TiO 2 to the visible and even near infrared (NIR) light region with high tissue penetration depth. When excited by NIR light, the nanoplatform shows markedly improved therapeutic efficacy attributed to the photocatalytic synergistic effect, and promotes separation or restrained recombination of electron and hole, which is verified by experimental results in vitro and in vivo. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Templated Atom-Precise Galvanic Synthesis and Structure Elucidation of a [Ag 24 Au(SR) 18 ] − Nanocluster

    KAUST Repository

    Bootharaju, Megalamane Siddaramappa

    2015-11-27

    Synthesis of atom-precise alloy nanoclusters with uniform composition is challenging when the alloying atoms are similar in size (for example, Ag and Au). A galvanic exchange strategy has been devised to produce a compositionally uniform [Ag24Au(SR)18]- cluster (SR: thiolate) using a pure [Ag25(SR)18]- cluster as a template. Conversely, the direct synthesis of Ag24Au cluster leads to a mixture of [Ag25-xAux(SR)18]-, x=1-8. Mass spectrometry and crystallography of [Ag24Au(SR)18]- reveal the presence of the Au heteroatom at the Ag25 center, forming Ag24Au. The successful exchange of the central Ag of Ag25 with Au causes perturbations in the Ag25 crystal structure, which are reflected in the absorption, luminescence, and ambient stability of the particle. These properties are compared with those of Ag25 and Ag24Pd clusters with same ligand and structural framework, providing new insights into the modulation of cluster properties with dopants at the single-atom level.

  16. Highly sensitive and selective detection of Pb2+ using a turn-on fluorescent aptamer DNA silver nanoclusters sensor.

    Science.gov (United States)

    Zhang, Baozhu; Wei, Chunying

    2018-05-15

    A novel turn-on fluorescent biosensor has been constructed using C-PS2.M-DNA-templated silver nanoclusters (Ag NCs) with an average diameter of about 1 nm. The proposed approach presents a low-toxic, simple, sensitive, and selective detection for Pb 2+ . The fluorescence intensity of C-PS2.M-DNA-Ag NCs enhances significantly in the presence of Pb 2+ , which is attributed to the special interaction between Pb 2+ and its aptamer DNA PS2.M. Pb 2+ induces the aptamer to form G-quadruplex and makes two darkish DNA/Ag NCs located at the 3' and 5' terminus close, resulting in the fluorescence light-up. Moreover, Pb 2+ can be detected as low as 3.0 nM within a good linear range from 5 to 50 nM (R = 0.9862). Furthermore, the application for detection of Pb 2+ in real water samples further demonstrates the reliability of the sensor. Thus, this sensor system shows a potential application for monitoring Pb 2+ in environmental samples. Copyright © 2018 Elsevier B.V. All rights reserved.

  17. Characterization of oxide film layers formed on A106 B carbon steel in simulated secondary coolant conditions of nuclear power plants

    International Nuclear Information System (INIS)

    Strack, M.; Bordoni, R.; Chocron, M.; Olmedo, A.M.; Zampieri, G.

    2011-01-01

    The water chemistry of the secondary coolant in the majority Nuclear Power Plants is controlled by AVT (All Volatile Treatment) procedure, wherein volatile amines are use to maintain the alkaline pH required for minimizing the corrosion of structural materials which one of them is Carbon Steel. In this procedure: hydrazine, morpholine and ethanolamine are used commonly as conditioning reagents. In this context, experiments were carried out by exposing carbon steel A106 B samples in a simulated secondary coolant in order to study the nature of the oxide films. The tests were performed in a static autoclave at 260 ºC using two media: 1) Hydrazine + morpholine and 2) Hydrazine + ethanolamine during different exposure periods up to ≈1020 h. The composition, surface morphology, X-ray diffraction, a chemical descaling procedure were used- XPS, was also employed, to analyze the films grown during ≈1020 h in both media. The characterization showed that magnetite was the main corrosion product formed in the films grown in the two media. The material weight loss (W) could be fitted by a law of the type W = k t n , up to 1020 h of exposure, resulting in n =0,42, k = 6,24 for films grown in medium 1) and n = 0,39, k =6,08 for films grown in medium 2); where W is in mg/d m 2 and t in h. (author) [es

  18. Liquid-crystalline dendrimer Cu(II) complexes and Cu(0) nanoclusters based on the Cu(II) complexes: An electron paramagnetic resonance investigation

    Science.gov (United States)

    Domracheva, N. E.; Mirea, A.; Schwoerer, M.; Torre-Lorente, L.; Lattermann, G.

    2007-07-01

    New nanostructured materials, namely, the liquid-crystalline copper(II) complexes that contain poly(propylene imine) dendrimer ligands of the first (ligand 1) and second (ligand 2) generations and which have a columnar mesophase and different copper contents (x = Cu/L), are investigated by EPR spectroscopy. The influence of water molecules and nitrate counterions on the magnetic properties of complex 2 (x = 7.3) is studied. It is demonstrated that water molecules can extract some of the copper ions from dendrimer complexes and form hexaaqua copper complexes with free ions. The dimer spectra of fully hydrated complex 2 (x = 7.3) are observed at temperatures T dendrimer copper(II) complex. The temperature-induced valence tautomerism attended by electron transport is revealed for the first time in blue dendrimer complexes 1 (x = 1.9) with a dimer structure. The activation energy for electron transport is estimated to be 0.35 meV. The coordination of the copper ion site (NO4) and the structural arrangement of green complexes 1 (x = 1.9) in the columnar mesophase are determined. Complexes of this type form linear chains in which nitrate counterions serve as bridges between copper centers. It is revealed that green complexes 1 (x = 1.9) dissolved in isotropic inert solvents can be oriented in the magnetic field (B 0 = 8000 G). The degree of orientation of these complexes is rather high (S z = 0.76) and close to that of systems with a complete ordering (S z = 1) in the magnetic field. Copper(0) nanoclusters prepared by reduction of complex 2 (x = 7.3) in two reducing agents (NaBH4, N2H4 · H2O) are examined. A model is proposed for a possible location of Cu(0) nanoclusters in a dendrimer matrix.

  19. Gradients of Rac1 Nanoclusters Support Spatial Patterns of Rac1 Signaling.

    Science.gov (United States)

    Remorino, Amanda; De Beco, Simon; Cayrac, Fanny; Di Federico, Fahima; Cornilleau, Gaetan; Gautreau, Alexis; Parrini, Maria Carla; Masson, Jean-Baptiste; Dahan, Maxime; Coppey, Mathieu

    2017-11-14

    Rac1 is a small RhoGTPase switch that orchestrates actin branching in space and time and protrusion/retraction cycles of the lamellipodia at the cell front during mesenchymal migration. Biosensor imaging has revealed a graded concentration of active GTP-loaded Rac1 in protruding regions of the cell. Here, using single-molecule imaging and super-resolution microscopy, we show an additional supramolecular organization of Rac1. We find that Rac1 partitions and is immobilized into nanoclusters of 50-100 molecules each. These nanoclusters assemble because of the interaction of the polybasic tail of Rac1 with the phosphoinositide lipids PIP2 and PIP3. The additional interactions with GEFs and possibly GAPs, downstream effectors, and other partners are responsible for an enrichment of Rac1 nanoclusters in protruding regions of the cell. Our results show that subcellular patterns of Rac1 activity are supported by gradients of signaling nanodomains of heterogeneous molecular composition, which presumably act as discrete signaling platforms. Copyright © 2017 The Author(s). Published by Elsevier Inc. All rights reserved.

  20. Synthesis and analysis of gold nanoclusters on silicon substrates by ion beams

    International Nuclear Information System (INIS)

    Sood, D.K.; Venkatachalam, D.K.; Bhargava, S.K.; Evans, P.J.

    2005-01-01

    To facilitate the growth of silica nanowires on silicon substrates, two different seeding techniques: 1) ion implantation and 2) chemical deposition of as-synthesised gold colloids have been compared for the formation of catalysing gold nanoclusters. The prepared substrates of both types were analysed using Rutherford backscattering spectrometry at ANSTO to determine the amount of gold and its depth distribution. The topography of the substrates deposited with chemically synthesised gold nanoparticles were studied under SEM. The preliminary ion beam (RBS) analysis has shown ion implantation as a novel technique for seeding Au nanoclusters on silicon substrates facilitating growth of nanowires. This method holds a great potential for using any metal across the periodic table that can act as catalysing seed nanoclusters for nanowire growth. The use of chemical deposition as a seeding technique to deposit as-synthesised gold nanoparticles requires further investigations. RBS results show significant difference in the depth distribution of the gold nanoparticles on silicon substrates seeded by two different techniques. (author). 6 refs., 4 figs

  1. Rapid fluorescence assay for Sudan dyes using polyethyleneimine-coated copper nanoclusters

    International Nuclear Information System (INIS)

    Ling, Yu; Li, Jia Xing; Li, Nian Bing; Luo, Hong Qun; Qu, Fei

    2014-01-01

    We report that the intensity of the blue fluorescence of copper nanoclusters coated with polyethyleneimine (PEI) is strongly reduced in the presence of the food dyestuffs Sudan I-IV. This finding was exploited in a label-free fluorescence assay for these Sudan dyes both in ethanol and aqueous solutions. The PEI-capped nanoclusters have an average diameter of 1.8 nm and are displaying, under 355 nm excitation, a blue emission at 480 nm that matches the absorption bands of the Sudan dyes. The clusters are stable in solution for at least 1 month. Under optimum conditions, this assay can be applied to the quantification of the dyes Sudan I, II, III, and IV, respectively, in the 0.1−30, 0.1–30, 0.1–25, and 0.1–25 μM concentration ranges, and the detection limits (3σ/slope) are 65, 70, 45, and 50 nM, respectively. The capability of reducing the fluorescence of the PEI-capped copper nanoclusters is directly related to the number of the functional groups in that Sudan III and IV give lower detection limits. This analytical scheme exhibits a remarkably high selectivity for the Sudan dyes over potentially interfering substances. The method was successfully applied to determine Sudan I, II, III, and IV in hot chilli powder. (author)

  2. Iron Oxide Colloidal Nanoclusters as Theranostic Vehicles and Their Interactions at the Cellular Level

    Directory of Open Access Journals (Sweden)

    Athanasia Kostopoulou

    2018-05-01

    Full Text Available Advances in surfactant-assisted chemical approaches have led the way for the exploitation of nanoscale inorganic particles in medical diagnosis and treatment. In this field, magnetically-driven multimodal nanotools that perform both detection and therapy, well-designed in size, shape and composition, are highly advantageous. Such a theranostic material—which entails the controlled assembly of smaller (maghemite nanocrystals in a secondary motif that is highly dispersible in aqueous media—is discussed here. These surface functionalized, pomegranate-like ferrimagnetic nanoclusters (40–85 nm are made of nanocrystal subunits that show a remarkable magnetic resonance imaging contrast efficiency, which is better than that of the superparamagnetic contrast agent Endorem©. Going beyond this attribute and with their demonstrated low cytotoxicity in hand, we examine the critical interaction of such nanoprobes with cells at different physiological environments. The time-dependent in vivo scintigraphic imaging of mice experimental models, combined with a biodistribution study, revealed the accumulation of nanoclusters in the spleen and liver. Moreover, the in vitro proliferation of spleen cells and cytokine production witnessed a size-selective regulation of immune system cells, inferring that smaller clusters induce mainly inflammatory activities, while larger ones induce anti-inflammatory actions. The preliminary findings corroborate that the modular chemistry of magnetic iron oxide nanoclusters stimulates unexplored pathways that could be driven to alter their function in favor of healthcare.

  3. Double surface plasmon enhanced organic light-emitting diodes by gold nanoparticles and silver nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Chia-Yuan; Chen, Ying-Chung [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); Huang, Chien-Jung, E-mail: chien@nuk.edu.tw [Department of Applied Physics, National University of Kaohsiung, Kaohsiung, Taiwan (China)

    2015-12-30

    Graphical abstract: - Highlights: • The buffer layer is inserted between PEDOT: PSS and the emitting layer in order to avoid that the nonradiative decay process of exciton is generated. • The silver nanoclusters will generate surface plasmon resonance effect, resulting that the localized electric field around the silver nanoclusters is enhanced. • When the recombination region of the excitons is too close to the nanoparticles of the hole-transport layer, the nonradiative quenching of excitons is generated. - Abstract: The influence of gold nanoparticles (GNPs) and silver nanoclusters (SNCs) on the performance of organic light-emitting diodes is investigated in this study. The GNPs are doped into (poly (3, 4-ethylenedioxythiophene) poly (styrenesulfonate)) (PEDOT: PSS) and the SNCs are introduced between the electron-injection layer and cathode alumina. The power efficiency of the device, at the maximum luminance, with double surface plasmon resonance and buffer layer is about 2.15 times higher than that of the device without GNPs and SNCs because the absorption peaks of GNPs and SNCs are as good as the photoluminescence peak of the emission layer, resulting in strong surface plasmon resonance effect in the device. In addition, the buffer layer is inserted between PEDOT: PSS and the emitting layer in order to avoid that the nonradiative decay process of exciton is generated.

  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. Iron Oxide Colloidal Nanoclusters as Theranostic Vehicles and Their Interactions at the Cellular Level.

    Science.gov (United States)

    Kostopoulou, Athanasia; Brintakis, Konstantinos; Fragogeorgi, Eirini; Anthousi, Amalia; Manna, Liberato; Begin-Colin, Sylvie; Billotey, Claire; Ranella, Anthi; Loudos, George; Athanassakis, Irene; Lappas, Alexandros

    2018-05-09

    Advances in surfactant-assisted chemical approaches have led the way for the exploitation of nanoscale inorganic particles in medical diagnosis and treatment. In this field, magnetically-driven multimodal nanotools that perform both detection and therapy, well-designed in size, shape and composition, are highly advantageous. Such a theranostic material—which entails the controlled assembly of smaller (maghemite) nanocrystals in a secondary motif that is highly dispersible in aqueous media—is discussed here. These surface functionalized, pomegranate-like ferrimagnetic nanoclusters (40⁻85 nm) are made of nanocrystal subunits that show a remarkable magnetic resonance imaging contrast efficiency, which is better than that of the superparamagnetic contrast agent Endorem © . Going beyond this attribute and with their demonstrated low cytotoxicity in hand, we examine the critical interaction of such nanoprobes with cells at different physiological environments. The time-dependent in vivo scintigraphic imaging of mice experimental models, combined with a biodistribution study, revealed the accumulation of nanoclusters in the spleen and liver. Moreover, the in vitro proliferation of spleen cells and cytokine production witnessed a size-selective regulation of immune system cells, inferring that smaller clusters induce mainly inflammatory activities, while larger ones induce anti-inflammatory actions. The preliminary findings corroborate that the modular chemistry of magnetic iron oxide nanoclusters stimulates unexplored pathways that could be driven to alter their function in favor of healthcare.

  6. High-rate synthesis of phosphine-stabilized undecagold nanoclusters using a multilayered micromixer

    International Nuclear Information System (INIS)

    Jin, Hyung Dae; Chang, Chih-Hung; Garrison, Anna; Tseng, T; Paul, Brian K

    2010-01-01

    Growth in the potential applications of nanomaterials has led to a focus on the development of new manufacturing approaches for these materials. In particular, an increased demand due to the unique properties of nanomaterials requires a substantial yield of high-performance materials and a simultaneous reduction in the environmental impact of these processes. In this paper, a high-rate production of phosphine-stabilized undecagold 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 μm thick was used to step up the production of phosphine-stabilized undecagold nanoclusters. The continuous production of highly monodispersed phosphine-stabilized undecagold nanoclusters at a rate of about 11.8 (mg s -1 ) was achieved using a microreactor with a size of 1.687 cm 3 . This result is about 500 times over conventional batch syntheses based on the production rate per reactor volume.

