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

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

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

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.

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.

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.

Reactivity of Monolayer Protected Silver Clusters Towards Excess Ligand: A Calorimetric Study

KAUST Repository

Baksi, Ananya; Bootharaju, Megalamane Siddaramappa; Chhotaray, Pratap K.; Chakraborty, Papri; Mondal, Biswajit; Bhat, Shridevi; Gardas, Ramesh L.; Pradeep, Thalappil

2017-01-01

Reactivity of monolayer protected atomically precise clusters of noble metals is of significant research interest. Till date very few experimental data are available on the reaction thermodynamics of such clusters. Here we report a calorimetric

Hydrophilic Cucurbit[7]uril-Pseudorotaxane-Anchored-Monolayer-Protected Gold Nanorods

Science.gov (United States)

2013-03-20

FULL PAPER DOI:10.1002/ejic.201300010 Hydrophilic Cucurbit[7]uril-Pseudorotaxane-Anchored- Monolayer-Protected Gold Nanorods Xiang Ma,[a] Yuhua Xue... Cao , Q. Wang, H. Tian, Chem. Commun. 2011, 47, 3559–3561. [8] a) I. Hwang, K. Baek, M. Jung, Y. Kim, K. M. Park, D. W. Lee, N. Selvapalam, K. Kim, J. Am

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

Determination of the activity of telomerase in cancer cells by using BSA-protected gold nanoclusters as a fluorescent probe.

Science.gov (United States)

Xu, Yujuan; Zhang, Peng; Wang, Zhen; Lv, Shaoping; Ding, Caifeng

2018-02-27

Gold nanoclusters (AuNCs) protected with a bovine serum albumin (BSA) coating are known to emit red fluorescence (peaking at 650 nm) on photoexcitation with ultraviolet light (365 nm). On addition of Cu(II) ions, fluorescence is quenched because Cu(II) complexes certain amino acid units in the BSA chain. Fluorescence is, however, restored if pyrophosphate (PPi) is added because it will chelate Cu(II) and remove it from the BSA coating on the AuNCs. Because PPi is involved in the function of telomerase, the BSA@AuNCs loaded with Cu(II) can act as a fluorescent probe for determination of the activity of telomerase. A fluorescent assay was worked out for telomerase that is highly sensitive and has a wide linear range (10 nU to 10 fM per mL). The fluorescent probe was applied to the determination of telomerase activity in cervix carcinoma cells via imaging. It is shown that tumor cells can be well distinguished from normal cells by monitoring the differences in intracellular telomerase activity. Graphical abstract Gold nanoclusters (AuNCs) protected by bovine serum albumin (BSA) and displaying red photoluminescence were prepared as fluorescent probe for the determination of telomerase activity and used for imaging of cervix carcinoma (HeLa) cells.

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.

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

Dendritic functionalization of monolayer-protected gold nanoparticles

International Nuclear Information System (INIS)

Cutler, Erin C.; Lundin, Erik; Garabato, B. Davis; Choi, Daeock; Shon, Young-Seok

2007-01-01

This paper describes the facile synthesis of nanoparticle-cored dendrimers (NCDs) and nanoparticle megamers from monolayer-protected gold clusters using either single or multi-step reactions. First, 11-mercaptoundecanoic acid/hexanethiolate-protected gold clusters were synthesized using the Schiffrin reaction followed by the ligand place-exchange reaction. A convergent approach for the synthesis of nanoparticle-cored dendrimers uses a single step reaction that is an ester coupling reaction of hydroxy-functionalized dendrons with carboxylic acid-functionalized gold clusters. A divergent approach, which is based on multi-step reactions, employs the repetition of an amide coupling reaction and a Michael addition reaction to build polyamidoamine dendritic architectures around a nanoparticle core. Nanoparticle megamers, which are large dendrimer-induced nanoparticle aggregates with an average diameter of more than 300 nm, were prepared by the amide coupling reaction between polyamiodoamine [G-2] dendrimers and carboxylic acid-functionalized gold clusters. 1 H NMR spectroscopy, FT-IR spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) were used for the characterization of these hybrid nanoparticles

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.

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.

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

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.

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

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.

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.

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.

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.

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.

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

Directory of Open Access Journals (Sweden)

Judit Váradi

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

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

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

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

KAUST Repository

Aljuhani, Maha A.

2016-12-17

While monothiols and simple phosphines are commonly exploited for size-controlled synthesis of atomically precise gold nanoclusters (NCs), dithiols or dithiol-phosphine combinations are seldom applied. Herein, we used a dithiol (benzene-1,3-dithiol, BDT) and a phosphine (triphenylphosphine, TPP) together as ligands and synthesized an atomically precise gold NC with the formula [Au28(BDT)4(TPP)9]2+. This NC exhibited multiple absorption features and a charge of +2, which are distinctly different from the reported all-thiolated [Au28(SR)20]0 NC (SR: monothiolate). The composition of [Au28(BDT)4(TPP)9]2+ NC was deduced from high-resolution electrospray ionization mass spectrometry (ESI MS) and it was further corroborated by thermogravimetric analysis (TGA). Differential pulse voltammetry (DPV) revealed a HOMO–LUMO gap of 1.27 eV, which is in good agreement with the energy gap of 1.3 eV obtained from its UV–vis spectrum. The successful synthesis of atomically precise, dithiol-protected Au28 NC would stimulate theoretical and experimental research into bidentate ligands as a new path for expanding the library of different metal NCs, which have so far been dominated by monodentate thiols.

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.

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)

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.

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

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.

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.

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.

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.

Monolayer-protected clusters of gold nanoparticles: impacts of stabilizing ligands on the heterogeneous electron transfer dynamics and voltammetric detection.

Science.gov (United States)

Pillay, Jeseelan; Ozoemena, Kenneth I; Tshikhudo, Robert T; Moutloali, Richard M

2010-06-01

Surface electrochemistry of novel monolayer-protected gold nanoparticles (MPCAuNPs) is described. Protecting ligands, (1-sulfanylundec-11-yl)tetraethylene glycol (PEG-OH) and (1-sulfanylundec-11-yl)poly(ethylene glycol)ic acid (PEG-COOH), of three different percent ratios (PEG-COOH:PEG-OH), 1:99 (MPCAuNP-COOH(1%)), 50:50 (MPCAuNP-COOH(50%)), and 99:1 (MPCAuNP-COOH(99%)), were studied. The electron transfer rate constants (k(et)/s(-1)) in organic medium decreased as the concentration of the surface-exposed -COOH group in the protecting monolayer ligand is increased: MPCAuNP-COOH(1%) (approximately 5 s(-1)) > MPCAuNP-COOH(50%) (approximately 4 s(-1)) > MPCAuNP-COOH(99%) (approximately 0.5 s(-1)). In aqueous medium, the trend is reversed. The surface pK(a) was estimated as approximately 8.2 for the MPCAuNP-COOH(1%), while both MPCAuNP-COOH(50%) and MPCAuNP-COOH(99%) showed two pK(a) values of about 5.0 and approximately 8.0. These results have been interpreted in terms of the quasi-solidity and quasi-liquidity of the terminal -OH and -COOH head groups, respectively. MPCAuNP-COOH(99%) excellently suppressed the voltammetric response of the ascorbic acid but enhanced the electrocatalytic detection of epinephrine compared to the other MPCAuNPs studied. This study reveals important factors that should be considered when designing electrode devices that employ monolayer-protected gold nanoparticles and possibly for some other redox-active metal nanoparticles.