  7. High methanol oxidation activity of electrocatalysts supported by directly grown nitrogen-containing carbon nanotubes on carbon cloth

    International Nuclear Information System (INIS)

    Wang, C.-H.; Shih, H.-C.; Tsai, Y.-T.; Du, H.-Y.; Chen, L.-C.; Chen, K.-H.

    2006-01-01

    The microstructure and electrochemical activity of the Pt-Ru supported by nitrogen-containing carbon nanotubes (CN x NTs) directly grown on the carbon cloth have been investigated. The CN x NTs directly grown on the carbon cloth (CN x NTs-carbon cloth composite electrode) were synthesized using microwave-plasma-enhanced chemical vapour deposition first and then use as the template to support the Pt-Ru nanoclusters subsequently sputtered on. The ferricyanide/ferrocyanide redox reaction in cyclic voltammetry (CV) measurements showed a faster electron transfer on the CN x NTs-carbon cloth composite electrode than the one with carbon cloth alone. Comparing their methanol oxidation abilities, it is found that the Pt-Ru nanoclusters supported by the CN x NTs-carbon cloth composite electrode have considerably higher electrocatalytic activity than the carbon cloth counterpart. This result suggests high performance of the CN x NTs-carbon cloth composite electrode, and demonstrates its suitability for direct methanol fuel cell applications

  8. High methanol oxidation activity of electrocatalysts supported by directly grown nitrogen-containing carbon nanotubes on carbon cloth

    Energy Technology Data Exchange (ETDEWEB)

    Wang, C.-H. [Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan (China); Shih, H.-C. [Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu, Taiwan (China); Institue of Materials Science and Nano Technology, Chinese Culture University, Taipei, Taiwan (China); Tsai, Y.-T. [Institue of Materials Science and Nano Technology, Chinese Culture University, Taipei, Taiwan (China); Du, H.-Y. [Institue of Materials Science and Nano Technology, Chinese Culture University, Taipei, Taiwan (China); Chen, L.-C. [Center for Condensed Matter Sciences, National Taiwan University, Taipei, Taiwan (China); Chen, K.-H. [Center for Condensed Matter Sciences, National Taiwan University, Taipei, Taiwan (China) and Institue of Atomic and Molecular Science, Academia Sinica, Taipei, Taiwan (China)]. E-mail: chenkh@pub.iams.sinica.edu.tw

    2006-12-01

    The microstructure and electrochemical activity of the Pt-Ru supported by nitrogen-containing carbon nanotubes (CN {sub x} NTs) directly grown on the carbon cloth have been investigated. The CN {sub x} NTs directly grown on the carbon cloth (CN {sub x} NTs-carbon cloth composite electrode) were synthesized using microwave-plasma-enhanced chemical vapour deposition first and then use as the template to support the Pt-Ru nanoclusters subsequently sputtered on. The ferricyanide/ferrocyanide redox reaction in cyclic voltammetry (CV) measurements showed a faster electron transfer on the CN {sub x} NTs-carbon cloth composite electrode than the one with carbon cloth alone. Comparing their methanol oxidation abilities, it is found that the Pt-Ru nanoclusters supported by the CN {sub x} NTs-carbon cloth composite electrode have considerably higher electrocatalytic activity than the carbon cloth counterpart. This result suggests high performance of the CN {sub x} NTs-carbon cloth composite electrode, and demonstrates its suitability for direct methanol fuel cell applications.

  9. In situ fluorescence activation of DNA-silver nanoclusters as a label-free and general strategy for cell nucleus imaging.

    Science.gov (United States)

    Li, Duo; Qiao, Zhenzhen; Yu, Yanru; Tang, Jinlu; He, Xiaoxiao; Shi, Hui; Ye, Xiaosheng; Lei, Yanli; Wang, Kemin

    2018-01-25

    A facile, general and turn-on nucleus imaging strategy was first developed based on in situ fluorescence activation of C-rich dark silver nanoclusters by G-rich telomeres. After a simple incubation without washing, nanoclusters could selectively stain the nucleus with intense red luminescence, which was confirmed using fixed/living cells and several cell lines.

  10. Strengthening Superconductivity in Macro-Arrays of Nanoclusters and Nanostructures

    Science.gov (United States)

    2015-02-11

    inner dia. ∼1.25 cm) of the SPS system (SPS, Dr Sinter 1020, Sumitomo Coal Mining Co., Ltd., Japan). The powdered samples were sintered at 1200 oC...Controlling the Optical, Electrical and Chemical Properties of Carbon Inverse Opal by Nitrogen Doping Morelos-Gomez, Aaron; Mani-Gonzalez, Pierre G...optical properties of B-doped single-walled carbon nanotube, Nanoscale accepted (2013) 7. Diamond Direct and Inverse Opal Matrices Produced by

  11. Electrochemical and in-situ Surface-Enhanced Raman Spectroscopic (SERS) study of passive films formed on low-carbon steel in highly alkaline environments

    Science.gov (United States)

    Mancio, Mauricio

    In reinforced concrete, a passive layer forms because of the alkaline conditions in the pores of the cement paste, where large concentrations of hydroxides create a solution with pH typically between 12 and 14. The corrosion resistance of the material depends on the characteristics and integrity of the passive film; however, currently very limited information is available about the passive films formed on carbon steel under such conditions. This work presents an electrochemical and in-situ Surface-Enhanced Raman Spectroscopic (SERS) study of passive films formed on low-carbon steel in highly alkaline environments. More specifically, the study focuses on the characterization of the films formed on ASTM A36 steel reinforcing bar exposed to aqueous solutions that aim to reproduce the chemistry of the environment typically found within the cement paste. Electrochemical techniques such as cyclic potentiodynamic polarization curves, galvanostatic cathodic polarization and linear polarization resistance were employed, in addition to in-situ Surface Enhanced Raman Spectroscopy (SERS). The experimental setup was built in a way that SERS experiments could be performed simultaneously with potentiodynamic polarization curves, enabling a detailed analysis of the formation and reduction of the surface films as a function of applied potential. Three solutions with different pH levels were used for the polarization and SERS experiments, namely 0.55M KOH + 0.16M NaOH ([OH-]=0.71), 0.08M KOH + 0.02M NaOH ([OH-]=0.10) and 0.008M KOH + 0.002M NaOH ([OH-]=0.01). Additional NaOH solutions in which the pH was varied from 13 to 9 and the ionic strength from 10 -5 to 10-1 were prepared for a pilot study using linear polarization resistance. Results show that the features observed in the cyclic potentiodynamic polarization curves correlated well with the potential arrests observed in the GCP plots as well as with the changes observed in the SERS spectra, providing valuable information about

  12. The role of minor alloying elements on the stability and dispersion of yttria nanoclusters in nanostructured ferritic alloys: An ab initio study

    International Nuclear Information System (INIS)

    Murali, D.; Panigrahi, B.K.; Valsakumar, M.C.; Chandra, Sharat; Sundar, C.S.; Raj, Baldev

    2010-01-01

    Nanostructured ferritic alloys derive their strength from the dispersion of oxide nanoclusters in the ferritic matrix. We have explored the relative role of minor alloying elements like Ti and Zr on the stability of nanoclusters of vacancy-Y-Ti-O by density functional theory calculations and shown that the binding energy of these clusters increases when we replace Ti with Zr. This could imply faster nucleation of the nanoclusters which, in turn, may lead to finer dispersion of nanoclusters resulting in improved performance of ferritic alloys. Further, we show a core/shell structure for these nanoclusters in which the core is enriched in Y, O, Ti while the shell is enriched in Cr.

  13. Stabilizing and Organizing Bi3 Cu4 and Bi7 Cu12 Nanoclusters in Two-Dimensional Metal-Organic Networks.

    Science.gov (United States)

    Yan, Linghao; Xia, Bowen; Zhang, Qiushi; Kuang, Guowen; Xu, Hu; Liu, Jun; Liu, Pei Nian; Lin, Nian

    2018-04-16

    Multinuclear heterometallic nanoclusters with controllable stoichiometry and structure are anticipated to possess promising catalytic, magnetic, and optical properties. Heterometallic nanoclusters with precise stoichiometry of Bi 3 Cu 4 and Bi 7 Cu 12 can be stabilized in the scaffold of two-dimensional metal-organic networks on a Cu(111) surface through on-surface metallosupramolecular self-assembly processes. The atomic structures of the nanoclusters were resolved using scanning tunneling microscopy and density functional theory calculations. The nanoclusters feature highly symmetric planar hexagonal shapes and core-shell charge modulation. The clusters are arranged as triangular lattices with a periodicity that can be tuned by choosing molecules of different size. This work shows that on-surface metallosupramolecular self-assembly creates unique possibilities for the design and synthesis of multinuclear heterometallic nanoclusters. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Protein-templated gold nanoclusters based sensor for off-on detection of ciprofloxacin with a high selectivity.

    Science.gov (United States)

    Chen, Zhanguang; Qian, Sihua; Chen, Junhui; Cai, Jie; Wu, Shuyan; Cai, Ziping

    2012-05-30

    In this contribution, bovine serum albumin stabilized gold nanoclusters as novel fluorescent probes were successfully utilized for the detection of ciprofloxacin for the first time. Our prepared gold nanoclusters exhibited strong emission with peak maximum at 635 nm. Cu(2+) was employed to quench the strong fluorescence of the gold nanoclusters, whereas the addition of ciprofloxacin caused the fluorescence intensity restoration of the Cu(2+)-gold nanoclusters system. The increase in fluorescence intensity of Cu(2+)-gold nanoclusters system caused by ciprofloxacin allows the sensitive detection of ciprofloxacin in the range of 0.4 ng mL(-1) to 50 ng mL(-1). The detection limit for ciprofloxacin is 0.3 ng mL(-1) at a signal-to-noise ratio of 3. The present sensor for ciprofloxacin detection possesses a low detection limit and wide linear range. In addition, the real samples were analyzed with satisfactory results. Copyright © 2012 Elsevier B.V. All rights reserved.

  15. Gold nanoclusters confined in a supercage of Y zeolite for aerobic oxidation of HMF under mild conditions.

    Science.gov (United States)

    Cai, Jiaying; Ma, Hong; Zhang, Junjie; Song, Qi; Du, Zhongtian; Huang, Yizheng; Xu, Jie

    2013-10-11

    Au nanoclusters with an average size of approximately 1 nm size supported on HY zeolite exhibit a superior catalytic performance for the selective oxidation of 5-hydroxymethyl-2-furfural (HMF) into 2,5-furandicarboxylic acid (FDCA). It achieved >99 % yield of 2,5-furandicarboxylic acid in water under mild conditions (60 °C, 0.3 MPa oxygen), which is much higher than that of Au supported on metal oxides/hydroxide (TiO2 , CeO2 , and Mg(OH)2 ) and channel-type zeolites (ZSM-5 and H-MOR). Detailed characterizations, such as X-ray diffraction, transmission electron microscopy, N2 -physisorption, and H2 -temperature-programmed reduction (TPR), revealed that the Au nanoclusters are well encapsulated in the HY zeolite supercage, which is considered to restrict and avoid further growing of the Au nanoclusters into large particles. The acidic hydroxyl groups of the supercage were proven to be responsible for the formation and stabilization of the gold nanoclusters. Moreover, the interaction between the hydroxyl groups in the supercage and the Au nanoclusters leads to electronic modification of the Au nanoparticles, which is supposed to contribute to the high efficiency in the catalytic oxidation of HMF to FDCA. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Ultrasmall Glutathione-Protected Gold Nanoclusters as Next Generation Radiotherapy Sensitizers with High Tumor Uptake and High Renal Clearance

    Science.gov (United States)

    Zhang, Xiao-Dong; Luo, Zhentao; Chen, Jie; Song, Shasha; Yuan, Xun; Shen, Xiu; Wang, Hao; Sun, Yuanming; Gao, Kai; Zhang, Lianfeng; Fan, Saijun; Leong, David Tai; Guo, Meili; Xie, Jianping

    2015-03-01

    Radiotherapy is often the most straightforward first line cancer treatment for solid tumors. While it is highly effective against tumors, there is also collateral damage to healthy proximal tissues especially with high doses. The use of radiosensitizers is an effective way to boost the killing efficacy of radiotherapy against the tumor while drastically limiting the received dose and reducing the possible damage to normal tissues. Here, we report the design and application of a good radiosensitizer by using ultrasmall Au29-43(SG)27-37 nanoclusters (protecting shell. The GSH-coated Au29-43(SG)27-37 nanoclusters can escape the RES absorption, leading to a good tumor uptake (~8.1% ID/g at 24 h post injection). As a result, the as-designed Au nanoclusters led to a strong enhancement for radiotherapy, as well as a negligible damage to normal tissues. After the treatment, the ultrasmall Au29-43(SG)27-37 nanoclusters can be efficiently cleared by the kidney, thereby avoiding potential long-term side-effects caused by the accumulation of gold atoms in the body. Our data suggest that the ultrasmall peptide-protected Au nanoclusters are a promising radiosensitizer for cancer radiotherapy.

  17. Evaluation of protective effect of deposits formed by naphthenic corrosion and sulfidation on carbon steel and steel 5Cr-0.5Mo exposed in atmospheric distillation fractions

    Directory of Open Access Journals (Sweden)

    Gloria Duarte

    2017-05-01

    Full Text Available Refining of so-called opportunity crude oils with a high level of naphthenic acids and sulfur compounds has been increasing interest due to limited availability of light crude oils, however, considerable corrosive effects in the processing to high temperature on pipes and distillation towers mainly by the attack of naphthenic acids and sulfur compounds; sulfur compounds could be corrosive or can reduce the attack of naphthenic acids due to the formation of sulfides layers on the metal surface. In this work was evaluated the performance of deposits formed on the surface of carbon steel AISI SAE 1020 and 5% Cr-0.5% Mo steel exposed in crude oil fractions obtained from atmospheric distillation tower. For this, gravimetric tests were performed in dynamic autoclave using metal samples pre-treated in a crude oil fraction obtained from the atmospheric distillation tower of the Crude Distillation Unit (CDU # 1 in order to form layers of sulfides on the surface of the two materials and subsequently to expose pre-treated and non-pretreated samples in two different crude oil fractions obtained from atmospheric distillation tower of Crude Distillation Unit (CDU # 2. The evaluation showed that the samples pretreated decreased tendency to corrosion by naphthenic acids and sulfidation compared to untreated samples.

  18. Teaching Form as Form

    DEFF Research Database (Denmark)

    Keiding, Tina Bering

    2012-01-01

    understanding of form per se, or, to use an expression from this text, of form as form. This challenge can be reduced to one question: how can design teaching support students in achieving not only the ability to recognize and describe different form-related concepts in existing design (i.e. analytical...

  19. Dolomitization of carbonated reservoirs of platforms. From geologic data to modeling. Example of the great Bahama bank; La dolomitisation des reservoirs carbonates de plate-forme. Des donnees geologiques a la modelisation. Exemple du Grand Banc des Bahamas

    Energy Technology Data Exchange (ETDEWEB)

    Caspard, E.

    2002-09-01

    Dolomitization has long been one of the most studied geological processes because of its economic interest (dolomitic rocks form a significant share of hydrocarbon reservoirs) as well as its academic interest, based on the fact that dolomite scarcely forms in current and recent marine environments whereas seawater is highly over-saturated; and that it is still not possible to synthesize it in laboratory under the same conditions. We used data collected by the University of Miami (Bahamas Drilling Project, ODP Leg 166) to understand the geological context of complete dolomitization of a Messinian 60 m thick reef unit. Classical methods of petrographic analysis of thin sections (optical microscopy, cathodoluminescence, scanning electron microscopy, in situ isotopic analyze using ionic microprobe) showed that the intensity of dolomitization is not controlled by the initial texture of the sediment, that the key parameter for dolomitization is the conservation of the initial mineralogy of magnesian bio-clasts, and that redox conditions, salinity and/or temperature of the precipitation fluid varied significantly during the process. Hydrodynamic modelling showed that during periods of high sea-level, Kohout thermal convection is a viable mechanism for driving marine fluids through the sediments. The key parameter for fluid circulations is the permeability anisotropy on the platform scale. Geochemical modelling showed that seawater is able to induce a complete dolomitization over durations of around one million years. Sensitivity tests showed that the critical parameter (as well as one of the less well-known) to describe diagenetic processes in carbonates is the water/rock reactions kinetics and in particular the precipitation kinetics of carbonate minerals. We finally propose that the dolomitization of the reef unit of the Unda well took place during the high sea-level period which extended over 1,1 My in the early Pliocene, according to the Kohout thermal convection

  20. Label-Free Platform for MicroRNA Detection Based on the Fluorescence Quenching of Positively Charged Gold Nanoparticles to Silver Nanoclusters.

    Science.gov (United States)

    Miao, Xiangmin; Cheng, Zhiyuan; Ma, Haiyan; Li, Zongbing; Xue, Ning; Wang, Po

    2018-01-16

    A novel strategy was developed for microRNA-155 (miRNA-155) detection based on the fluorescence quenching of positively charged gold nanoparticles [(+)AuNPs] to Ag nanoclusters (AgNCs). In the designed system, DNA-stabilized Ag nanoclusters (DNA/AgNCs) were introduced as fluorescent probes, and DNA-RNA heteroduplexes were formed upon the addition of target miRNA-155. Meanwhile, the (+)AuNPs could be electrostatically adsorbed on the negatively charged single-stranded DNA (ssDNA) or DNA-RNA heteroduplexes to quench the fluorescence signal. In the presence of duplex-specific nuclease (DSN), DNA-RNA heteroduplexes became a substrate for the enzymatic hydrolysis of the DNA strand to yield a fluorescence signal due to the diffusion of AgNCs away from (+)AuNPs. Under the optimal conditions, (+)AuNPs displayed very high quenching efficiency to AgNCs, which paved the way for ultrasensitive detection with a low detection limit of 33.4 fM. In particular, the present strategy demonstrated excellent specificity and selectivity toward the detection of target miRNA against control miRNAs, including mutated miRNA-155, miRNA-21, miRNA-141, let-7a, and miRNA-182. Moreover, the practical application value of the system was confirmed by the evaluation of the expression levels of miRNA-155 in clinical serum samples with satisfactory results, suggesting that the proposed sensing platform is promising for applications in disease diagnosis as well as the fundamental research of biochemistry.

  1. Seeking sunlight: rapid phototactic motility of filamentous mat-forming cyanobacteria optimize photosynthesis and enhance carbon burial in Lake Huron’s submerged sinkholes

    Directory of Open Access Journals (Sweden)

    Bopaiah A Biddanda

    2015-09-01

    Full Text Available We studied the motility of filamentous mat-forming cyanobacteria consisting primarily of Oscillatoria-like cells growing under low-light, low-oxygen and high-sulfur conditions in Lake Huron’s submerged sinkholes using in situ observations, in vitro measurements and time-lapse microscopy. Gliding movement of the cyanobacterial trichomes (100-10,000 µm long filaments, composed of cells ~10 µm wide and ~3 µm tall revealed individual as well as group-coordinated motility. When placed in a petri dish and dispersed in ground water from the sinkhole, filaments re-aggregated into defined colonies within minutes, then dispersed again. Speed of individual filaments increased with temperature from ~50 µm minute-1 or ~15 body lengths minute-1 at 10°C to ~215 µm minute-1 or ~70 body lengths minute-1 at 35°C – rates that are rapid relative to non-flagellated/ciliated microbes. Filaments exhibited precise and coordinated positive phototaxis towards pinpoints of light and congregated under the light of foil cutouts. Such light-responsive clusters showed an increase in photosynthetic yield – suggesting phototactic motility aids in light acquisition as well as photosynthesis. Once light source was removed, filaments slowly spread out evenly and re-aggregated, demonstrating coordinated movement through inter-filament communication regardless of light. Pebbles and pieces of broken shells placed upon intact mat were quickly covered by vertically motile filaments within hours and became fully buried in the anoxic sediments over 3-4 diurnal cycles – likely facilitating the preservation of falling debris. Coordinated horizontal and vertical filament motility optimize mat cohesion and dynamics, photosynthetic efficiency and sedimentary carbon burial in modern-day sinkhole habitats that resemble the shallow seas in Earth’s early history. Analogous cyanobacterial motility may have played a key role in the oxygenation of the planet by optimizing

  2. Seeking sunlight: rapid phototactic motility of filamentous mat-forming cyanobacteria optimize photosynthesis and enhance carbon burial in Lake Huron's submerged sinkholes.

    Science.gov (United States)

    Biddanda, Bopaiah A; McMillan, Adam C; Long, Stephen A; Snider, Michael J; Weinke, Anthony D

    2015-01-01

    We studied the motility of filamentous mat-forming cyanobacteria consisting primarily of Oscillatoria-like cells growing under low-light, low-oxygen, and high-sulfur conditions in Lake Huron's submerged sinkholes using in situ observations, in vitro measurements and time-lapse microscopy. Gliding movement of the cyanobacterial trichomes (100-10,000 μm long filaments, composed of cells ∼10 μm wide and ∼3 μm tall) revealed individual as well as group-coordinated motility. When placed in a petri dish and dispersed in ground water from the sinkhole, filaments re-aggregated into defined colonies within minutes, then dispersed again. Speed of individual filaments increased with temperature from ∼50 μm min(-1) or ∼15 body lengths min(-1) at 10°C to ∼215 μm min(-1) or ∼70 body lengths min(-1) at 35°C - rates that are rapid relative to non-flagellated/ciliated microbes. Filaments exhibited precise and coordinated positive phototaxis toward pinpoints of light and congregated under the light of foil cutouts. Such light-responsive clusters showed an increase in photosynthetic yield - suggesting phototactic motility aids in light acquisition as well as photosynthesis. Once light source was removed, filaments slowly spread out evenly and re-aggregated, demonstrating coordinated movement through inter-filament communication regardless of light. Pebbles and pieces of broken shells placed upon intact mat were quickly covered by vertically motile filaments within hours and became fully buried in the anoxic sediments over 3-4 diurnal cycles - likely facilitating the preservation of falling debris. Coordinated horizontal and vertical filament motility optimize mat cohesion and dynamics, photosynthetic efficiency and sedimentary carbon burial in modern-day sinkhole habitats that resemble the shallow seas in Earth's early history. Analogous cyanobacterial motility may have played a key role in the oxygenation of the planet by optimizing photosynthesis while favoring

  3. Cu Nanoparticles Improved Thermal Property of Form-Stable Phase Change Materials Made with Carbon Nanofibers and LA-MA-SA Eutectic Mixture.

    Science.gov (United States)

    Song, Xiaofei; Cai, Yibing; Huang, Cong; Gu, Ying; Zhang, Junhao; Qiao, Hui; Wei, Qufu

    2018-04-01

    A novel form-stable phase change materials (FSPCMs) was fabricated by incorporating fatty acid eutectics with electrospun carbon nanofibers (CNFs) surface-attached with copper (Cu) nanoparticles. Three different Cu/CNFs mats were made through combining the technique and principle of electrospinning, pre-oxidation/carbonization and in-situ reduction, while lauric-myristic-stearic acid (LA-MA-SA) ternary eutectic mixture was prepared as the model PCM. The morphology and crystal structure of Cu/CNFs were characterized by Fourier transfer infrared (FT-IR) spectra, Scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray energy dispersive spectroscopy (EDS), respectively. The results showed that Cu nanoparticles dispersed uniformly on the surface of CNFs mats without agglomeration, and Cu/CNFs mats could provide the mechanical support for FSPCMs and effectively prevent the flow/leakage of molten fatty acid. Morphological structures, as well as the properties of thermal energy storage and thermal energy storage/retrieval rates, of the resulting FSPCMs were investigated by SEM, Differential scanning calorimetry (DSC), and measurement of melting/freezing times, respectively. The results indicated that the fabricated FSPCMs exhibited desired structural morphology, and LA-MA-SA well dispersed in three-dimensional porous structure of Cu/CNFs mats. The melting and crystallization enthalpies of the fabricated FSPCMs were in the range of 117.1-140.7 kJ/kg and 117.2-142.4 kJ/kg, respectively. In comparison with melting/freezing times of LA-MA-SA ternary eutectic mixture, the melting/freezing times of fabricated FSPCMs were respectively decreased ~27.0-49.2% and ~44.1-63.0%. The fabricated FSPCMs possessed good thermal energy storage/retrieval property, and might have great potential for renewable energy storage applications.

  4. Electrooxidation of Indomethacin at Multiwalled Carbon Nanotubes-Modified GCE and Its Determination in Pharmaceutical Dosage Form and Human Biological Fluids

    OpenAIRE

    Sataraddi, Sanjeevaraddi R.; Patil, Shreekant M.; Bagoji, Atmanand M.; Pattar, Vijay P.; Nandibewoor, Sharanappa T.

    2014-01-01

    A simple, rapid, selective, and sensitive electrochemical method for the direct determination of indomethacin was developed. The electrochemical behavior of indomethacin was carried at multiwalled carbon nanotube- (MWCNTs-) modified glassy carbon electrode (GCE). The cyclic voltammetric results indicated that MWCNT-modified glassy carbon electrode remarkably enhanced electrocatalytic activity towards the oxidation of indomethacin in slightly acidic solutions. It led to a considerable improvem...

  5. 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.

  6. Oxidative generation of guanine radicals by carbonate radicals and their reactions with nitrogen dioxide to form site specific 5-guanidino-4-nitroimidazole lesions in oligodeoxynucleotides.

    Science.gov (United States)

    Joffe, Avrum; Mock, Steven; Yun, Byeong Hwa; Kolbanovskiy, Alexander; Geacintov, Nicholas E; Shafirovich, Vladimir

    2003-08-01

    A simple photochemical approach is described for synthesizing site specific, stable 5-guanidino-4-nitroimidazole (NIm) adducts in single- and double-stranded oligodeoxynucleotides containing single and multiple guanine residues. The DNA sequences employed, 5'-d(ACC CG(1)C G(2)TC CG(3)C G(4)CC) and 5'-d(ACC CG(1)C G(2)TC C), were a portion of exon 5 of the p53 tumor suppressor gene, including the codons 157 (G(2)) and 158 (G(3)) mutation hot spots in the former sequence with four Gs and the codon 157 (G(2)) mutation hot spot in the latter sequence with two Gs. The nitration of oligodeoxynucleotides was initiated by the selective photodissociation of persulfate anions to sulfate radicals induced by UV laser pulses (308 nm). In aqueous solutions, of bicarbonate and nitrite anions, the sulfate radicals generate carbonate anion radicals and nitrogen dioxide radicals by one electron oxidation of the respective anions. The guanine residue in the oligodeoxynucleotide is oxidized by the carbonate anion radical to form the neutral guanine radical. While the nitrogen dioxide radicals do not react with any of the intact DNA bases, they readily combine with the guanine radicals at either the C8 or the C5 positions. The C8 addition generates the well-known 8-nitroguanine (8-nitro-G) lesions, whereas the C5 attack produces unstable adducts, which rapidly decompose to NIm lesions. The maximum yields of the nitro products (NIm + 8-nitro-G) were typically in the range of 20-40%, depending on the number of guanine residues in the sequence. The ratio of the NIm to 8-nitro-G lesions gradually decreases from 3.4 in the model compound, 2',3',5'-tri-O-acetylguanosine, to 2.1-2.6 in the single-stranded oligodeoxynucleotides and to 0.8-1.1 in the duplexes. The adduct of the 5'-d(ACC CG(1)C G(2)TC C) oligodeoxynucleotide containing the NIm lesion in codon 157 (G(2)) was isolated in HPLC-pure form. The integrity of this adduct was established by a detailed analysis of exonuclease digestion

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

    Science.gov (United States)

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

    2016-08-01

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

  8. Evidence for a Proton Transfer Network and a Required Persulfide-Bond-Forming Cysteine Residue in Ni-Containing Carbon Monoxide Dehydrogenases

    International Nuclear Information System (INIS)

    Eun Jin Kim; Jian Feng; Bramlett, Matthew R.; Lindahl, Paul A.

    2004-01-01

    OAK-B135 Carbon monoxide dehydrogenase from Moorella thermoacetica catalyzes the reversible oxidation of CO to CO2 at a nickel-iron-sulfur active-site called the C-cluster. Mutants of a proposed proton transfer pathway and of a cysteine residue recently found to form a persulfide bond with the C-cluster were characterized. Four semi-conserved histidine residues were individually mutated to alanine. His116 and His122 were essential to catalysis, while His113 and His119 attenuated catalysis but were not essential. Significant activity was ''rescued'' by a double mutant where His116 was replaced by Ala and His was also introduced at position 115. Activity was also rescued in double mutants where His122 was replaced by Ala and His was simultaneously introduced at either position 121 or 123. Activity was also ''rescued'' by replacing His with Cys at position 116. Mutation of conserved Lys587 near the C-cluster attenuated activity but did not eliminate it. Activity was virtually abolished in a double mutant where Lys587 and His113 were both changed to Ala. Mutations of conserved Asn284 also attenuated activity. These effects suggest the presence of a network of amino acid residues responsible for proton transfer rather than a single linear pathway. The Ser mutant of the persulfide-forming Cys316 was essentially inactive and displayed no EPR signals originating from the C-cluster. Electronic absorption and metal analysis suggests that the C-cluster is absent in this mutant. The persulfide bond appears to be essential for either the assembly or stability of the C-cluster, and/or for eliciting the redox chemistry of the C-cluster required for catalytic activity

  9. Thermally Stable Ni-rich Austenite Formed Utilizing Multistep Intercritical Heat Treatment in a Low-Carbon 10 Wt Pct Ni Martensitic Steel

    Science.gov (United States)

    Jain, Divya; Isheim, Dieter; Zhang, Xian J.; Ghosh, Gautam; Seidman, David N.