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.

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

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

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

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.

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.

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.

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.

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.

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

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...

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.

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.

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

Science.gov (United States)

Zheng, Ming; Li, Zhigang; Huang, Xueying

2004-05-11

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

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.

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.

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.

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.

Construction of multilayers of bare and Pd modified gold nanoclusters and their electrocatalytic properties for oxygen reduction

Directory of Open Access Journals (Sweden)

Motoko Harada, Hidenori Noguchi, Nikolas Zanetakis, Satoru Takakusagi, Wenbo Song and Kohei Uosaki

2011-01-01

Full Text Available Multilayers of gold nanoclusters (GNCs coated with a thin Pd layer were constructed using GNCs modified with self-assembled monolayers (SAMs of mercaptoundecanoic acid and a polyallylamine hydrochloride (PAH multilayer assembly, which has been reported to act as a three-dimensional electrode. SAMs were removed from GNCs by electrochemical anodic decomposition and then a small amount of Pd was electrochemically deposited on the GNCs. The kinetics of the oxygen reduction reaction (ORR on the Pd modified GNC/PAH multilayer assembly was studied using a rotating disk electrode, and a significant increase in the ORR rate was observed after Pd deposition. Electrocatalytic activities in alkaline and acidic solutions were compared both for the GNC multilayer electrode and Pd modified GNC electrode.

Reactivity of Monolayer Protected Silver Clusters Towards Excess Ligand: A Calorimetric Study

KAUST Repository

Baksi, Ananya

2017-10-31

Reactivity of monolayer protected atomically precise clusters of noble metals is of significant research interest. Till date very few experimental data are available on the reaction thermodynamics of such clusters. Here we report a calorimetric study of the reaction of glutathione (GSH) protected silver clusters in presence of excess ligand, GSH using isothermal titration calorimetry (ITC). We have studied Ag11(SG)7 and Ag32(SG)19 clusters and compared their reactivity with GSH protected silver nanoparticles (AgNPs) and silver ions. Clusters show intermediate reactivity towards excess ligand com-pared to nanoparticles and silver ions. Several control experiments were performed to understand the degradation mech-anism of these silver clusters and nanoparticles. Effect of dissolved oxygen in the degradation process was studied in de-tail and found that it did not have a significant role, although alternate pathways of degradation with the involvement of oxygen cannot be ruled out. Direct confirmation of the fact that functionalized metal clusters fall in-between NPs and atomic systems in their stability is obtained experimentally for the first time. Several other thermophysical parameters of these clusters were also determined including, density, speed of sound, isentropic compressibility and coefficient of thermal expansion.

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.

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.

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.

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.

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.

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}.

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.

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

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.)

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.

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.

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.

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.

Configuration-controlled Au nanocluster arrays on inverse micelle nano-patterns: versatile platforms for SERS and SPR sensors

Science.gov (United States)

Jang, Yoon Hee; Chung, Kyungwha; Quan, Li Na; Špačková, Barbora; Šípová, Hana; Moon, Seyoung; Cho, Won Joon; Shin, Hae-Young; Jang, Yu Jin; Lee, Ji-Eun; Kochuveedu, Saji Thomas; Yoon, Min Ji; Kim, Jihyeon; Yoon, Seokhyun; Kim, Jin Kon; Kim, Donghyun; Homola, Jiří; Kim, Dong Ha

2013-11-01

Nanopatterned 2-dimensional Au nanocluster arrays with controlled configuration are fabricated onto reconstructed nanoporous poly(styrene-block-vinylpyridine) inverse micelle monolayer films. Near-field coupling of localized surface plasmons is studied and compared for disordered and ordered core-centered Au NC arrays. Differences in evolution of the absorption band and field enhancement upon Au nanoparticle adsorption are shown. The experimental results are found to be in good agreement with theoretical studies based on the finite-difference time-domain method and rigorous coupled-wave analysis. The realized Au nanopatterns are exploited as substrates for surface-enhanced Raman scattering and integrated into Kretschmann-type SPR sensors, based on which unprecedented SPR-coupling-type sensors are demonstrated.Nanopatterned 2-dimensional Au nanocluster arrays with controlled configuration are fabricated onto reconstructed nanoporous poly(styrene-block-vinylpyridine) inverse micelle monolayer films. Near-field coupling of localized surface plasmons is studied and compared for disordered and ordered core-centered Au NC arrays. Differences in evolution of the absorption band and field enhancement upon Au nanoparticle adsorption are shown. The experimental results are found to be in good agreement with theoretical studies based on the finite-difference time-domain method and rigorous coupled-wave analysis. The realized Au nanopatterns are exploited as substrates for surface-enhanced Raman scattering and integrated into Kretschmann-type SPR sensors, based on which unprecedented SPR-coupling-type sensors are demonstrated. Electronic supplementary information (ESI) available: TEM image and UV-vis absorption spectrum of citrate-capped Au NPs, AFM images of Au NC arrays on the PS-b-P4VP (41k-24k) template, ImageJ-analyzed results of PS-b-P4VP (41k-24k)-templated Au NC arrays, calculated %-surface coverage values, SEM images of Au NC arrays on the PS-b-P2VP (172k-42k

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...

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)

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.

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.

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).

Controlled assembly and single electron charging of monolayer protected Au144 clusters: an electrochemistry and scanning tunneling spectroscopy study

Science.gov (United States)

Bodappa, Nataraju; Fluch, Ulrike; Fu, Yongchun; Mayor, Marcel; Moreno-García, Pavel; Siegenthaler, Hans; Wandlowski, Thomas

2014-11-01

Single gold particles may serve as room temperature single electron memory units because of their size dependent electronic level spacing. Here, we present a proof-of-concept study by electrochemically controlled scanning probe experiments performed on tailor-made Au particles of narrow dispersity. In particular, the charge transport characteristics through chemically synthesized hexane-1-thiol and 4-pyridylbenzene-1-thiol mixed monolayer protected Au144 clusters (MPCs) by differential pulse voltammetry (DPV) and electrochemical scanning tunneling spectroscopy (EC-STS) are reported. The pyridyl groups exposed by the Au-MPCs enable their immobilization on Pt(111) substrates. By varying the humidity during their deposition, samples coated by stacks of compact monolayers of Au-MPCs or decorated with individual, laterally separated Au-MPCs are obtained. DPV experiments with stacked monolayers of Au144-MPCs and EC-STS experiments with laterally separated individual Au144-MPCs are performed both in aqueous and ionic liquid electrolytes. Lower capacitance values were observed for individual clusters compared to ensemble clusters. This trend remains the same irrespective of the composition of the electrolyte surrounding the Au144-MPC. However, the resolution of the energy level spacing of the single clusters is strongly affected by the proximity of neighboring particles.Single gold particles may serve as room temperature single electron memory units because of their size dependent electronic level spacing. Here, we present a proof-of-concept study by electrochemically controlled scanning probe experiments performed on tailor-made Au particles of narrow dispersity. In particular, the charge transport characteristics through chemically synthesized hexane-1-thiol and 4-pyridylbenzene-1-thiol mixed monolayer protected Au144 clusters (MPCs) by differential pulse voltammetry (DPV) and electrochemical scanning tunneling spectroscopy (EC-STS) are reported. The pyridyl groups

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.