    2017-08-01

    Austenite reversion and its thermal stability attained during the transformation is key to enhanced toughness and blast resistance in transformation-induced-plasticity martensitic steels. We demonstrate that the thermal stability of Ni-stabilized austenite and kinetics of the transformation can be controlled by forming Ni-rich regions in proximity of pre-existing (retained) austenite. Atom probe tomography (APT) in conjunction with thermodynamic and kinetic modeling elucidates the role of Ni-rich regions in enhancing growth kinetics of thermally stable austenite, formed utilizing a multistep intercritical ( Quench- Lamellarization- Tempering (QLT)-type) heat treatment for a low-carbon 10 wt pct Ni steel. Direct evidence of austenite formation is provided by dilatometry, and the volume fraction is quantified by synchrotron X-ray diffraction. The results indicate the growth of nm-thick austenite layers during the second intercritical tempering treatment (T-step) at 863 K (590 °C), with austenite retained from first intercritical treatment (L-step) at 923 K (650 °C) acting as a nucleation template. For the first time, the thermal stability of austenite is quantified with respect to its compositional evolution during the multistep intercritical treatment of these steels. Austenite compositions measured by APT are used in combination with the thermodynamic and kinetic approach formulated by Ghosh and Olson to assess thermal stability and predict the martensite-start temperature. This approach is particularly useful as empirical relations cannot be extrapolated for the highly Ni-enriched austenite investigated in the present study.

  10. Surface analytical and electrochemical characterization of oxide films formed on Incoloy-800 and carbon steel in simulated secondary water chemistry conditions of PHWRs

    International Nuclear Information System (INIS)

    Rangarajan, S.; Sinu, C.; Balaji, V.; Narasimhan, S.V.

    2010-01-01

    The water chemistry in the Steam Generator (SG) Circuits of Indian Pressurized Heavy Water Reactors (PHWRs) is controlled by the all volatile treatment (AVT) procedure, wherein volatile amines are used to maintain the alkaline pH required for minimizing the corrosion of the structural materials. Earlier, Monel and morpholine were used as the Steam Generator material and the alkalizing agent respectively. However, currently they are replaced by Incoloy-800 and Ethanolamine (ETA). ETA was chosen because of its beneficial effects due to low pK b and K d values, loading behaviour on condensate polishing unit (CPU) and also on cost comparison with other amines. Since we have Incoloy-800 on the tube side and Carbon steel(CS) on the shell side in the SG circuits, efforts were taken to study the nature of the oxide films formed on these surfaces and to evaluate the corrosion resistance and electrochemical properties of the same, under simulated secondary water chemistry conditions of PHWRs containing different dissolved oxygen (DO) concentration. In this context, experiments were carried out by exposing finely polished CS and Incoloy -800 coupons to ETA based medium in the presence and absence of Hydrazine (pH: 9.2) at 240 o C under two different DO conditions (< 10 ppb and 200 ppb) for 24 hours. Oxide films formed under these conditions were characterized using SEM, Raman spectroscopy, electrochemical impedance, polarization and Mott-Schottky techniques. Further, studies at a controlled DO level ( < 10 ppb) were carried out for different time durations viz., 7- and 30- days. The composition, surface morphology, oxide thickness, resistance, type of semi-conductivity and defect density of the oxide films were evaluated and correlated with the DO levels and discussed elaborately in this paper. (author)

  11. Sorption of Poly- and Perfluoroalkyl Substances (PFASs) Relevant to Aqueous Film-Forming Foam (AFFF)-Impacted Groundwater by Biochars and Activated Carbon.

    Science.gov (United States)

    Xiao, Xin; Ulrich, Bridget A; Chen, Baoliang; Higgins, Christopher P

    2017-06-06

    Despite growing concerns about human exposure to perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS), other poly- and perfluoroalkyl substances (PFASs) derived from aqueous film-forming foams (AFFFs) have garnered little attention. While these other PFASs may also be present in AFFF-impacted drinking water, their removal by conventional drinking-water treatment is poorly understood. This study compared the removal of 30 PFASs, including 13 recently discovered PFASs, from an AFFF-impacted drinking water using carbonaceous sorbents (i.e., granular activated carbon, GAC). The approach combined laboratory batch experiments and modeling: batch sorption data were used to determine partition coefficients (K d ) and calibrate a transport model based on intraparticle diffusion-limited sorption kinetics, which was used to make forward predictions of PFAS breakthrough during GAC adsorption. While strong retention was predicted for PFOS and PFOA, nearly all of the recently discovered polyfluorinated chemicals and PFOS-like PFASs detected in the AFFF-impacted drinking water were predicted to break through GAC systems before both PFOS and PFOA. These model breakthrough results were used to evaluate a simplified approach to predicting PFAS removal by GAC using compound-specific retention times on a C18 column (RT C18 ). Overall, this study reveals that GAC systems for the treatment of AFFF-impacted sources of water for PFOA and PFOS likely achieve poor removal, when operated only for the treatment of PFOS and PFOA, of many unmonitored PFASs of unknown toxicity.

  12. How Does Amino Acid Ligand Modulate Au Core Structure and Characteristics in Peptide Coated Au Nanocluster?

    Science.gov (United States)

    Li, Nan; Li, Xu; Zhao, Hongkang; Zhao, Lina

    2018-03-01

    The atomic structures and the corresponding physicochemical properties of peptide coated Au nanoclusters determine their distinctive biological targeting applications. To learn the modulation of amino acid ligand on the atomic structure and electronic characteristics of coated Au core is the fundamental knowledge for peptide coated Au nanocluster design and construction. Based on our recent coated Au nanocluster configuration study (Nanoscale, 2016, 8, 11454), we built the typically simplified Au13(Cys-Au-Cys) system to more clearly learn the basic modulation information of amino acid ligand on Au core by the density functional theory (DFT) calculations. There are two isomers as ligand adjacent bonding (Iso1) and diagonal bonding (Iso2) to Au13 cores. The geometry optimizations indicate the adjacent bonding Iso1 is more stable than Iso2. More important, the Au13 core of Iso1 distorts much more significantly than that of Iso2 by Cys-Au-Cys bonding through the root-mean-square deviation (RMSD) analysis, which modulate their electronic characteristics in different ways. In addition, the frontier molecular orbital results of Au13(Cys-Au-Cys) isomers confirm that the Au cores mainly determine the blue shifts of Au13(Cys-Au-Cys) systems versus the original Au13 core in their UV-visible absorption spectrum studies. The configuration of Au13 core performs deformation under Cys-Au-Cys ligand modulation to reach new stability with distinct atomic structure and electronic properties, which could be the theory basis for peptide coated AuNCs design and construction.

  13. Evolution of magnetism of Cr nanoclusters on a Au(111) surface

    Science.gov (United States)

    Gotsis, Harry; Kioussis, Nicholas; Papaconstantopoulos, Dimitri

    2004-03-01

    Advances in low-temperature scanning tunneling microscopy under ultrahigh vacuum have provided new opportunities for investigating the magnetic structures of nanoclusters adsorbed on surfaces. Recent STM studies of Cr trimers on the Au(111) surface suggest a switching between two distinct electronic states. We have carried out ab initio electronic structure calculations to investigate the structural, electronic and magnetic properties of isolated Cr atoms, Cr dimers and trimers in different geometry. We will present results for the evolution of magnetic behavior including noncollinear magnetism and provide insight in the connection between magnetism and geometry.

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

    DEFF Research Database (Denmark)

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

    2017-01-01

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

  15. Seed-mediated direct growth of CdSe nanoclusters on substrates

    International Nuclear Information System (INIS)

    Pan Shangke; Ebrahim, Shaker; Soliman, Moataz; Qiao Qiquan

    2013-01-01

    Different shapes of CdSe nanostructures were obtained by hydrothermal method with varied Se sources and buffer layers. Hexagonal nanoparticles of CdSe with Wurtzite structure were synthesized from Se powder resource, while CdSe nanoclusters with Wurtzite structure were grown from Na 2 SeO 3 aqueous solution resources at 165 °C using cetyltrimethylammonium bromide as surfactant. Using ZnO nanoparticles as a seed layer, CdSe nanostructures only partially covered the indium tin oxide (ITO) substrates. With ZnO/CdSe quantum dots composite seed layer, CdSe nanostructures fully covered the ITO substrates.

  16. Ultrafast static and diffusion-controlled electron transfer at Ag 29 nanocluster/molecular acceptor interfaces

    KAUST Repository

    Aly, Shawkat Mohammede; AbdulHalim, Lina G.; Besong, Tabot M.D.; Soldan, Giada; Bakr, Osman; Mohammed, Omar F.

    2015-01-01

    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.

  17. DFT investigation of the interaction of gold nanoclusters with poly(amidoamine) PAMAM G0 dendrimer

    Science.gov (United States)

    Camarada, M. B.

    2016-06-01

    The interaction between PAMAM G0 and gold nanoclusters Aun (n = 2, 4, 6, and 8) was studied theoretically at DFT level. Different coordination sites were explored, including internal and superficial coordination. All stable complexes exhibited external interaction with the amine or carbonyl site, while the core site coordination was not favored. The more stable binding of Aun was registered with the terminal amine group, while the binding at the amide site was relatively weaker. The vertical first ionization potential, electron affinity, Fermi level, and the HOMO-LUMO gap of PAMAM and Aun-PAMAM G0 complexes were also analyzed.

  18. Magnetic interaction reversal in watermelon nanostructured Cr-doped Fe nanoclusters

    International Nuclear Information System (INIS)

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

    2013-01-01

    Cr-doped core-shell Fe/Fe-oxide nanoclusters (NCs) were synthesized at varied atomic percentages of Cr from 0 at. % to 8 at. %. The low concentrations of Cr ( 2 O 3 and the Fe core to FeCr alloy. The magnetic interaction in Fe/Fe-oxide NCs (∼25 nm) can be controlled by antiferromagnetic Cr-dopant. We report the origin of σ-FeCr phase at very low Cr concentration (2 at. %) unlike in previous studies, and the interaction reversal from dipolar to exchange interaction in watermelon-like Cr-doped core-shell NCs

  19. 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.

  20. Super-oxidation of silicon nanoclusters: magnetism and reactive oxygen species at the surface

    Energy Technology Data Exchange (ETDEWEB)

    Lepeshkin, Sergey; Baturin, Vladimir; Tikhonov, Evgeny; Matsko, Nikita; Uspenskii, Yurii; Naumova, Anastasia; Feya, Oleg; Schoonen, Martin A.; Oganov, Artem R.

    2016-01-01

    Oxidation of silicon nanoclusters depending on the temperature and oxygen pressure is explored from first principles using the evolutionary algorithm, and structural and thermodynamic analysis. From our calculations of 90 SinOm clusters we found that under normal conditions oxidation does not stop at the stoichiometric SiO2 composition, as it does in bulk silicon, but goes further placing extra oxygen atoms on the cluster surface. These extra atoms are responsible for light emission, relevant to reactive oxygen species and many of them are magnetic. We argue that the super-oxidation effect is size-independent and discuss its relevance to nanotechnology and miscellaneous applications, including biomedical ones.

  1. Radiation Stability of Nanoclusters in Nano-structured Oxide Dispersion Strengthened (ODS) Steels

    International Nuclear Information System (INIS)

    Certain, Alicia G.; Kuchibhatla, Satyanarayana; Shutthanandan, V.; Allen, T. R.

    2013-01-01

    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.

  2. Hydrogen interactions with ZrCo nanoclusters: a first-principles study

    International Nuclear Information System (INIS)

    Chattaraj, D.; Parida, S.C.; Dash, Smruti; Bhattacharya, Saswata; Majumder, C.

    2014-01-01

    Tritium is one of the fuels going to be used in fusion reactor program. But, this radioactive isotope should be stored safely. ZrCo intermetallic has been chosen as a tritium storage material in ITER program. It is important to study how hydrogen interacts with ZrCo in its different dimensions. In this study we have investigated the hydrogen interaction with the Zr m Co n (m+n = 2, 4 and 6) nanoclusters using the state-of-the-art first principles method

  3. Seeking sunlight: rapid phototactic motility of filamentous mat-forming cyanobacteria optimize photosynthesis and enhance carbon burial in Lake Huron’s submerged sinkholes

    Science.gov (United States)

    Biddanda, Bopaiah A.; McMillan, Adam C.; Long, Stephen A.; Snider, Michael J.; Weinke, Anthony D.

    2015-01-01

    We studied the motility of filamentous mat-forming cyanobacteria consisting primarily of Oscillatoria-like cells growing under low-light, low-oxygen, and high-sulfur conditions in Lake Huron’s submerged sinkholes using in situ observations, in vitro measurements and time-lapse microscopy. Gliding movement of the cyanobacterial trichomes (100–10,000 μm long filaments, composed of cells ∼10 μm wide and ∼3 μm tall) revealed individual as well as group-coordinated motility. When placed in a petri dish and dispersed in ground water from the sinkhole, filaments re-aggregated into defined colonies within minutes, then dispersed again. Speed of individual filaments increased with temperature from ∼50 μm min-1 or ∼15 body lengths min-1 at 10°C to ∼215 μm min-1 or ∼70 body lengths min-1 at 35°C – rates that are rapid relative to non-flagellated/ciliated microbes. Filaments exhibited precise and coordinated positive phototaxis toward pinpoints of light and congregated under the light of foil cutouts. Such light-responsive clusters showed an increase in photosynthetic yield – suggesting phototactic motility aids in light acquisition as well as photosynthesis. Once light source was removed, filaments slowly spread out evenly and re-aggregated, demonstrating coordinated movement through inter-filament communication regardless of light. Pebbles and pieces of broken shells placed upon intact mat were quickly covered by vertically motile filaments within hours and became fully buried in the anoxic sediments over 3–4 diurnal cycles – likely facilitating the preservation of falling debris. Coordinated horizontal and vertical filament motility optimize mat cohesion and dynamics, photosynthetic efficiency and sedimentary carbon burial in modern-day sinkhole habitats that resemble the shallow seas in Earth’s early history. Analogous cyanobacterial motility may have played a key role in the oxygenation of the planet by optimizing photosynthesis while

  4. Rigid rod spaced fullerene as building block for nanoclusters

    Indian Academy of Sciences (India)

    Unknown

    The general method adopted for the synthesis of the monofullerene ..... derivatives form small nanoparticles with narrow size distribution,30 whereas template- ... tapping mode AFM (TM-AFM), since this method is more suited for studying soft.

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

    International Nuclear Information System (INIS)

    Dhoubhadel, Mangal S.; Lakshantha, Wickramaarachchige J.; Rout, Bibhudutta; McDaniel, Floyd D.; Lightbourne, Sherard; D’Souza, Francis

    2015-01-01

    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 16 to ∼1 × 10 17 atoms/cm 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 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 − -h + pairs produced by the incident light

  6. Preparation, characterization and nonlinear absorption studies of cuprous oxide nanoclusters, micro-cubes and micro-particles

    Science.gov (United States)

    Sekhar, H.; Narayana Rao, D.

    2012-07-01

    Cuprous oxide nanoclusters, micro-cubes and micro-particles were successfully synthesized by reducing copper(II) salt with ascorbic acid in the presence of sodium hydroxide via a co-precipitation method. The X-ray diffraction and FTIR studies revealed that the formation of pure single-phase cubic. Raman and EPR spectral studies show the presence of CuO in as-synthesized powders of Cu2O. Transmission electron microscopy and field emission scanning electron microscopy data revealed that the morphology evolves from nanoclusters to micro-cubes and micro-particles by increasing the concentration of NaOH. Linear optical measurements show absorption peak maximum shifts towards red with changing morphology from nanoclusters to micro-cubes and micro-particles. The nonlinear optical properties were studied using open aperture Z-scan technique with 532 nm 6 ns laser pulses. Samples-exhibited both saturable as well as reverse saturable absorption. Due to confinement effects (enhanced band gap), we observed enhanced nonlinear absorption coefficient (β) in the case of nanoclusters compared to their micro-cubes and micro-particles.