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.

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

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.

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.

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...

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}.

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

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...

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...

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

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.

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

Science.gov (United States)

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

2012-05-02

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

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).

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...

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.

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

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.

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)

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

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...

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.

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

Science.gov (United States)

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

2016-01-01

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

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.

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.

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.

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.

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.

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

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

TiO2 Films Modified with Au Nanoclusters as Self-Cleaning Surfaces under Visible Light

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Ting-Wei Liao

2018-01-01

Full Text Available In this study, we applied cluster beam deposition (CBD as a new approach for fabricating efficient plasmon-based photocatalytic materials. Au nanoclusters (AuNCs produced in the gas phase were deposited on TiO2 P25-coated silicon wafers with coverage ranging from 2 to 8 atomic monolayer (ML equivalents. Scanning Electron Microscopy (SEM images of the AuNCs modified TiO2 P25 films show that the surface is uniformly covered by the AuNCs that remain isolated at low coverage (2 ML, 4 ML and aggregate at higher coverage (8 ML. A clear relationship between AuNCs coverage and photocatalytic activity towards stearic acid photo-oxidation was measured, both under ultraviolet and green light illumination. TiO2 P25 covered with 4 ML AuNCs showed the best stearic acid photo-oxidation performance under green light illumination (Formal Quantum Efficiency 1.6 × 10−6 over a period of 93 h. These results demonstrate the large potential of gas-phase AuNCs beam deposition technology for the fabrication of visible light active plasmonic photocatalysts.

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

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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.

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.

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

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

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.

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

Design, Synthesis, and Characterization of Novel Thiol-Derivatized Ibuprofen Monolayer Protected Gold Clusters

International Nuclear Information System (INIS)

Lee, K.H.; Lee, K.H.; Lin, Y.Sh.; Huang, P.J.

2013-01-01

A series of new thiol-derivatized ibuprofen monolayer protected gold clusters have been prepared by amidation of ibuprofen with alkyl alcohol or aminophenol affording the carboxamide, N-hydroxyalkyl amide 2, and N-hydroxyphenyl amide 6, which were then tosylate with p-toluenesulfonyl chloride at hydroxyl group to give 3 and 7. Reactions of 3 and 7 with NaSH afforded the mercapto derivatives 4 and 8. Conducting Brust’s reaction with a 3:1 mole ratio of thiolate ibuprofen/ AuCl 4 - yielded polydisperse thiol-derivatized ibuprofen-MPCs 5 and 9. All compounds have been identified by NMR, MS, UV, and IR spectroscopies. Compounds 4 and 8 and the MPCs 5 and 9 have been investigated by using the method of 1 H NMR spectroscopy. The broadening of the signals from 0.8 to 2.0 ppm in 1 H NMR spectrum of MPCs 5 and 9 confirmed the success of the conjugation of thiol-containing derivatives with nano gold cluster.

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.

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

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

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.

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

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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.

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.

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.

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.)

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

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

Science.gov (United States)

Kairdolf, Brad A.; Nie, Shuming

2011-01-01

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

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.

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

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.

Effects of hyperthermal proton bombardment on alkanethiol self-assembled monolayer on Au(1 1 1)

Energy Technology Data Exchange (ETDEWEB)

Xi Luan [Surface Science Western, University of Western Ontario, London, Ontario N6A 5B7 (Canada); Zheng Zhi; Lam, N.-S. [Department of Physics, Chinese University of Hong Kong, Shatin, Hong Kong (China); Grizzi, Oscar [Centro Atomico Bariloche, 8400 San Carlos de Bariloche, Rio Negro (Argentina); Lau, W.-M. [Surface Science Western, University of Western Ontario, London, Ontario N6A 5B7 (Canada)], E-mail: llau22@uwo.ca

2007-10-31

The effects of hyperthermal proton bombardment on alkanethiol self-assembled monolayer (SAM) on Au(1 1 1) are studied with scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS). The STM and XPS results show that proton bombardment with proton energy as low as 2 eV can induce cross-linking of the adsorbed alkanethiols and transform the original ordered SAM lattice to an array of nanoclusters of the cross-linked alkanethiols. For a bombardment at 3 eV with a fluence of 3x10{sup 15} cm{sup -2}, the typical cluster size is about 5 nm. In addition, the cluster size distribution is narrow, with no cluster larger than 8 nm. The cluster growth can be promoted by increasing the fluence at a fixed bombardment energy or increasing the energy at a fixed fluence. This indicates that surface diffusion of alkanethiols and cluster growth can be harnessed by the control of the bombardment energy and fluence.

Effects of hyperthermal proton bombardment on alkanethiol self-assembled monolayer on Au(1 1 1)

International Nuclear Information System (INIS)

Xi Luan; Zheng Zhi; Lam, N.-S.; Grizzi, Oscar; Lau, W.-M.

2007-01-01

The effects of hyperthermal proton bombardment on alkanethiol self-assembled monolayer (SAM) on Au(1 1 1) are studied with scanning tunneling microscopy (STM) and X-ray photoemission spectroscopy (XPS). The STM and XPS results show that proton bombardment with proton energy as low as 2 eV can induce cross-linking of the adsorbed alkanethiols and transform the original ordered SAM lattice to an array of nanoclusters of the cross-linked alkanethiols. For a bombardment at 3 eV with a fluence of 3x10 15 cm -2 , the typical cluster size is about 5 nm. In addition, the cluster size distribution is narrow, with no cluster larger than 8 nm. The cluster growth can be promoted by increasing the fluence at a fixed bombardment energy or increasing the energy at a fixed fluence. This indicates that surface diffusion of alkanethiols and cluster growth can be harnessed by the control of the bombardment energy and fluence

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.

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.

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.

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

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

"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

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.

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.

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.

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.

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

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.

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.

Analyte Kinetics in a Nanocluster-Based Chemiresistor: A Case Study

Science.gov (United States)

2013-01-01

of vapor-induced resistivity changes in gold- thiolate monolayer-protected nanoparticle sensor films, Ana- lytical Chemistry 79 (2007) 4977–4986. [27...1971, followed by brief military service, then graduated from the City University of New York in 1977 with a Ph.D. in polymer chemistry. After a year...staff member as a research chemist in 1979. His research interests are polymer synthesis, electroac- tive polymers , low-dielectric polymers , chemical

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.

Transport properties in monolayer-bilayer-monolayer graphene planar junctions

Institute of Scientific and Technical Information of China (English)

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

2017-01-01

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

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.

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.

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.

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...

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.)

Diamondoid monolayers as electron emitters

Science.gov (United States)

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

2012-04-10

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

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 ...

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.

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

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.

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.

A fluorescence detection of D-penicillamine based on Cu(2+)-induced fluorescence quenching system of protein-stabilized gold nanoclusters.