  7. Highly selective GaN-nanowire/TiO2-nanocluster hybrid sensors for detection of benzene and related environment pollutants

    International Nuclear Information System (INIS)

    Aluri, Geetha S; Motayed, Abhishek; Davydov, Albert V; Oleshko, Vladimir P; Bertness, Kris A; Sanford, Norman A; Rao, Mulpuri V

    2011-01-01

    Nanowire-nanocluster hybrid chemical sensors were realized by functionalizing gallium nitride (GaN) nanowires (NWs) with titanium dioxide (TiO 2 ) nanoclusters for selectively sensing benzene and other related aromatic compounds. Hybrid sensor devices were developed by fabricating two-terminal devices using individual GaN NWs followed by the deposition of TiO 2 nanoclusters using RF magnetron sputtering. The sensor fabrication process employed standard microfabrication techniques. X-ray diffraction and high-resolution analytical transmission electron microscopy using energy-dispersive x-ray and electron energy-loss spectroscopies confirmed the presence of the anatase phase in TiO 2 clusters after post-deposition anneal at 700 deg. C. A change of current was observed for these hybrid sensors when exposed to the vapors of aromatic compounds (benzene, toluene, ethylbenzene, xylene and chlorobenzene mixed with air) under UV excitation, while they had no response to non-aromatic organic compounds such as methanol, ethanol, isopropanol, chloroform, acetone and 1,3-hexadiene. The sensitivity range for the noted aromatic compounds except chlorobenzene were from 1% down to 50 parts per billion (ppb) at room temperature. By combining the enhanced catalytic properties of the TiO 2 nanoclusters with the sensitive transduction capability of the nanowires, an ultra-sensitive and selective chemical sensing architecture is demonstrated. We have proposed a mechanism that could qualitatively explain the observed sensing behavior.

  8. Characterization and Application of DNA-templated Silver Nanoclusters and Polarized Spectroscopy of Self-Assembled Nanostructures

    DEFF Research Database (Denmark)

    Carro-Temboury, Miguel R.

    In this thesis two different systems are investigated envisioning their potential applications: DNA-templated silver nanoclusters (DNA-AgNCs) and ionic self-assembled (ISA) nanostructures based on azo-dyes. Mainly Visible-NIR spectroscopy was used to probe electronic transitions with absorbance a...

  9. Fluorescent silver nanoclusters capped by polyethyleneimine with different molecular weights: Universal synthesis and application as a temperature sensor

    Energy Technology Data Exchange (ETDEWEB)

    Qu, Fei, E-mail: qufei3323@163.com [The Key Laboratory of Life-Organic Analysis, Qufu Normal University, Qufu 273165, Shandong (China); Key Laboratory of Pharmaceutical Intermediates and Analysis of Natural Medicine, Qufu Normal University, Qufu 273165, Shandong (China); Li, Qingjin [The Key Laboratory of Life-Organic Analysis, Qufu Normal University, Qufu 273165, Shandong (China); Key Laboratory of Pharmaceutical Intermediates and Analysis of Natural Medicine, Qufu Normal University, Qufu 273165, Shandong (China); You, Jinmao, E-mail: jmyou6304@163.com [The Key Laboratory of Life-Organic Analysis, Qufu Normal University, Qufu 273165, Shandong (China); Key Laboratory of Pharmaceutical Intermediates and Analysis of Natural Medicine, Qufu Normal University, Qufu 273165, Shandong (China); Northwest Institute of Plateau Biology, Chinese Academy of Sciences, Xining 810001 (China)

    2016-09-15

    In this paper, we developed a universal, applicable and simple synthetic method of Ag nanoclusters capped by polyethyleneimine (PEI) with different molecular weights (AgNC-PEIs), including Mw 600, 1300, 1800, 2000, 10,000, 25,000, 70,000, and 750,000. Using formaldehyde as the sole reducing agent, silver nanoclusters could be successfully prepared by using these templates. Subsequently, several characterization techniques were employed to investigate the properties of AgNC-PEIs, and the results suggested that these AgNC-PEIs had similar sizes, structures, and optical features. However, besides the common characteristics, different temperature sensitivities were found for these nanoclusters, in which AgNC-PEI 25000 was proper to be applied as a temperature sensor. With increasing temperature, the fluorescence quenched dramatically, and this change could be readily observed by naked eyes under UV light. Injection of these temperature sensitive nanoclusters into a glass tube, a simple thermometer could be fabricated easily, thus AgNC-PEI 25000 would be a promising candidate for temperature sensing as a visible indicator.

  10. Systematic Study on the Self-Assembled Hexagonal Au Voids, Nano-Clusters and Nanoparticles on GaN (0001.

    Directory of Open Access Journals (Sweden)

    Puran Pandey

    Full Text Available Au nano-clusters and nanoparticles (NPs have been widely utilized in various electronic, optoelectronic, and bio-medical applications due to their great potentials. The size, density and configuration of Au NPs play a vital role in the performance of these devices. In this paper, we present a systematic study on the self-assembled hexagonal Au voids, nano-clusters and NPs fabricated on GaN (0001 by the variation of annealing temperature and deposition amount. At relatively low annealing temperatures between 400 and 600°C, the fabrication of hexagonal shaped Au voids and Au nano-clusters are observed and discussed based on the diffusion limited aggregation model. The size and density of voids and nano-clusters can systematically be controlled. The self-assembled Au NPs are fabricated at comparatively high temperatures from 650 to 800°C based on the Volmer-Weber growth model and also the size and density can be tuned accordingly. The results are symmetrically analyzed and discussed in conjunction with the diffusion theory and thermodynamics by utilizing AFM and SEM images, EDS maps and spectra, FFT power spectra, cross-sectional line-profiles and size and density plots.

  11. Microwave-Assisted Synthesis of Red-Light Emitting Au Nanoclusters with the Use of Egg White

    Science.gov (United States)

    Tian, Jinghan; Yan, Lei; Sang, Aohua; Yuan, Hongyan; Zheng, Baozhan; Xiao, Dan

    2014-01-01

    We developed a simple, cost-effective, and eco-friendly method to synthesize gold nanoclusters (AuNCs) with red fluorescence. The experiment was performed using HAuCl[subscript 4], egg white, Na[subscript 2]CO[subscript 3] (known as soda ash or washing soda), and a microwave oven. In our experiment, fluorescent AuNCs were prepared within a…

  12. Reductive Deprotection of Monolayer Protected Nanoclusters: An Efficient Route to Supported Ultrasmall Au Nanocatalysts for Selective Oxidation

    Czech Academy of Sciences Publication Activity Database

    Das, S.; Goswami, A.; Hesari, M.; Al-Sharab, J. F.; Mikmeková, Eliška; Maran, F.; Asefa, T.

    2014-01-01

    Roč. 10, č. 8 (2014), s. 1473-1478 ISSN 1613-6810 R&D Projects: GA MŠk(CZ) LO1212 Keywords : gold nanoclusters * selective oxidation * heterogeneous nanocatalysis * styrene oxidation * borohydride reduction Subject RIV: JA - Electronics ; Optoelectronics, Electrical Engineering Impact factor: 8.368, year: 2014

  13. Polyoxotungstate nanoclusters supported on silica as an efficient solid-phase microextraction fiber of polycyclic aromatic hydrocarbons

    International Nuclear Information System (INIS)

    Abolghasemi, Mir Mahdi; Yousefi, Vahid; Rafiee, Ezzat

    2014-01-01

    A highly porous silica-supported tungstophosphoric acid (PW) nanocluster was prepared for use in solid-phase microextraction (SPME) of polycyclic aromatic hydrocarbons (PAHs). The PWs represent a class of discrete transition metal-oxide nanoclusters and their structures resemble discrete fragments of metal-oxide structures of definite size and shape. Transition metal-oxide nanoclusters display large structural diversity, and their monodisperse sizes can be tuned from several Ångstroms up to 10 nm. The highly porous silica-supported tungstophosphoric acid nanocluster material is found to be capable of efficiently extracting PAHs from aqueous sample solutions. The nanomaterial was immobilized on a stainless steel wire for fabrication of the SPME fiber. Following thermal desorption, the PAHs were quantified by GC-MS. Analytical merits include limits of detection that range from 0.02 to 0.1 pg mL −1 and a dynamic range as wide as from 0.001 to 100 ng mL −1 . Under optimum conditions, the repeatability for one fiber (n = 3), expressed as the relative standard deviation, is between 4.3 % and 8.6 %. The method is simple, rapid, and inexpensive. The thermal stability of the fiber and the high relative recovery make this method superior to conventional methods of extraction. (author)

  14. Theoretical Investigation of the Structural Stabilities of Ceria Surfaces and Supported Metal Nanocluster in Vapor and Aqueous Phases

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Zhibo [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China; Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Liu, Ning [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China; Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Chen, Biaohua [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China; Li, Jianwei [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China; Mei, Donghai [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States

    2018-01-25

    Understanding the structural stability and dynamics at the interface between the solid metal oxide and aqueous phase is significant in a variety of industrial applications including heterogeneous catalysis and environmental remediation. In the present work, the stabilities of three low-index ceria (CeO2) surfaces, i.e., (111), (110) and (100) in vapor and aqueous phases were studied using ab initio molecular dynamics simulations and density functional theory (DFT) calculations. Gibbs surface free energies as a function of temperature, water partial pressure, and water coverages were calculated using DFT based atomistic thermodynamic approach. On the basis of surface free energies, the morphology and exposed surface structures of the CeO2 nanoparticle were predicted using Wulff construction principle. It is found that the partially hydroxylated (111) and (100) are two major surface structures of CeO2 nanoparticles in vapor phase at ambient temperature (300 K). As the temperature increases, the fully dehydrated (111) surface gradually becomes the most dominant surface structure. While in aqueous phase, the exposed surface of the CeO2 nanoparticle is dominated by the hydroxylated (110) structure at 393 K. Finally, the morphology and stability of a cuboctahedron Pt13 nanocluster supported on CeO2 surfaces in both gas and aqueous phases were investigated. In gas phase, the supported Pt13 nanocluster has the tendency to wetting the CeO2 surface due to the strong metal-support interaction. The calculated interaction energies suggest the CeO2(110) surface provides the best stability for the Pt13 nanocluster. The CeO2 supported Pt13 nanoclusters are oxidized. Compared to the gas phase, the morphology of the CeO2 supported Pt13 nanocluster is less distorted due to the solvation effect provided by surrounding water molecules in aqueous phase. More electrons are transferred from the Pt13 nanocluster to the CeO2 support, implying the supported Pt13 nanocluster is further

  15. Mechanisms for catalytic carbon nanofiber growth studied by ab initio density functional theory calculations

    DEFF Research Database (Denmark)

    Abild-Pedersen, Frank; Nørskov, Jens Kehlet; Rostrup-Nielsen, Jens

    2006-01-01

    Mechanisms and energetics of graphene growth catalyzed by nickel nanoclusters were studied using ab initio density functional theory calculations. It is demonstrated that nickel step-edge sites act as the preferential growth centers for graphene layers on the nickel surface. Carbon is transported......, and it is argued how these processes may lead to different nanofiber structures. The proposed growth model is found to be in good agreement with previous findings....

  16. Ferromagnetic resonance of cobalt nanoparticles used as a catalyst for the carbon nanotubes synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Duraia, El-Shazly M. [Suez Canal University, Faculty of Science, Physics Department, Ismailia (Egypt); Al-Farabi Kazakh National University, Almaty (Kazakhstan); Institute of Physics and Technology, Almaty (Kazakhstan)], E-mail: duraia_physics@yahoo.com; Abdullin, Kh.A. [Institute of Physics and Technology, Almaty (Kazakhstan)

    2009-12-15

    Catalyst is considered to be the most crucial parameter for the growth of carbon nanotubes. In this work we study the ferromagnetic resonance (FMR) spectra of the catalyst nanoclusters. Moreover we report for the first time the angle FMR studies of catalyst particles with and without CNT layer. The dependencies of the FMR spectra, X-ray diffraction (XRD) patterns, Raman spectra and morphology of the CNT layers on the growth conditions are discussed.

  17. In vivo target bio-imaging of Alzheimer's disease by fluorescent zinc oxide nanoclusters.

    Science.gov (United States)

    Lai, Lanmei; Zhao, Chunqiu; Su, Meina; Li, Xiaoqi; Liu, Xiaoli; Jiang, Hui; Amatore, Christian; Wang, Xuemei

    2016-07-21

    Alzheimer's disease (AD) is an irreversible neurodegenerative disease which is difficult to cure. When Alzheimer's disease occurs, the level of zinc ions in the brain changes, and the relevant amount of zinc ions continue decreasing in the cerebrospinal fluid and plasma of Alzheimer's patients with disease exacerbation. In view of these considerations, we have explored a new strategy for the in vivo rapid fluorescence imaging of Alzheimer's disease through target bio-labeling of zinc oxide nanoclusters which were biosynthesized in vivo in the Alzheimer's brain via intravenous injection of zinc gluconate solution. By using three-month-old and six-month-old Alzheimer's model mice as models, our observations demonstrate that biocompatible zinc ions could pass through the blood-brain barrier of the Alzheimer's disease mice and generate fluorescent zinc oxide nanoclusters (ZnO NCs) through biosynthesis, and then the bio-synthesized ZnO NCs could readily accumulate in situ on the hippocampus specific region for the in vivo fluorescent labeling of the affected sites. This study provides a new way for the rapid diagnosis of Alzheimer's disease and may have promising prospects in the effective diagnosis of Alzheimer's disease.

  18. One-step aqueous synthesis of fluorescent copper nanoclusters by direct metal reduction

    International Nuclear Information System (INIS)

    Fernández-Ujados, Mónica; Trapiella-Alfonso, Laura; Costa-Fernández, José M; Pereiro, Rosario; Sanz-Medel, Alfredo

    2013-01-01

    A one-step aqueous synthesis of highly fluorescent water-soluble copper nanoclusters (CuNCs) is here described, based on direct reduction of the metal precursor with NaBH 4 in the presence of bidentate ligands (made of lipoic acid anchoring groups, appended with a poly(ethylene glycol) short chain). A complete optical and structural characterization was carried out: the optical emission was centred at 416 nm, with a luminescence quantum yield in water of 3.6% (the highest one reported so far in water for this kind of nanocluster). The structural characterization reveals a homogeneous size distribution (of 2.5 nm diameter) with spherical shape. The CuNCs obtained offer long-term stability (the luminescence emission remained unaltered after more than two months) under a broad range of chemical conditions (e.g. stored at pH 3–12 or even in a high ionic strength medium such as 1 M NaCl) and high photostability, keeping their fluorescence emission intact after more than 2 h of daylight and UV-light exposition. All those advantageous features warrant synthesized CuNCs being promising fluorescent nanoprobes for further developments including (bio)applications. (paper)

  19. Probing phosphate ion via the europium(III)-modulated fluorescence of gold nanoclusters

    International Nuclear Information System (INIS)

    Ding, Shou-Nian; Li, Chun-Mei; Gao, Bu-Hong; Kargbo, Osman; Zhou, Chan; Chen, Xi; Wan, Neng

    2014-01-01

    Fluorescent gold nanoclusters (Au-NCs) were synthesized by a one-pot method using 11-mercaptoundecanoic acid as a reducing and capping reagent. It is found that the red fluorescence of the Au-NCs is quenched by the introduction of Eu(III) at pH 7.0, but that fluorescence is restored on addition of phosphate. The Au-NCs were investigated by transmission electron microscopy and fluorescence photographs. The effect of pH on fluorescence was studied in the range from pH 6 to 10 and is found to be strong. Based on these findings, we have developed an assay for phosphate. Ions such as citrate, Fe(CN) 6 3− , SO 4 2− , S 2 O 8 2− , Cl − , HS − , Br − , AcO − , NO 2 − , SCN − , ClO 4 − , HCO 3 − , NO 3 − , Cd 2+ , Ba 2+ , Zn 2+ , Mg 2+ , and glutamate do not interfere, but ascorbate and Fe 3+ can quench Au-NCs fluorescence. The fluorescent nanocluster probe responds to phosphate in the range from 0.18 to 250 μM, and the detection limit is 180 nM. The probe also responds to pyrophosphate and ATP. (author)

  20. Sizing protein-templated gold nanoclusters by time resolved fluorescence anisotropy decay measurements

    Science.gov (United States)

    Soleilhac, Antonin; Bertorelle, Franck; Antoine, Rodolphe

    2018-03-01

    Protein-templated gold nanoclusters (AuNCs) are very attractive due to their unique fluorescence properties. A major problem however may arise due to protein structure changes upon the nucleation of an AuNC within the protein for any future use as in vivo probes, for instance. In this work, we propose a simple and reliable fluorescence based technique measuring the hydrodynamic size of protein-templated gold nanoclusters. This technique uses the relation between the time resolved fluorescence anisotropy decay and the hydrodynamic volume, through the rotational correlation time. We determine the molecular size of protein-directed AuNCs, with protein templates of increasing sizes, e.g. insulin, lysozyme, and bovine serum albumin (BSA). The comparison of sizes obtained by other techniques (e.g. dynamic light scattering and small-angle X-ray scattering) between bare and gold clusters containing proteins allows us to address the volume changes induced either by conformational changes (for BSA) or the formation of protein dimers (for insulin and lysozyme) during cluster formation and incorporation.

  1. Sizing protein-templated gold nanoclusters by time resolved fluorescence anisotropy decay measurements.

    Science.gov (United States)

    Soleilhac, Antonin; Bertorelle, Franck; Antoine, Rodolphe

    2018-03-15

    Protein-templated gold nanoclusters (AuNCs) are very attractive due to their unique fluorescence properties. A major problem however may arise due to protein structure changes upon the nucleation of an AuNC within the protein for any future use as in vivo probes, for instance. In this work, we propose a simple and reliable fluorescence based technique measuring the hydrodynamic size of protein-templated gold nanoclusters. This technique uses the relation between the time resolved fluorescence anisotropy decay and the hydrodynamic volume, through the rotational correlation time. We determine the molecular size of protein-directed AuNCs, with protein templates of increasing sizes, e.g. insulin, lysozyme, and bovine serum albumin (BSA). The comparison of sizes obtained by other techniques (e.g. dynamic light scattering and small-angle X-ray scattering) between bare and gold clusters containing proteins allows us to address the volume changes induced either by conformational changes (for BSA) or the formation of protein dimers (for insulin and lysozyme) during cluster formation and incorporation. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. High Performance Electrocatalytic Reaction of Hydrogen and Oxygen on Ruthenium Nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Ruquan; Liu, Yuanyue; Peng, Zhiwei; Wang, Tuo; Jalilov, Almaz S.; Yakobson, Boris I.; Wei, Su-Huai; Tour, James M.

    2017-01-18

    The development of catalytic materials for the hydrogen oxidation, hydrogen evolution, oxygen reduction or oxygen evolution reactions with high reaction rates and low overpotentials are key goals for the development of renewable energy. We report here Ru(0) nanoclusters supported on nitrogen-doped graphene as high-performance multifunctional catalysts for the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR), showing activities similar to that of commercial Pt/C in alkaline solution. For HER performance in alkaline media, sample Ru/NG-750 reaches 10 mA cm-2 at an overpotential of 8 mV with a Tafel slope of 30 mV dec-1. The high HER performance in alkaline solution is advantageous because most catalysts for ORR and oxygen evolution reaction (OER) also prefer alkaline solution environment whereas degrade in acidic electrolytes. For ORR performance, Ru/NG effectively catalyzes the conversion of O2 into OH- via a 4e process at a current density comparable to that of Pt/C. The unusual catalytic activities of Ru(0) nanoclusters reported here are important discoveries for the advancement of renewable energy conversion reactions.

  3. Design and mechanistic study of a novel gold nanocluster-based drug delivery system.

    Science.gov (United States)

    Li, Qinzhen; Pan, Yiting; Chen, Tiankai; Du, Yuanxin; Ge, Honghua; Zhang, Buchang; Xie, Jianping; Yu, Haizhu; Zhu, Manzhou

    2018-05-22

    Chemically-triggered drug delivery systems (DDSs) have been extensively studied as they do not require specialized equipment to deliver the drug and can deeply penetrate human tissue. However, their syntheses are complicated and they tend to be cytotoxic, which restricts their clinical utility. In this work, the self-regulated drug loading and release capabilities of peptide-protected gold nanoclusters (Pep-Au NCs) are investigated using vancomycin (Van) as the model drug. Gold nanoclusters (Au NCs) coated with a custom-designed pentapeptide are synthesized as drug delivery nanocarriers and loaded with Van - a spontaneous process reliant on the specific binding between Van and the custom-designed peptide. The Van-loaded Au NCs show comparable antimicrobial activity with Van on its own, and the number of Van released by the Pep-Au NCs is found to be proportional to the amount of bacteria present. The controlled nature of the Van release is very encouraging, and predominantly due to the stronger binding affinity of Van with bacteria than that with Au NCs. In addition, these fluorescent Au NCs could also be used to construct temperature sensors, which enable the in vitro and in vivo bioimaging.

  4. Heterogeneous Photodecolorization of Methyl Green Catalyzed by Fe(II-o-Phenanthroline/Zeolite Y Nanocluster

    Directory of Open Access Journals (Sweden)

    Alireza Nezamzadeh-Ejhieh

    2011-01-01

    Full Text Available The potential of Fe(II-orthophenatrolin, as doped with synthetic zeolite Y nanocluster (Na-Y via complexation process, after wet impregnation of parent zeolite with FeSO4 aqueous solution, was studied as a photocatalyst in decolorization of Methyl Green (MG under UV irradiation. The characterization of the synthesized zeolite nanocluster and the prepared catalyst was studied using X-ray powder diffraction (XRD, infrared spectroscopy (FT-IR, thermal analysis, and SEM methods. The dye photodecolorization process was studied considering the influence of experimental parameters and it was observed that photoreactivity of the photocatalyst was varied with catalyst amount, initial dye concentration, pH of dye solution, temperature, and the presence of KBrO3. The optimal experimental parameters were obtained as follows: catalyst amount: 1 gL−1, dye concentration: 40 ppm, pH: 9, and active component value: 100 mg Fe(II-orthophenatrolin per g catalyst. The reusability of the intended catalyst was also investigated. The degradation process obeyed first-order kinetics.

  5. Hydrogen generation from hydrolysis of sodium borohydride using Ru(0) nanoclusters as catalyst

    International Nuclear Information System (INIS)

    Ozkar, S.; Zahmakiran, M.

    2005-01-01

    Sodium borohydride is stable in aqueous alkaline solution, however, it hydrolyses in water to hydrogen gas in the presence of suitable catalyst. By this way hydrogen can be generated safely for the fuel cells. Generating H 2 catalytically from NaBH 4 solutions has many advantages: NaBH 4 solutions are nonflammable, reaction products are environmentally benign, rate of H 2 generation is easily controlled, the reaction product NaBO 2 can be recycled, H 2 can be generated even at low temperatures. All of the catalysts that has been used in hydrolysis of sodium borohydride are bulk metals and they act as heterogeneous catalysts. The limited surface area of the heterogeneous catalysts causes lower catalytic activity as the activity of catalyst is directly related to its surface area. Thus, the use of metal nanoparticles with large surface area provides potential route to increase the catalytic activity. Here, we report, for the first time, the use of ruthenium(0) nanoclusters as catalyst in the hydrolysis of sodium borohydride liberating hydrogen gas. The ruthenium nanoparticles are generated from the reduction of ruthenium(III) chloride by sodium borohydride in water and stabilized by specific ligand. The ruthenium(0) nanoclusters are found to be highly active catalyst for the hydrolysis of sodium borohydride

  6. Photoconductivity, photoluminescence and optical Kerr nonlinear effects in zinc oxide films containing chromium nanoclusters

    International Nuclear Information System (INIS)

    Torres-Torres, C.; García-Cruz, M.L.; Castañeda, L.; Rangel Rojo, R.; Tamayo-Rivera, L.; Maldonado, A.; Avendaño-Alejo, M.

    2012-01-01

    Chromium doped zinc oxide thin solid films were deposited on soda–lime glass substrates. The photoconductivity of the material and its influence on the optical behavior was evaluated. A non-alkoxide sol–gel synthesis approach was used for the preparation of the samples. An enhancement of the photoluminescence response exhibited by the resulting photoconductive films with embedded chromium nanoclusters is presented. The modification in the photoconduction induced by a 445 nm wavelength was measured and then associated with the participation of the optical absorptive response. In order to investigate the third order optical nonlinearities of the samples, a standard time-resolved Optical Kerr Gate configuration with 80 fs pulses at 830 nm was used and a quasi-instantaneous pure electronic nonlinearity without the contribution of nonlinear optical absorption was observed. We estimate that from the inclusion of Cr nanoclusters into the sample results a strong optical Kerr effect originated by quantum confinement. The large photoluminescence response and the important refractive nonlinearity of the photoconductive samples seem to promise potential applications for the development of multifunctional all-optical nanodevices. - Highlights: ► Enhancement in photoluminescence for chromium doped zinc oxide films is presented. ► A strong and ultrafast optical Kerr effect seems to result from quantum confinement. ► Photoconductive properties for optical and optoelectronic functions were observed.

  7. Photoconductivity, photoluminescence and optical Kerr nonlinear effects in zinc oxide films containing chromium nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Torres-Torres, C., E-mail: crstorres@yahoo.com.mx [Seccion de Estudios de Posgrado e Investigacion, ESIME-Z, Instituto Politecnico Nacional, Mexico, DF 07738 (Mexico); Garcia-Cruz, M.L. [Centro de Investigacion en Dispositivos Semiconductores, Benemerita Universidad Autonoma de Puebla, A. P. J-48, Puebla 72570, Mexico (Mexico); Castaneda, L., E-mail: luisca@sirio.ifuap.buap.mx [Instituto de Fisica, Benemerita Universidad Autonoma de Puebla, A. P. J-48, Puebla 72570, Mexico (Mexico); Rangel Rojo, R. [CICESE/Depto. de Optica, A. P. 360, Ensenada, BC 22860 (Mexico); Tamayo-Rivera, L. [Instituto de Fisica, Universidad Nacional Autonoma de Mexico, Mexico, DF 01000 (Mexico); Maldonado, A. [Depto. de Ing. Electrica, CINVESTAV IPN-SEES, A. P. 14740, Mexico DF 07000 (Mexico); Avendano-Alejo, M., E-mail: imax_aa@yahoo.com.mx [Centro de Ciencias Aplicadas y Desarrollo Tecnologico, Universidad Nacional Autonoma de Mexico, A. P. 70-186, 04510, DF (Mexico); and others

    2012-04-15

    Chromium doped zinc oxide thin solid films were deposited on soda-lime glass substrates. The photoconductivity of the material and its influence on the optical behavior was evaluated. A non-alkoxide sol-gel synthesis approach was used for the preparation of the samples. An enhancement of the photoluminescence response exhibited by the resulting photoconductive films with embedded chromium nanoclusters is presented. The modification in the photoconduction induced by a 445 nm wavelength was measured and then associated with the participation of the optical absorptive response. In order to investigate the third order optical nonlinearities of the samples, a standard time-resolved Optical Kerr Gate configuration with 80 fs pulses at 830 nm was used and a quasi-instantaneous pure electronic nonlinearity without the contribution of nonlinear optical absorption was observed. We estimate that from the inclusion of Cr nanoclusters into the sample results a strong optical Kerr effect originated by quantum confinement. The large photoluminescence response and the important refractive nonlinearity of the photoconductive samples seem to promise potential applications for the development of multifunctional all-optical nanodevices. - Highlights: Black-Right-Pointing-Pointer Enhancement in photoluminescence for chromium doped zinc oxide films is presented. Black-Right-Pointing-Pointer A strong and ultrafast optical Kerr effect seems to result from quantum confinement. Black-Right-Pointing-Pointer Photoconductive properties for optical and optoelectronic functions were observed.

  8. Exploring luminescence-based temperature sensing using protein-passivated gold nanoclusters

    Science.gov (United States)

    Chen, Xi; Essner, Jeremy B.; Baker, Gary A.

    2014-07-01

    We explore the analytical performance and limitations of optically monitoring aqueous-phase temperature using protein-protected gold nanoclusters (AuNCs). Although not reported elsewhere, we find that these bio-passivated AuNCs show pronounced hysteresis upon thermal cycling. This unwanted behaviour can be eliminated by several strategies, including sol-gel coating and thermal denaturation of the biomolecular template, introducing protein-templated AuNC probes as viable nanothermometers.We explore the analytical performance and limitations of optically monitoring aqueous-phase temperature using protein-protected gold nanoclusters (AuNCs). Although not reported elsewhere, we find that these bio-passivated AuNCs show pronounced hysteresis upon thermal cycling. This unwanted behaviour can be eliminated by several strategies, including sol-gel coating and thermal denaturation of the biomolecular template, introducing protein-templated AuNC probes as viable nanothermometers. Electronic supplementary information (ESI) available: Supplemental figures and experimental details. See DOI: 10.1039/c4nr02069c

  9. Rigid rod spaced fullerene as building block for nanoclusters

    Indian Academy of Sciences (India)

    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 ...

  10. Determining Inorganic and Organic Carbon.

    Science.gov (United States)

    Koistinen, Jaana; Sjöblom, Mervi; Spilling, Kristian

    2017-11-21

    Carbon is the element which makes up the major fraction of lipids and carbohydrates, which could be used for making biofuel. It is therefore important to provide enough carbon and also follow the flow into particulate organic carbon and potential loss to dissolved organic forms of carbon. Here we present methods for determining dissolved inorganic carbon, dissolved organic carbon, and particulate organic carbon.

  11. Rapid synthesis of tin oxide decorated carbon nanotube nanocomposities as anode materials for lithium-ion batteries

    International Nuclear Information System (INIS)

    Lin, Jeng-Yu; Chou, Ming-Hung; Kuo, Yi-Chen

    2014-01-01

    Highlights: • SnO 2 –CNTs nanocomposite was synthesized by microwave-assisted hydrothermal route. • Adding glucose assisted SnO 2 nanoclusters uniformly grow on the surfaces of CNTs. • SnO 2 –CNTs nanocomposite shows improved electrochemical properties. -- Abstract: In this study, the tin oxide decorated carbon nanotubes (SnO 2 –CNTs) nanocomposites have been successfully synthesized using an ultrafast and environmentally friendly microwave-assisted hydrothermal method. According to X-ray diffraction pattern, field emission scanning electron microscopy and transmission electron microscopy, the SnO 2 nanoclusters can directly grow on the surfaces of CNTs with uniform coverage along the longitudinal axis by using glucose as a binding agent. The electrochemical properties of the SnO 2 –CNTs nanocomposite electrode have been further characterized by galvanostatic discharge/charge cycling tests, cyclic voltammetry and electrochemical impedance spectroscopy. Results demonstrate that the SnO 2 –CNTs nanocomposite electrode exhibited a superior reversible discharge capacity, cycling stability and rate capability as an anode material for Li-ion batteries compared to the pristine SnO 2 electrode. Such synergic improvements can be attributed to combining the SnO 2 nanoclusters onto the conductive CNTs matrix by taking advantage of the relatively high specific capacity of SnO 2 nanoclusters and the excellent cycling capability of the CNTs

  12. Study of Thermal-Field Emission Properties and Investigation of Temperature dependent Noise in the Emission Current form vertical Carbon nanotube emitters

    KAUST Repository

    Kolekar, Sadhu; Patole, Shashikant P.; Patil, Sumati; Yoo, J.B.; Dharmadhikari, C.V.