Science.gov (United States)

Wang, Peng; Li, Bang Lin; Li, Nian Bing; Luo, Hong Qun

2015-01-25

In this contribution, a luminescent gold nanoclusters which were synthesized by bovine serum albumin as novel fluorescent probes were successfully utilized for the determination of D-penicillamine for the first time. Cupric ion was employed to quench the strong fluorescence of the gold nanoclusters, whereas the addition of D-penicillamine caused obvious restoration of fluorescence intensity of the Cu(2+)-gold nanoclusters system. Under optimum conditions, the increment in fluorescence intensity of Cu(2+)-gold nanoclusters system caused by D-penicillamine was linearly proportional to the concentration of D-penicillamine in the range of 2.0×10(-5)-2.39×10(-4) M. The detection limit for D-penicillamine was 5.4×10(-6) M. With the off-on fluorescence signal at 650 nm approaching the near-infrared region, the present sensor for D-penicillamine detection had high sensitivity and low spectral interference. Furthermore, the novel gold nanoclusters-based fluorescent sensor has been applied to the determination of D-penicillamine in real biological samples with satisfactory results. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Photocarrier dynamics in monolayer phosphorene and bulk black phosphorus.

Science.gov (United States)

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

2018-06-13

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

Failure mechanism of monolayer graphene under hypervelocity impact of spherical projectile

Science.gov (United States)

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

2016-09-01

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

Gold nanocluster-based vaccines for dual-delivery of antigens and immunostimulatory oligonucleotides

Science.gov (United States)

Tao, Yu; Zhang, Yan; Ju, Enguo; Ren, Hui; Ren, Jinsong

2015-07-01

We here report a facile one-pot synthesis of fluorescent gold nanoclusters (AuNCs) via the peptide biomineralization method, which can elicit specific immunological responses. The as-prepared peptide-protected AuNCs (peptide-AuNCs) display strong red fluorescence, and more importantly, as compared to the peptide alone, the immune stimulatory ability of the resulting peptide-AuNCs can not only be retained, but can also be efficaciously enhanced. Moreover, through a dual-delivery of antigen peptides and cytosine-phosphate-guanine (CpG) oligodeoxynucleotides (ODNs), the as-prepared peptide-AuNC-CpG conjugates can also act as smart self-vaccines to assist in the generation of high immunostimulatory activity, and be applied as a probe for intracellular imaging. Both in vitro and in vivo studies provide strong evidence that the AuNC-based vaccines may be utilized as safe and efficient immunostimulatory agents that are able to prevent and/or treat a variety of ailments.We here report a facile one-pot synthesis of fluorescent gold nanoclusters (AuNCs) via the peptide biomineralization method, which can elicit specific immunological responses. The as-prepared peptide-protected AuNCs (peptide-AuNCs) display strong red fluorescence, and more importantly, as compared to the peptide alone, the immune stimulatory ability of the resulting peptide-AuNCs can not only be retained, but can also be efficaciously enhanced. Moreover, through a dual-delivery of antigen peptides and cytosine-phosphate-guanine (CpG) oligodeoxynucleotides (ODNs), the as-prepared peptide-AuNC-CpG conjugates can also act as smart self-vaccines to assist in the generation of high immunostimulatory activity, and be applied as a probe for intracellular imaging. Both in vitro and in vivo studies provide strong evidence that the AuNC-based vaccines may be utilized as safe and efficient immunostimulatory agents that are able to prevent and/or treat a variety of ailments. Electronic supplementary information (ESI

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.

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

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.

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.

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

Energy Technology Data Exchange (ETDEWEB)

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

2017-06-15

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

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

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

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

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.

Engineering ultrasmall water-soluble gold and silver nanoclusters for biomedical applications.

Science.gov (United States)

Luo, Zhentao; Zheng, Kaiyuan; Xie, Jianping

2014-05-25

Gold and silver nanoclusters or Au/Ag NCs with core sizes smaller than 2 nm have been an attractive frontier of nanoparticle research because of their unique physicochemical properties such as well-defined molecular structure, discrete electronic transitions, quantized charging, and strong luminescence. As a result of these unique properties, ultrasmall size, and good biocompatibility, Au/Ag NCs have great potential for a variety of biomedical applications, such as bioimaging, biosensing, antimicrobial agents, and cancer therapy. In this feature article, we will first discuss some critical biological considerations, such as biocompatibility and renal clearance, of Au/Ag NCs that are applied for biomedical applications, leading to some design criteria for functional Au/Ag NCs in the biological settings. According to these biological considerations, we will then survey some efficient synthetic strategies for the preparation of protein- and peptide-protected Au/Ag NCs with an emphasis on our recent contributions in this fast-growing field. In the last part, we will highlight some potential biomedical applications of these protein- and peptide-protected Au/Ag NCs. It is believed that with continued efforts to understand the interactions of biomolecule-protected Au/Ag NCs with the biological systems, scientists can largely realize the great potential of Au/Ag NCs for biomedical applications, which could finally pave their way towards clinical use.

Methanol, ethanol and hydrogen sensing using metal oxide and metal (TiO(2)-Pt) composite nanoclusters on GaN nanowires: a new route towards tailoring the selectivity of nanowire/nanocluster chemical sensors.

Science.gov (United States)

Aluri, Geetha S; Motayed, Abhishek; Davydov, Albert V; Oleshko, Vladimir P; Bertness, Kris A; Sanford, Norman A; Mulpuri, Rao V

2012-05-04

We demonstrate a new method for tailoring the selectivity of chemical sensors using semiconductor nanowires (NWs) decorated with metal and metal oxide multicomponent nanoclusters (NCs). Here we present the change of selectivity of titanium dioxide (TiO(2)) nanocluster-coated gallium nitride (GaN) nanowire sensor devices on the addition of platinum (Pt) nanoclusters. The hybrid sensor devices were developed by fabricating two-terminal devices using individual GaN NWs followed by the deposition of TiO(2) and/or Pt nanoclusters (NCs) using the sputtering technique. This paper present the sensing characteristics of GaN/(TiO(2)-Pt) nanowire-nanocluster (NWNC) hybrids and GaN/(Pt) NWNC hybrids, and compare their selectivity with that of the previously reported GaN/TiO(2) sensors. The GaN/TiO(2) NWNC hybrids showed remarkable selectivity to benzene and related aromatic compounds, with no measurable response for other analytes. Addition of Pt NCs to GaN/TiO(2) sensors dramatically altered their sensing behavior, making them sensitive only to methanol, ethanol and hydrogen, but not to any other chemicals we tested. The GaN/(TiO(2)-Pt) hybrids were able to detect ethanol and methanol concentrations as low as 100 nmol mol(-1) (ppb) in air in approximately 100 s, and hydrogen concentrations from 1 µmol mol(-1) (ppm) to 1% in nitrogen in less than 60 s. However, GaN/Pt NWNC hybrids showed limited sensitivity only towards hydrogen and not towards any alcohols. All these hybrid sensors worked at room temperature and are photomodulated, i.e. they responded to analytes only in the presence of ultraviolet (UV) light. We propose a qualitative explanation based on the heat of adsorption, ionization energy and solvent polarity to explain the observed selectivity of the different hybrids. These results are significant from the standpoint of applications requiring room-temperature hydrogen sensing and sensitive alcohol monitoring. These results demonstrate the tremendous potential for

Controllable 5-sulfosalicylic acid assisted solvothermal synthesis of monodispersed superparamagnetic Fe{sub 3}O{sub 4} nanoclusters with tunable size

Energy Technology Data Exchange (ETDEWEB)