    2017-01-01

    We have investigated temperature dependent field electron emission characteristics of vertical carbon nanotubes (CNTs). The generalized expression for electron emission from well defined cathode surface is given by Millikan and Lauritsen [1

  13. Composite carbon foam electrode

    Science.gov (United States)

    Mayer, Steven T.; Pekala, Richard W.; Kaschmitter, James L.

    1997-01-01

    Carbon aerogels used as a binder for granularized materials, including other forms of carbon and metal additives, are cast onto carbon or metal fiber substrates to form composite carbon thin film sheets. The thin film sheets are utilized in electrochemical energy storage applications, such as electrochemical double layer capacitors (aerocapacitors), lithium based battery insertion electrodes, fuel cell electrodes, and electrocapacitive deionization electrodes. The composite carbon foam may be formed by prior known processes, but with the solid particles being added during the liquid phase of the process, i.e. prior to gelation. The other forms of carbon may include carbon microspheres, carbon powder, carbon aerogel powder or particles, graphite carbons. Metal and/or carbon fibers may be added for increased conductivity. The choice of materials and fibers will depend on the electrolyte used and the relative trade off of system resistivty and power to system energy.

  14. A model for the ethylene and acetylene adsorption on the surface of Cu{sub n}(n = 10–15) nanoclusters: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Farmanzadeh, Davood, E-mail: d.farmanzad@umz.ac.ir; Abdollahi, Tahereh

    2016-11-01

    Highlights: • The most stable structures of Cu{sub n} (n = 10–15) were structures with C{sub S} symmetry. • It is expected that even clusters are better electron donors than the odd clusters. • Acetylene and ethylene adsorb molecularly on the Cu nanoclusters surface. • Acetylene never orient toward di-σ mode for Cu−Cu bond in odd copper nanoclusters. • For di- σ-Cu{sub n}C{sub 2}H{sub 4}, no stable structure is identified. - Abstract: In this work, we report the results of density functional theory calculations of ethylene and acetylene adsorption on the most stable Cu{sub n} (n = 10–15) nanoclusters, in two π and di- σ adsorption modes. Both the hydrocarbons molecularly adsorbed on the surface. Our results show that the quality of interaction of ethylene and acetylene with odd copper nanoclusters (n = 11, 13, 15) is different from what is found on even copper nanoclusters (n = 10, 12, 14). One of the interesting features of this adsorption is that acetylene never orient toward di-σ mode for Cu−Cu bond in odd copper nanoclusters. Also, for di- σ-Cu{sub n}C{sub 2}H{sub 4}, no stable structure is identified. The highest interaction and deformation energies are seen for the adsorption of acetylene and ethylene on Cu{sub 11} in π-mode.

  15. Porous carbons

    Indian Academy of Sciences (India)

    R. Narasimhan (Krishtel eMaging) 1461 1996 Oct 15 13:05:22

    Abstract. Carbon in dense as well as porous solid form is used in a variety of applications. Activated porous carbons are made through pyrolysis and activation of carbonaceous natural as well as synthetic precursors. Pyrolysed woods replicate the structure of original wood but as such possess very low surface areas and ...

  16. Formas de carbono orgánico en suelos con diferentes usos en el departamento del Magdalena (Colombia Some forms of organic carbon in soil with different uses in the Department of Magdalena (Colombia

    Directory of Open Access Journals (Sweden)

    José Rafael Vásquez-Polo

    2011-12-01

    Full Text Available Las fracciones de materia orgánica del suelo (MOS lábiles y humificadas pueden ser afectadas por las prácticas de uso y manejo; sin embargo el impacto de estos cambios no se ha evaluado en suelos y ambientes tropicales. El presente estudio tuvo como objetivo evaluar los contenidos y algunas formas de carbono orgánico del suelo (COS en cinco zonas de clima cálido tropical (0 - 1110 m.s.n.m. del departamento del Magdalena (Colombia y el efecto que sobre ellas han tenido las prácticas asociadas a suelos cultivados con café (Coffea arabica, banano (Musa sp., palma africana (Elaeis guineensis y sábila (Aloe vera, comparados con suelos de bosques naturales. No se encontraron diferencias (P Fractions of soil organic matter (SOM labile and humified, can be affected by use and management practices, but the impact of these changes has not been evaluated in soils of tropical environments. The present study investigated the contents and some forms of soil organic carbon (SOC in five warm tropical climate zones of the Department of Magdalena (Colombia, and the effect of the cropping practices on these forms of organic carbon in cultivated soils, associated with Coffee (Coffea arabica, Banana (Musa sp., African palm (Elaeis guineensis, Aloe (Aloe vera compared to natural forest soils. Significant differences (P < 0.05 were not found between zones as much use soil as. Low average values of SOM in the study areas and higher contents of total carbon in forest soils than in cultivated soils were reported. Forest soils had an average carbon accumulation total of 42.4 mg/ha at 20 cm, compared to 33.8 mg/ha in the cultivated soils, this equates to an average loss of 23% total C by the effect of crop management in these soils, compared to C humified (C extracted with sodium pyrophosphate, values are observed very low in cultivated soils and almost zero in forest soils, but forest soils had a higher number of stable forms of C (Cnox. In the soil cultivated

  17. The Bern Simple Climate Model (BernSCM) v1.0: an extensible and fully documented open-source re-implementation of the Bern reduced-form model for global carbon cycle-climate simulations

    Science.gov (United States)

    Strassmann, Kuno M.; Joos, Fortunat

    2018-05-01

    The Bern Simple Climate Model (BernSCM) is a free open-source re-implementation of a reduced-form carbon cycle-climate model which has been used widely in previous scientific work and IPCC assessments. BernSCM represents the carbon cycle and climate system with a small set of equations for the heat and carbon budget, the parametrization of major nonlinearities, and the substitution of complex component systems with impulse response functions (IRFs). The IRF approach allows cost-efficient yet accurate substitution of detailed parent models of climate system components with near-linear behavior. Illustrative simulations of scenarios from previous multimodel studies show that BernSCM is broadly representative of the range of the climate-carbon cycle response simulated by more complex and detailed models. Model code (in Fortran) was written from scratch with transparency and extensibility in mind, and is provided open source. BernSCM makes scientifically sound carbon cycle-climate modeling available for many applications. Supporting up to decadal time steps with high accuracy, it is suitable for studies with high computational load and for coupling with integrated assessment models (IAMs), for example. Further applications include climate risk assessment in a business, public, or educational context and the estimation of CO2 and climate benefits of emission mitigation options.

  18. The Bern Simple Climate Model (BernSCM v1.0: an extensible and fully documented open-source re-implementation of the Bern reduced-form model for global carbon cycle–climate simulations

    Directory of Open Access Journals (Sweden)

    K. M. Strassmann

    2018-05-01

    Full Text Available The Bern Simple Climate Model (BernSCM is a free open-source re-implementation of a reduced-form carbon cycle–climate model which has been used widely in previous scientific work and IPCC assessments. BernSCM represents the carbon cycle and climate system with a small set of equations for the heat and carbon budget, the parametrization of major nonlinearities, and the substitution of complex component systems with impulse response functions (IRFs. The IRF approach allows cost-efficient yet accurate substitution of detailed parent models of climate system components with near-linear behavior. Illustrative simulations of scenarios from previous multimodel studies show that BernSCM is broadly representative of the range of the climate–carbon cycle response simulated by more complex and detailed models. Model code (in Fortran was written from scratch with transparency and extensibility in mind, and is provided open source. BernSCM makes scientifically sound carbon cycle–climate modeling available for many applications. Supporting up to decadal time steps with high accuracy, it is suitable for studies with high computational load and for coupling with integrated assessment models (IAMs, for example. Further applications include climate risk assessment in a business, public, or educational context and the estimation of CO2 and climate benefits of emission mitigation options.

  19. Synthesis of Au-Pd Nanoflowers Through Nanocluster Assembly

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Jianguang [Duke University; Howe, Jane Y [ORNL; Chi, Miaofang [ORNL; Wilson, Adria [Duke University; Rathmall, Aaron [Duke University; Wiley, Benjamin J [ORNL

    2011-01-01

    Reduction of Pd ions by hydroquinone in the presence of gold nanoparticles and polyvinylpyrrolidone resulted in the formation of nanoflowers with a Au core and Pd petals. Addition of HCl to the synthesis halted the reduction by hydroquinone and enabled the acquisition of snapshots of the nanoflowers at different stages of growth. TEM images of the reaction after 10 s show that the nanoflower morphology resulted from the homogeneous nucleation of Pd clusters in solution and their subsequent attachment to gold seeds coated with a thin (0.8 {+-} 0.1 nm) shell of Pd. UV-visible spectra also indicate Pd clusters formed in the early stages of the reaction and disappeared as the nanoflowers grew. The speed at which this reaction can be halted is useful not only for producing a variety of bimetallic nanostructures with precisely controlled dimensions and morphologies but also for understanding the growth mechanism of these structures. The ability of the AuPd core-shell structure to catalyze the Suzuki coupling reaction of iodobenzene to phenylboronic acid was probed and compared against the activity of Pd nanocubes and thin-shelled AuPd core-shell nanoparticles. The results of this study suggest that Suzuki coupling was not affected by the surface structure or subsurface composition of the nanoparticles, but instead was primarily catalyzed by molecular Pd species that leached from the nanostructures.

  20. Protein coated gold nanoparticles as template for the directed synthesis of highly fluorescent gold nanoclusters

    Science.gov (United States)

    Zhang, Lingyan; Han, Fei

    2018-04-01

    Bovine serum albumin (BSA) modified gold nanoparticles (AuNPs) was selected as template for the synthesis of AuNPs@gold nanoclusters (AuNCs) core/shell nanoparticles, in which BSA not only acted as dual functions agent for both anchoring and reducing Au3+ ions, but also was employed as a bridge between the AuNPs and AuNCs. Optical properties of AuNPs@AuNCs core/shell nanoparticles were studied using UV-visible and fluorescence spectroscopy. The prepared AuNPs@AuNCs core/shell nanoparticles exhibited sphere size uniformity with improved monodispersity, excellent fluorescence and fluorescent stability. Compared with AuNCs, AuNPs@AuNCs core/shell nanoparticles possessed large size and strong fluorescence intensity due to the effect of AuNPs as core. Moreover, the mechanism of the AuNPs induced fluorescence changes of the core/shell nanoparticles was first explored.

  1. Investigating the adsorption of H2O on ZnO nanoclusters by first principle calculations

    KAUST Repository

    Al-Sunaidi, Abdullah A.

    2011-04-01

    The interaction of a single H2O molecule on selected ZnO nanoclusters is investigated by carrying out calculations based on the density-functional theory at the hybrid-GGA (B97-2) level. These clusters have ring, drum, tube and bubble shapes and their physical properties like the binding energy and the band gap energy depend strongly on the shape and size of the cluster. Depending on the stability of the cluster, H2O show both chemisorption and dissociation on the surfaces of the clusters. We analyzed the effect of H2O adsorption on the properties of clusters of size n = 12 via the density of state, HOMO-LUMO orbitals and the changes in the IR frequencies. © 2011 Elsevier B.V. All rights reserved.

  2. Probing the photoluminescence properties of gold nanoclusters by fluorescence lifetime correlation spectroscopy

    International Nuclear Information System (INIS)

    Yuan, C. T.; Lin, T. N.; Shen, J. L.; Lin, C. A.; Chang, W. H.; Cheng, H. W.; Tang, J.

    2013-01-01

    Gold nanoclusters (Au NCs) have attracted much attention for promising applications in biological imaging owing to their tiny sizes and biocompatibility. So far, most efforts have been focused on the strategies for fabricating high-quality Au NCs and then characterized by conventional ensemble measurement. Here, a fusion single-molecule technique combining fluorescence correlation spectroscopy and time-correlated single-photon counting can be successfully applied to probe the photoluminescence (PL) properties for sparse Au NCs. In this case, the triplet-state dynamics and diffusion process can be observed simultaneously and the relevant time constants can be derived. This work provides a complementary insight into the PL mechanism at the molecular levels for Au NCs in solution

  3. Highly fluorescent silver nanoclusters in alumina-silica composite optical fiber

    Energy Technology Data Exchange (ETDEWEB)

    Halder, A.; Chattopadhyay, R.; Majumder, S.; Paul, M. C.; Das, S.; Bhadra, S. K., E-mail: skbhadra@cgcri.res.in [Fiber Optics and Photonics Division, CSIR-Central Glass and Ceramic Research Institute, 196, Raja S. C. Mullick Road, Kolkata 700032 (India); Bysakh, S.; Unnikrishnan, M. [Material Characterization Division, CSIR-Central Glass and Ceramic Research Institute, 196, Raja S. C. Mullick Road, Kolkata 700032 (India)

    2015-01-05

    An efficient visible fluorescent optical fiber embedded with silver nanoclusters (Ag-NCs) having size ∼1 nm, uniformly distributed in alumina-silica composite core glass, is reported. Fibers are fabricated in a repetitive controlled way through modified chemical vapour deposition process associated with solution doping technique. Fibers are drawn from the transparent preforms by conventional fiber drawing process. Structural characteristics of the doped fibers are studied using transmission electron microscopy and electron probe micro analysis. The oxidation state of Ag within Ag-NCs is investigated by X-ray photo electron spectroscopy. The observed significant fluorescence of the metal clusters in fabricated fibers is correlated with electronic model. The experimentally observed size dependent absorption of the metal clusters in fabricated fibers is explained with the help of reported results calculated by ab-initio density functional theory. These optical fibers may open up an opportunity of realizing tunable wavelength fiber laser without the help of rare earth elements.

  4. 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.

  5. Algorithm based on the Thomson problem for determination of equilibrium structures of metal nanoclusters

    Science.gov (United States)

    Arias, E.; Florez, E.; Pérez-Torres, J. F.

    2017-06-01

    A new algorithm for the determination of equilibrium structures suitable for metal nanoclusters is proposed. The algorithm performs a stochastic search of the minima associated with the nuclear potential energy function restricted to a sphere (similar to the Thomson problem), in order to guess configurations of the nuclear positions. Subsequently, the guessed configurations are further optimized driven by the total energy function using the conventional gradient descent method. This methodology is equivalent to using the valence shell electron pair repulsion model in guessing initial configurations in the traditional molecular quantum chemistry. The framework is illustrated in several clusters of increasing complexity: Cu7, Cu9, and Cu11 as benchmark systems, and Cu38 and Ni9 as novel systems. New equilibrium structures for Cu9, Cu11, Cu38, and Ni9 are reported.

  6. 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.

  7. Three-Dimensional Atomic Structure of Metastable Nanoclusters in Doped Semiconductors

    Science.gov (United States)

    Couillard, Martin; Radtke, Guillaume; Knights, Andrew P.; Botton, Gianluigi A.

    2011-10-01

    Aberration-corrected scanning transmission electron microscopy is used to determine the atomic structure of nanoclusters of cerium dopant atoms embedded in silicon. By channeling electrons along two crystallographic orientations, we identify a characteristic zinc-blende chemical ordering within CeSi clusters coherent with the silicon host matrix. Strain energy limits the size of these ordered arrangements to just above 1 nm. With the local order identified, we then determine the atomic configuration of an individual subnanometer cluster by quantifying the scattering intensity under weak channeling condition in terms of the number of atoms. Analysis based on single-atom visualization also evidences the presence of split-vacancy impurity complexes, which supports the hypothesis of a vacancy-assisted formation of these metastable CeSi nanophases.

  8. Contribution of Metal Defects in the Assembly Induced Emission of Cu Nanoclusters

    KAUST Repository

    Wu, Zhennan

    2017-03-20

    Aggregation/assembly induced emission (AIE) has been observed for metal nanoclusters (NCs), but the origin of the enhanced emission is not fully understood, yet. In this work, the significant contribution of metal defects on AIE is revealed by engineering the self-assembly process of Cu NCs using ethanol. The presence of ethanol leads to a rapid assembly of NCs into ultrathin nanosheets, promoting the formation of metal defects-rich surface. Detailed studies and computer simulation confirm that the metal defects-rich nanosheets possess increased Cu(I)-to-Cu(0) ratio, which greatly influences ligand-to-metal-metal charge transfer and therewith facilitates the radiative relaxation of excitons. Consequently, the Cu NCs self-assembly nanosheets exhibit obvious emission enhancement.

  9. Fluorescent turn-on determination of the activity of peptidases using peptide templated gold nanoclusters

    International Nuclear Information System (INIS)

    Luo, Junjun; Wang, Liqiang; Zeng, Ke; Shen, Congcong; Qian, Pin; Yang, Minghui; Rasooly, Avraham; Qu, Fengli

    2016-01-01

    The fluorescence intensity of gold nanoclusters (AuNCs) is inversely related to the length of a peptide immobilized on its surface. This finding has been exploited to design a turn-on fluorescent method for the determination of the activity of peptidase. The β-site amyloid precursor protein-cleaving enzyme 1 (BACE1) was chosen as a model peptidase. BACE1 cleaves the peptide substrates on AuNCs, and the fluorescence intensity of the AuNCs (at exCitation/emission wavelengths of 320/405 nm) carrying the rest of the cleaved peptide is significantly higher than that of the AuNCs with uncleaved peptide. Transmission electron microscopy revealed a decrease in the size of the AuNCs which is assumed cause fluorescence enhancement. The assay was applied to the determination of BACE1 activity in spiked cell lysates, and recoveries were between 96.9 and 104.0 %. (author)

  10. Magnetic interaction reversal in watermelon nanostructured Cr-doped Fe nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Kaur, Maninder; Qiang, You, E-mail: youqiang@uidaho.edu [Department of Physics, University of Idaho, Moscow, Idaho 83844 (United States); Dai, Qilin; Tang, Jinke [Department of Physics and Astronomy, University of Wyoming, Laramie, Wyoming 82071 (United States); Bowden, Mark; Engelhard, Mark [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352 (United States); Wu, Yaqiao [Department of Materials Science and Engineering, Boise State University, Boise, Idaho 83725 (United States); Center for Advanced Energy Studies, Idaho Falls, Idaho 83401 (United States)

    2013-11-11

    Cr-doped core-shell Fe/Fe-oxide nanoclusters (NCs) were synthesized at varied atomic percentages of Cr from 0 at. % to 8 at. %. The low concentrations of Cr (<10 at. %) were selected in order to inhibit the complete conversion of the Fe-oxide shell to Cr{sub 2}O{sub 3} and the Fe core to FeCr alloy. The magnetic interaction in Fe/Fe-oxide NCs (∼25 nm) can be controlled by antiferromagnetic Cr-dopant. We report the origin of σ-FeCr phase at very low Cr concentration (2 at. %) unlike in previous studies, and the interaction reversal from dipolar to exchange interaction in watermelon-like Cr-doped core-shell NCs.

  11. 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.

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

    International Nuclear Information System (INIS)

    Yang, Hee-Man; Jang, Sung-Chan; Lee, Kune Woo; Seo, Bum-Kyoung; Moon, Jei Kwon

    2014-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-10-15

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

  14. Dispersion of gold nanoclusters in TMBPA-polycarbonate by a combination of thermal embedding and vapour-induced crystallization

    International Nuclear Information System (INIS)

    Kruse, J; Dolgner, K; Greve, H; Zaporojtchenko, V; Faupel, F

    2006-01-01

    Gold nanoclusters can be dispersed into the surface of a bisphenol-A polycarbonate film by acetone vapour induced crystallization, an effect which has been demonstrated in a previous publication of our group. Gold nanoclusters were deposited by physical vapour deposition on an amorphous thin film of polycarbonate. After vapour induced crystallization these clusters were detected by depth profiling to be embedded into the surface, with a concentration maximum in a depth of approximately 100 nm. In this work, we replaced the BPA by the modified tetramethyl bisphenol-A polycarbonate, which shows a slower crystallization kinetics. A strong enhancement of the dispersion depth has been achieved by thermal pre-embedding of the clusters into the surface. Surface analysis by means of atomic force microscopy reflects the rearrangement of polymer material in the course of crystallization

  15. Thermodynamics, kinetics, and catalytic effect of dehydrogenation from MgH2 stepped surfaces and nanocluster: a DFT study

    Science.gov (United States)

    Reich, Jason; Wang, Linlin; Johnson, Duane

    2013-03-01

    We detail the results of a Density Functional Theory (DFT) based study of hydrogen desorption, including thermodynamics and kinetics with(out) catalytic dopants, on stepped (110) rutile and nanocluster MgH2. We investigate competing configurations (optimal surface and nanoparticle configurations) using simulated annealing with additional converged results at 0 K, necessary for finding the low-energy, doped MgH2 nanostructures. Thermodynamics of hydrogen desorption from unique dopant sites will be shown, as well as activation energies using the Nudged Elastic Band algorithm. To compare to experiment, both stepped structures and nanoclusters are required to understanding and predict the effects of ball milling. We demonstrate how these model systems relate to the intermediary sized structures typically seen in ball milling experiments.

  16. Ab initio study of structural, electronic, optical, and vibrational properties of Zn{sub x}S{sub y} (x + y = 2 to 5) nanoclusters

    Energy Technology Data Exchange (ETDEWEB)

    Yadav, P. S.; Pandey, D. K., E-mail: pdhiraj2000@gmail.com; Agrawal, S.; Agrawal, B. K. [Allahabad University, Department of Physics (India)

    2010-03-15

    An ab initio study of the stability, structural, electronic. and optical properties has been performed for 46 zinc sulfide nanoclusters Zn{sub x}S{sub y} (x + y = n = 2 to 5). Five out of them are seen to be unstable as their vibrational frequencies are found to be imaginary. A B3LYP-DFT/6-311G(3df) method is employed to optimize the geometries and a TDDFT method is used for the study of the optical properties. The binding energies (BE), HOMO-LUMO gaps and the bond lengths have been obtained for all the clusters. For the ZnS{sub 2}, ZnS{sub 3}, and ZnS{sub 4} nanoclusters, our stable structures are seen to be different from those obtained earlier by using the effective core potentials. We have also considered the zero point energy (ZPE) corrections ignored by the earlier workers. For a fixed value of n, we designate the most stable structure the one, which has maximum final binding energy per atom. The adiabatic and vertical ionization potentials (IP) and electron affinities (EA), charges on the atoms, dipole moments, optical properties, vibrational frequencies, infrared intensities, relative infrared intensities, and Raman scattering activities have been investigated for the most stable structures. The nanoclusters containing large number of S atoms for each n is found to be most stable. The HOMO-LUMO gap decreases from n = 2-3 and then increases above n = 3. The IP and EA both fluctuate with the cluster size n. The optical absorption is quite weak in visible region but strong in the ultraviolet region in most of the nanoclusters except a few. The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every nanocluster and may be used to characterize a specific nanocluster. The growth of most stable nanoclusters may be possible in the experiments.

  17. Ab initio study of structural, electronic, optical, and vibrational properties of Zn x S y ( x + y = 2 to 5) nanoclusters

    Science.gov (United States)

    Yadav, P. S.; Pandey, D. K.; Agrawal, S.; Agrawal, B. K.

    2010-03-01

    An ab initio study of the stability, structural, electronic. and optical properties has been performed for 46 zinc sulfide nanoclusters Zn x S y ( x + y = n = 2 to 5). Five out of them are seen to be unstable as their vibrational frequencies are found to be imaginary. A B3LYP-DFT/6-311G(3df) method is employed to optimize the geometries and a TDDFT method is used for the study of the optical properties. The binding energies (BE), HOMO-LUMO gaps and the bond lengths have been obtained for all the clusters. For the ZnS2, ZnS3, and ZnS4 nanoclusters, our stable structures are seen to be different from those obtained earlier by using the effective core potentials. We have also considered the zero point energy (ZPE) corrections ignored by the earlier workers. For a fixed value of n, we designate the most stable structure the one, which has maximum final binding energy per atom. The adiabatic and vertical ionization potentials (IP) and electron affinities (EA), charges on the atoms, dipole moments, optical properties, vibrational frequencies, infrared intensities, relative infrared intensities, and Raman scattering activities have been investigated for the most stable structures. The nanoclusters containing large number of S atoms for each n is found to be most stable. The HOMO-LUMO gap decreases from n = 2-3 and then increases above n = 3. The IP and EA both fluctuate with the cluster size n. The optical absorption is quite weak in visible region but strong in the ultraviolet region in most of the nanoclusters except a few. The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every nanocluster and may be used to characterize a specific nanocluster. The growth of most stable nanoclusters may be possible in the experiments.

  18. Hydrothermal synthesis of polyethylenimine-protected high luminescent Pt-nanoclusters and their application to the detection of nitroimidazoles

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Na [State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, 130012 (China); College of Materials Science and Engineering, Jilin Institute of Chemical Technology, Jilin, 132022 (China); Li, Hong-Wei, E-mail: lihongwei@jlu.edu.cn [State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, 130012 (China); Wu, Yuqing, E-mail: yqwu@jlu.edu.cn [State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun, 130012 (China)

    2017-03-15

    A novel one-step hydrothermal synthesis of highly fluorescent platinum nanoclusters protected by polyethylenimine (Pt-NCs@PEI) is described. The products are characterized well by UV–vis absorption, fluorescence spectra, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) imaging. The Pt-NCs@PEI possess high quantum yield at 28%, which is the relatively high one among the reported Pt-NCs; especially, the synthesis is in one-step and the reaction time is much shorter (<1 h) than the related methods. In addition, the Pt-NCs@PEI have large Stocks-shift (∼150 nm), high tolerability to the extreme pH and high ionic strengths, and excellent photo-stability under UV–vis irradiation, lay the foundation for the practical bio-applications. Finally, the obtained Pt-NCs@PEI are used to determine trace amount of metronidazole (MTZ) in buffer solution in showing a linear response over a concentration range of 0.25–300 μM and a low detection limit of 0.1 μM. Furthermore, the related investigation on response mechanism will be helpful to design and synthesize new metal nanoclusters as fluorescent probe to detect the trace amount of harmful medicine residuum as nitroimidazoles in human body. - Highlights: • This paper provides the first hydrothermal synthesis of platinum nanoclusters. • The prepared polyethylenimine-protected platinum nanoclusters possess high quantum yield of 28%. • A new method to detect trace amount of metronidazole in urine is proposed.

  19. One-step synthesis and applications of fluorescent Cu nanoclusters stabilized by L-cysteine in aqueous solution

    International Nuclear Information System (INIS)

    Yang, Xiaoming; Feng, Yuanjiao; Zhu, Shanshan; Luo, Yawen; Zhuo, Yan; Dou, Yao

    2014-01-01

    Graphical abstract: An innovative and simple strategy for synthesizing high-fluorescent Cu nanoclusters stabilized with L-cysteine has been successfully established in aqueous solution. Significantly, the Cu nanoclusters were employed for sensitive and selective detections of Hg 2+ , coding and fluorescent staining, suggesting their potential toward various applications. - Highlights: • A novel, one-step strategy for synthesizing water-soluble CuNCs was established. • A simple, selective, and cost-effective assay for Hg 2+ was developed. • CuNCs may broaden ways for fluorescent staining and coding. - Abstract: Herein, an innovative and simple strategy for synthesizing high fluorescent Cu nanoclusters was successfully established while L-cysteine played a role as the stabilizer. Meaningfully, the current Cu nanoclusters together with a quantum yield of 14.3% were prepared in aqueous solution, indicating their extensive applications. Subsequently, the possible fluorescence mechanism was elucidated by fluorescence, UV–vis, HR-TEM, FTIR, XPS, and MS. Additionally, the CuNCs were employed for assaying Hg 2+ on the basis of the interactions between Hg 2+ and L-cysteine; thus facilitating the quenching of their fluorescence. The proposed analytical strategy permitted detections of Hg 2+ in a linear range of 1.0 × 10 −7 mol L −1 × 10 −3 mol L −1 , with a detection limit of 2.4 × 10 −8 mol L −1 at a signal-to-noise ratio of 3. Significantly, this CuNCs described here were further applied for coding and fluorescent staining, suggesting may broaden avenues toward diverse applications

  20. One-step synthesis and applications of fluorescent Cu nanoclusters stabilized by L-cysteine in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Xiaoming, E-mail: ming4444@swu.edu.cn; Feng, Yuanjiao; Zhu, Shanshan; Luo, Yawen; Zhuo, Yan; Dou, Yao

    2014-10-17

    Graphical abstract: An innovative and simple strategy for synthesizing high-fluorescent Cu nanoclusters stabilized with L-cysteine has been successfully established in aqueous solution. Significantly, the Cu nanoclusters were employed for sensitive and selective detections of Hg{sup 2+}, coding and fluorescent staining, suggesting their potential toward various applications. - Highlights: • A novel, one-step strategy for synthesizing water-soluble CuNCs was established. • A simple, selective, and cost-effective assay for Hg{sup 2+} was developed. • CuNCs may broaden ways for fluorescent staining and coding. - Abstract: Herein, an innovative and simple strategy for synthesizing high fluorescent Cu nanoclusters was successfully established while L-cysteine played a role as the stabilizer. Meaningfully, the current Cu nanoclusters together with a quantum yield of 14.3% were prepared in aqueous solution, indicating their extensive applications. Subsequently, the possible fluorescence mechanism was elucidated by fluorescence, UV–vis, HR-TEM, FTIR, XPS, and MS. Additionally, the CuNCs were employed for assaying Hg{sup 2+} on the basis of the interactions between Hg{sup 2+} and L-cysteine; thus facilitating the quenching of their fluorescence. The proposed analytical strategy permitted detections of Hg{sup 2+} in a linear range of 1.0 × 10{sup −7} mol L{sup −1} × 10{sup −3} mol L{sup −1}, with a detection limit of 2.4 × 10{sup −8} mol L{sup −1} at a signal-to-noise ratio of 3. Significantly, this CuNCs described here were further applied for coding and fluorescent staining, suggesting may broaden avenues toward diverse applications.