Wang, Wentao [State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Tang, Bingtao, E-mail: tangbt@dlut.edu.cn [State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Wu, Suli; Gao, Zhanming; Ju, Benzhi [State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China); Teng, Xiaoxu [School of Chemistry and Chemical Engineering, Yangtze Normal University, Chongqing 408100 (China); Zhang, Shufen [State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024 (China)

2017-02-01

Monodispersed Fe{sub 3}O{sub 4} nanoclusters were synthesized in a one-pot solvothermal route with 5-sulfosalicylic acid (SSA) as the functional ligand in a mixed-solvent system of diethylene glycol/ethylene glycol (DEG/EG). Nucleation and aggregation growth model was responsible for the formation of secondary structure of the clusters. In the process, the size of the clusters can be effectively controlled by varying the amounts of SSA and the volume ratio of DEG/EG. The nanoclusters exhibited superparamagnetic properties with high saturation magnetization value of about 68.7 emu g{sup −1} at room temperature. The water-soluble small-molecule SSA grafted on the surface of Fe{sub 3}O{sub 4} nanocrystals rendered the superparamagnetic clusters dispersible in water, which is crucial for potential applications in biomedical fields. - Graphical abstract: 5-sulfosalicylic acid assisted solvothermal synthesis of monodispersed superparamagnetic Fe{sub 3}O{sub 4} nanoclusters with tunable size by a mixed-solvent system of DEG/EG. - Highlights: • Monodispersed Fe{sub 3}O{sub 4} nanoclusters were synthesized in a one-pot 5-sulfosalicylic acid assisted solvothermal route. • The size of the clusters are tunable by varying the amounts of 5-sulfosalicylic acid and the volume ratio of DEG/EG. • The nanoclusters exhibited superparamagnetic properties with high saturation magnetization value. • The 5-sulfosalicylic acid grafted Fe{sub 3}O{sub 4} nanoclusters can be dispersed in water.

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

Packing of ganglioside-phospholipid monolayers

DEFF Research Database (Denmark)

Majewski, J.; Kuhl, T.L.; Kjær, K.

2001-01-01

Using synchrotron grazing-incidence x-ray diffraction (GIXD) and reflectivity, the in-plane and out-of-plane structure of mixed ganglioside-phospholipid monolayers was investigated at the air-water interface. Mixed monolayers of 0, 5, 10, 20, and 100 mol% ganglioside GM, and the phospholipid...... monolayers did not affect hydrocarbon tail packing (fluidization or condensation of the hydrocarbon region). This is in contrast to previous investigations of lipopolymer-lipid mixtures, where the packing structure of phospholipid monolayers was greatly altered by the inclusion of lipids bearing hydrophilic...

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)

Phase transitions in surfactant monolayers

International Nuclear Information System (INIS)

Casson, B.D.

1998-01-01

Two-dimensional phase transitions have been studied in surfactant monolayers at the air/water interface by sum-frequency spectroscopy and ellipsometry. In equilibrium monolayers of medium-chain alcohols C n H 2n+1 OH (n = 9-14) a transition from a two-dimensional crystalline phase to a liquid was observed at temperatures above the bulk melting point. The small population of gauche defects in the solid phase increased only slightly at the phase transition. A model of the hydrocarbon chains as freely rotating rigid rods allowed the area per molecule and chain tilt in the liquid phase to be determined. The area per molecule, chain tilt and density of the liquid phase all increased with increasing chain length, but for each chain length the density was higher than in a bulk liquid hydrocarbon. In a monolayer of decanol adsorbed at the air/water interface a transition from a two-dimensional liquid to a gas was observed. A clear discontinuity in the coefficient of ellipticity as a function of temperature showed that the transition is first-order. This result suggests that liquid-gas phase transitions in surfactant monolayers may be more widespread than once thought. A solid-liquid phase transition has also been studied in mixed monolayers of dodecanol with an anionic surfactant (sodium dodecyl sulphate) and with a homologous series of cationic surfactants (alkyltrimethylammonium bromides: C n TABs, n = 12, 14, 16). The composition and structure of the mixed monolayers was studied above and below the phase transition. At low temperatures the mixed monolayers were as densely packed as a monolayer of pure dodecanol in its solid phase. At a fixed temperature the monolayers under-went a first-order phase transition to form a phase that was less dense and more conformationally disordered. The proportion of ionic surfactant in the mixed monolayer was greatest in the high temperature phase. As the chain length of the C n TAB increased the number of conformational defects

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.

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)

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.

"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.

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.

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2011-03-25

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

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

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.

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.

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

Directory of Open Access Journals (Sweden)

Xiang Ling

Full Text Available Zonulin protein is a newly discovered modulator which modulates the permeability of the intestinal epithelial barrier by disassembling intercellular tight junctions (TJ. Disruption of TJ is associated with neonatal necrotizing enterocolitis (NEC. It has been shown bifidobacterium could protect the intestinal barrier function and prophylactical administration of bifidobacterium has beneficial effects in NEC patients and animals. However, it is still unknown whether the zonulin is involved in the gut barrier dysfunction of NEC, and the protective mechanisms of bifidobacterium on intestinal barrier function are also not well understood. The present study aims to investigate the effects of bifidobacterium on intestinal barrier function, zonulin regulation, and TJ integrity both in LPS-induced enterocyte barrier injury of Caco-2 monolayers and in a rat NEC model. Our results showed bifidobacterium markedly attenuated the decrease in transepithelial electrical resistance and the increase in paracellular permeability in the Caco-2 monolayers treated with LPS (P < 0.01. Compared with the LPS group, bifidobacterium significantly decreased the production of IL-6 and TNF-α (P < 0.01 and suppressed zonulin release (P < 0.05. In addition, bifidobacterium pretreatment up-regulated occludin, claudin-3 and ZO-1 expression (P < 0.01 and also preserved these proteins localization at TJ compared with the LPS group. In the in vivo study, bifidobacterium decreased the incidence of NEC from 88 to 47% (P < 0.05 and reduced the severity in the NEC model. Increased levels of IL-6 and TNF-α in the ileum of NEC rats were normalized in bifidobacterium treated rats (P < 0.05. Moreover, administration of bifidobacterium attenuated the increase in intestinal permeability (P < 0.01, decreased the levels of serum zonulin (P < 0.05, normalized the expression and localization of TJ proteins in the ileum compared with animals with NEC. We concluded that bifidobacterium may

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.

Toward high value sensing: monolayer-protected metal nanoparticles in multivariable gas and vapor sensors.

Science.gov (United States)

Potyrailo, Radislav A

2017-08-29

For detection of gases and vapors in complex backgrounds, "classic" analytical instruments are an unavoidable alternative to existing sensors. Recently a new generation of sensors, known as multivariable sensors, emerged with a fundamentally different perspective for sensing to eliminate limitations of existing sensors. In multivariable sensors, a sensing material is designed to have diverse responses to different gases and vapors and is coupled to a multivariable transducer that provides independent outputs to recognize these diverse responses. Data analytics tools provide rejection of interferences and multi-analyte quantitation. This review critically analyses advances of multivariable sensors based on ligand-functionalized metal nanoparticles also known as monolayer-protected nanoparticles (MPNs). These MPN sensing materials distinctively stand out from other sensing materials for multivariable sensors due to their diversity of gas- and vapor-response mechanisms as provided by organic and biological ligands, applicability of these sensing materials for broad classes of gas-phase compounds such as condensable vapors and non-condensable gases, and for several principles of signal transduction in multivariable sensors that result in non-resonant and resonant electrical sensors as well as material- and structure-based photonic sensors. Such features should allow MPN multivariable sensors to be an attractive high value addition to existing analytical instrumentation.

Melamine dependent fluorescence of glutathione protected gold nanoclusters and ratiometric quantification of melamine in commercial cow milk and infant formula

Science.gov (United States)

Kalaiyarasan, Gopi; K, Anusuya; Joseph, James

2017-10-01

Companies processing the milk for the further production of powdered infant formulation normally check the protein level through a test measuring nitrogen content. The addition of melamine which is a nitrogen-rich organic chemical in milk increases the nitrogen content and therefore enhances its apparent protein content. However, the melamine causes kidney failure and death owing to the formation of kidney stone. Thus the determination of melamine in humans and milk products have gained great significance in recent years. The gold nanoclusters (AuNCs) have attracting features due to its unique electronic and optical properties like fluorescence nature. Therefore one can use AuNCs in the field of biosensor, bio-imaging, nanobiotechnology, drug delivery, diagnosis etc. We report, a new ratiometric nanosensor established for the selective and sensitive detection of melamine based optical sensing using glutathione stabilized AuNCs. The AuNCs were characterized by high-resolution transmission electron microscopy (HR-TEM), UV-visible and Photoluminescence (PL) spectroscopic techniques. In the presence of melamine, the PL intensity at 430 nm increases owing to the (turn-on) enhancement in fluorescence, whereas PL intensity at 610 nm decreases due to the melamine-induced aggregation and subsequent aggregation-enhanced emission quenching. The observed changes were ascribed to the hydrogen bonding interaction between melamine and AuNCs, which led to the aggregation of the nanoclusters. This was confirmed by dynamic light scattering and HR-TEM measurements. The present probe showed an extreme selectivity towards the determination of 28.2 μM melamine in the presence of 100-fold excess of common interfering molecules such as Alanine, Glycine, Glucose, Cystine etc. The proposed method was successfully applied to determine melamine in cow milk.

Superior Valley Polarization and Coherence of 2s Excitons in Monolayer WSe_{2}.

Science.gov (United States)

Chen, Shao-Yu; Goldstein, Thomas; Tong, Jiayue; Taniguchi, Takashi; Watanabe, Kenji; Yan, Jun

2018-01-26

We report the experimental observation of 2s exciton radiative emission from monolayer tungsten diselenide, enabled by hexagonal boron nitride protected high-quality samples. The 2s luminescence is highly robust and persists up to 150 K, offering a new quantum entity for manipulating the valley degree of freedom. Remarkably, the 2s exciton displays superior valley polarization and coherence than 1s under similar experimental conditions. This observation provides evidence that the Coulomb-exchange-interaction-driven valley-depolarization process, the Maialle-Silva-Sham mechanism, plays an important role in valley excitons of monolayer transition metal dichalcogenides.

Superior Valley Polarization and Coherence of 2 s Excitons in Monolayer WSe2

Science.gov (United States)

Chen, Shao-Yu; Goldstein, Thomas; Tong, Jiayue; Taniguchi, Takashi; Watanabe, Kenji; Yan, Jun

2018-01-01

We report the experimental observation of 2 s exciton radiative emission from monolayer tungsten diselenide, enabled by hexagonal boron nitride protected high-quality samples. The 2 s luminescence is highly robust and persists up to 150 K, offering a new quantum entity for manipulating the valley degree of freedom. Remarkably, the 2 s exciton displays superior valley polarization and coherence than 1 s under similar experimental conditions. This observation provides evidence that the Coulomb-exchange-interaction-driven valley-depolarization process, the Maialle-Silva-Sham mechanism, plays an important role in valley excitons of monolayer transition metal dichalcogenides.

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

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.

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.

First-principles study of MoS2 and MoSe2 nanoclusters in the framework of evolutionary algorithm and density functional theory

Science.gov (United States)

Hashemi, Zohreh; Rafiezadeh, Shohreh; Hafizi, Roohollah; Hashemifar, S. Javad; Akbarzadeh, Hadi

2018-04-01

Evolutionary algorithm is combined with full-potential ab initio calculations to investigate conformational space of (MoS2)n and (MoSe2)n (n = 1-10) nanoclusters and to identify the lowest energy structural isomers of these systems. It is argued that within both BLYP and PBE functionals, these nanoclusters favor sandwiched planar configurations, similar to their ideal planar sheets. The second order difference in total energy (Δ2 E) of the lowest energy isomers is computed to estimate the abundance of the clusters at different sizes and to determine the magic sizes of (MoS2)n and (MoSe2)n nanoclusters. In order to investigate the electronic properties of nanoclusters, their energy gap is calculated by several methods, including hybrid functionals (B3LYP and PBE0), GW approach, and Δ scf method. At the end, the vibrational modes of the lowest lying isomers are calculated by using the force constants method and the IR active modes of the systems are identified. The vibrational spectra are used to calculate the Helmholtz free energy of the systems and then to investigate abundance of the nanoclusters at finite temperatures.

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.

Methanol, ethanol and hydrogen sensing using metal oxide and metal (TiO2–Pt) composite nanoclusters on GaN nanowires: a new route towards tailoring the selectivity of nanowire/nanocluster chemical sensors

International Nuclear Information System (INIS)

Aluri, Geetha S; Motayed, Abhishek; Davydov, Albert V; Oleshko, Vladimir P; Bertness, Kris A; Sanford, Norman A; Mulpuri, Rao V

2012-01-01

We demonstrate a new method for tailoring the selectivity of chemical sensors using semiconductor nanowires (NWs) decorated with metal and metal oxide multicomponent nanoclusters (NCs). Here we present the change of selectivity of titanium dioxide (TiO 2 ) nanocluster-coated gallium nitride (GaN) nanowire sensor devices on the addition of platinum (Pt) nanoclusters. The hybrid sensor devices were developed by fabricating two-terminal devices using individual GaN NWs followed by the deposition of TiO 2 and/or Pt nanoclusters (NCs) using the sputtering technique. This paper present the sensing characteristics of GaN/(TiO 2 –Pt) nanowire–nanocluster (NWNC) hybrids and GaN/(Pt) NWNC hybrids, and compare their selectivity with that of the previously reported GaN/TiO 2 sensors. The GaN/TiO 2 NWNC hybrids showed remarkable selectivity to benzene and related aromatic compounds, with no measurable response for other analytes. Addition of Pt NCs to GaN/TiO 2 sensors dramatically altered their sensing behavior, making them sensitive only to methanol, ethanol and hydrogen, but not to any other chemicals we tested. The GaN/(TiO 2 –Pt) hybrids were able to detect ethanol and methanol concentrations as low as 100 nmol mol −1 (ppb) in air in approximately 100 s, and hydrogen concentrations from 1 µmol mol −1 (ppm) to 1% in nitrogen in less than 60 s. However, GaN/Pt NWNC hybrids showed limited sensitivity only towards hydrogen and not towards any alcohols. All these hybrid sensors worked at room temperature and are photomodulated, i.e. they responded to analytes only in the presence of ultraviolet (UV) light. We propose a qualitative explanation based on the heat of adsorption, ionization energy and solvent polarity to explain the observed selectivity of the different hybrids. These results are significant from the standpoint of applications requiring room-temperature hydrogen sensing and sensitive alcohol monitoring. These results demonstrate the tremendous potential

Influence of molecular packing on the corrosion inhibition properties of self-assembled octadecyltrichlorosilane monolayers on silicon

International Nuclear Information System (INIS)

Hsieh, Shuchen; Chao, Wei-Jay; Lin, Pei-Ying; Hsieh, Chiung-Wen

2014-01-01

Highlights: •Molecular packing plays an important role in determining SAM film properties. •Loose-packed OTS monolayers on silicon were corroded by exposure to KMnO 4 . •Dense-packed OTS SAM films exhibited excellent corrosion protection efficacy. -- Abstract: The corrosion inhibition properties of octadecyltrichlorosilane (OTS) self-assembled monolayers (SAMs) on silicon were investigated. Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), contact angle (CA), and lateral force microscopy (LFM) were used to determine the OTS film formation time, packing density, and corrosion protection efficacy. The OTS films reached adsorption saturation after 15 s; however, the molecular density continued to increase up to 24 h. The films were exposed to the strong oxidant KMnO 4 , and while 15-s film samples exhibited corrosion after a 1 min exposure, samples with films grown for 24 h were protected even after 24 h

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.

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...

Quasi-Dual-Packed-Kerneled Au49 (2,4-DMBT)27 Nanoclusters and the Influence of Kernel Packing on the Electrochemical Gap.

Science.gov (United States)

Liao, Lingwen; Zhuang, Shengli; Wang, Pu; Xu, Yanan; Yan, Nan; Dong, Hongwei; Wang, Chengming; Zhao, Yan; Xia, Nan; Li, Jin; Deng, Haiteng; Pei, Yong; Tian, Shi-Kai; Wu, Zhikun

2017-10-02

Although face-centered cubic (fcc), body-centered cubic (bcc), hexagonal close-packed (hcp), and other structured gold nanoclusters have been reported, it was unclear whether gold nanoclusters with mix-packed (fcc and non-fcc) kernels exist, and the correlation between kernel packing and the properties of gold nanoclusters is unknown. A Au 49 (2,4-DMBT) 27 nanocluster with a shell electron count of 22 has now been been synthesized and structurally resolved by single-crystal X-ray crystallography, which revealed that Au 49 (2,4-DMBT) 27 contains a unique Au 34 kernel consisting of one quasi-fcc-structured Au 21 and one non-fcc-structured Au 13 unit (where 2,4-DMBTH=2,4-dimethylbenzenethiol). Further experiments revealed that the kernel packing greatly influences the electrochemical gap (EG) and the fcc structure has a larger EG than the investigated non-fcc structure. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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)

Evaluation of monolayers and mixed monolayers formed from mercaptobenzothiazole and decanethiol as sensing platforms

International Nuclear Information System (INIS)

Mary Vergheese, T.; Berchmans, Sheela

2004-01-01

In this investigation, the characterisation of monolayer and mixed monolayers formed from mercaptobenzothiazole (MBT) and decanethiol (DT) has been carried out with cyclic voltammetry. The SAMs have been tested for their stability and electron transfer blocking properties. The redox probes used in the present study are [Fe(China) 6 ] 4- , [Ru(NH 3 ) 6 ] 2+ and Cu underpotential deposition (upd). The electron transfer kinetics is investigated in acid and neutral pH range. Electron transfer kinetics is altered by the nature of charge on the redox probe and the charge on the monolayer. Electron transfer kinetics of negatively charged redox probes like ferrocyanide ions is blocked when the surface pK a medium and at pK a >pH medium reversible features is observed for negatively charged probes. An exactly reverse effect is observed in the case of positively charged redox species like [Ru(NH 3 ) 6 ] 2+/3+ . Cu under potential deposition studies reflects the structural integrity and compactness of the SAM layer. The utility of these monolayers and mixed monolayer for selective sensing of dopamine is discussed based on their ability to discriminate between positively and negatively charged redox species at different pH

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

NARCIS (Netherlands)

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

2011-01-01

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

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.

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

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.

Redox-Triggered Bonding-Induced Emission of Thiol-Functionalized Gold Nanoclusters for Luminescence Turn-On Detection of Molecular Oxygen.

Science.gov (United States)

Ao, Hang; Feng, Hui; Zhao, Mengting; Zhao, Meizhi; Chen, Jianrong; Qian, Zhaosheng

2017-11-22

Most optical sensors for molecular oxygen were developed based on the quenching effect of the luminescence of oxygen-sensitive probes; however, the signal turn-off mode of these probes is undesirable to quantify and visualize molecular oxygen. Herein, we report a novel luminescence turn-on detection strategy for molecular oxygen via the specific oxygen-triggered bonding-induced emission of thiol-functionalized gold nanoclusters. Thiol-functionalized gold nanoclusters were prepared by a facile one-step synthesis, and as-prepared gold nanoclusters possess significant aggregation-induced emission (AIE) property. It is the first time to discover the oxygen-triggered bonding-induced emission (BIE) behavior of gold nanoclusters, which results in disulfide-linked covalent bonding assemblies with intensely red luminescence. This specific redox-triggered BIE is capable of quantitatively detecting dissolved oxygen in aqueous solution in a light-up manner, and trace amount of dissolved oxygen at ppb level is achieved based on this detection method. A facile and convenient test strip for oxygen detection was also developed to monitor molecular oxygen in a gas matrix. Covalent bonding-induced emission is proven to be a more efficient way to attain high brightness of AIEgens than a physical aggregation-induced emission process, and provides a more convenient and desirable detection method for molecular oxygen than the previous sensors.

Structures and shear response of lipid monolayers

International Nuclear Information System (INIS)

Dutta, P.; Ketterson, J.B.

1993-02-01

This report discusses our work during the last 3 years using x-ray diffraction and shear measurements to study lipid monolayers (membranes). The report is divided into: (1) structure: phase diagram of saturated fatty acid Langmuir monolayers, effect of head group interactions, studies of transferred monolayers (LB films); (2) mechanical properties: fiber=optic capillary wave probe and centrosymmetric trough, mechanical behavior of heneicosanoic acid monolayer phases

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

Synthesis and Structure Determination of a New Au₂₀ Nanocluster Protected by Tripodal Tetraphosphine Ligands

Energy Technology Data Exchange (ETDEWEB)

Chen, Jing [Brown Univ., Providence, RI (United States); Zhang, Qianfan [Brown Univ., Providence, RI (United States); Williard, Paul G. [Brown Univ., Providence, RI (United States); Wang, Lai-Sheng [Brown Univ., Providence, RI (United States)

2014-03-31

We report the synthesis and structure determination of a new Au₂₀ nanocluster coordinated by four tripodal tetraphosphine (PP₃) ligands {PP₃ = tris[2-(diphenylphosphino)ethyl]phosphine}. Single-crystal Xray crystallography and electrospray ionization mass spectrometry show that the cluster assembly can be formulated as [Au₂₀(PP₃)₄]Cl₄. The Au₂₀ cluster consists of an icosahedral Au₁₃ core and a seven-Au-atom partial outer shell arranged in a local C₃ symmetry. One PP₃ ligand coordinates to four Au atoms in the outer shell, while the other three PP₃ ligands coordinate to one Au atom from the outer shell and three Au atoms from the surface of the Au₁₃ core, giving rise to an overall chiral 16-electron Au cluster core with C3 symmetry.

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

Solution-processable septithiophene monolayer transistor

NARCIS (Netherlands)

Defaux, M.; Gholamrezaie, F.; Wang, J.; Kreyes, A.; Ziener, U.; Anokhin, D.V.; Ivanov, D.A.; Moser, A.; Neuhold, A.; Salzmann, I.; Resel, R.; Leeuw, de D.M.; Meskers, S.C.J.; Moeller, M.; Mourran, A.

2012-01-01

Septithiophene with endgroups designed to form liquid crystalline phases and allows controlled deposition of an electrically connected monolayer. Field effect mobilies mobilities of charge carriers and spectroscopic properties of the monolayer provide evidence of sustainable transport and

Solution-Processable Septithiophene Monolayer Transistor

NARCIS (Netherlands)

Defaux, Matthieu; Gholamrezaie, Fatemeh; Wang, Jingbo; Kreyes, Andreas; Ziener, Ulrich; Anokhin, Denis V.; Ivanov, Dimitri A.; Moser, Armin; Neuhold, Alfred; Salzmann, Ingo; Resel, Roland; de Leeuw, Dago M.; Meskers, Stefan C. J.; Moeller, Martin; Mourran, Ahmed

2012-01-01

Septithiophene with endgroups designed to form liquid crystalline phases and allows controlled deposition of an electrically connected monolayer. Field effect mobilies mobilities of charge carriers and spectroscopic properties of the monolayer provide evidence of sustainable transport and

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.

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

Evaluation of monolayers and mixed monolayers formed from mercaptobenzothiazole and decanethiol as sensing platforms

Energy Technology Data Exchange (ETDEWEB)

Mary Vergheese, T.; Berchmans, Sheela

2004-02-15

In this investigation, the characterisation of monolayer and mixed monolayers formed from mercaptobenzothiazole (MBT) and decanethiol (DT) has been carried out with cyclic voltammetry. The SAMs have been tested for their stability and electron transfer blocking properties. The redox probes used in the present study are [Fe(China){sub 6}]{sup 4-}, [Ru(NH{sub 3}){sub 6}]{sup 2+} and Cu underpotential deposition (upd). The electron transfer kinetics is investigated in acid and neutral pH range. Electron transfer kinetics is altered by the nature of charge on the redox probe and the charge on the monolayer. Electron transfer kinetics of negatively charged redox probes like ferrocyanide ions is blocked when the surface pK{sub a}pH{sub medium} reversible features is observed for negatively charged probes. An exactly reverse effect is observed in the case of positively charged redox species like [Ru(NH{sub 3}){sub 6}]{sup 2+/3+}. Cu under potential deposition studies reflects the structural integrity and compactness of the SAM layer. The utility of these monolayers and mixed monolayer for selective sensing of dopamine is discussed based on their ability to discriminate between positively and negatively charged redox species at different pH.

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.

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.)

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

The Size of Activating and Inhibitory Killer Ig-like Receptor Nanoclusters Is Controlled by the Transmembrane Sequence and Affects Signaling

Directory of Open Access Journals (Sweden)

Anna Oszmiana

2016-05-01

Full Text Available Super-resolution microscopy has revealed that immune cell receptors are organized in nanoscale clusters at cell surfaces and immune synapses. However, mechanisms and functions for this nanoscale organization remain unclear. Here, we used super-resolution microscopy to compare the surface organization of paired killer Ig-like receptors (KIR, KIR2DL1 and KIR2DS1, on human primary natural killer cells and cell lines. Activating KIR2DS1 assembled in clusters two-fold larger than its inhibitory counterpart KIR2DL1. Site-directed mutagenesis established that the size of nanoclusters is controlled by transmembrane amino acid 233, a lysine in KIR2DS1. Super-resolution microscopy also revealed two ways in which the nanoscale clustering of KIR affects signaling. First, KIR2DS1 and DAP12 nanoclusters are juxtaposed in the resting cell state but coalesce upon receptor ligation. Second, quantitative super-resolution microscopy revealed that phosphorylation of the kinase ZAP-70 or phosphatase SHP-1 is favored in larger KIR nanoclusters. Thus, the size of KIR nanoclusters depends on the transmembrane sequence and affects downstream signaling.

Janus Monolayer Transition-Metal Dichalcogenides.

Science.gov (United States)

Zhang, Jing; Jia, Shuai; Kholmanov, Iskandar; Dong, Liang; Er, Dequan; Chen, Weibing; Guo, Hua; Jin, Zehua; Shenoy, Vivek B; Shi, Li; Lou, Jun

2017-08-22

The crystal configuration of sandwiched S-Mo-Se structure (Janus SMoSe) at the monolayer limit has been synthesized and carefully characterized in this work. By controlled sulfurization of monolayer MoSe 2 , the top layer of selenium atoms is substituted by sulfur atoms, while the bottom selenium layer remains intact. The structure of this material is systematically investigated by Raman, photoluminescence, transmission electron microscopy, and X-ray photoelectron spectroscopy and confirmed by time-of-flight secondary ion mass spectrometry. Density functional theory (DFT) calculations are performed to better understand the Raman vibration modes and electronic structures of the Janus SMoSe monolayer, which are found to correlate well with corresponding experimental results. Finally, high basal plane hydrogen evolution reaction activity is discovered for the Janus monolayer, and DFT calculation implies that the activity originates from the synergistic effect of the intrinsic defects and structural strain inherent in the Janus structure.

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.

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...

Preparation and Photoluminescence of Tungsten Disulfide Monolayer

Directory of Open Access Journals (Sweden)

Yanfei Lv

2018-05-01

Full Text Available Tungsten disulfide (WS2 monolayer is a direct band gap semiconductor. The growth of WS2 monolayer hinders the progress of its investigation. In this paper, we prepared the WS2 monolayer through chemical vapor transport deposition. This method makes it easier for the growth of WS2 monolayer through the heterogeneous nucleation-and-growth process. The crystal defects introduced by the heterogeneous nucleation could promote the photoluminescence (PL emission. We observed the strong photoluminescence emission in the WS2 monolayer, as well as thermal quenching, and the PL energy redshift as the temperature increases. We attribute the thermal quenching to the energy or charge transfer of the excitons. The redshift is related to the dipole moment of WS2.

Preparation of Au Nanoclusters-Modified Polylactic Acid Fiber with Bright Red Fluorescence and its Use as Sensing Probe.

Science.gov (United States)

Zhu, Wenli; Li, Huili; Wan, Ajun; Liu, Lanbo

2017-01-01

In present work, the Au nanoclusters-modified polylactic acid fiber (PLA-Au NCs) with bright red fluorescence were fabricated by the encapsulation of Au nanoclusters (Au NCs) in the PLA fiber treated with H 2 O 2 . The Au 25 nanoclusters stabilized by bovine serum albumin (BSA-Au NCs) were prepared via an improved "green" synthetic routine. With pretreatment of the PLA fiber in H 2 O 2 concentration of 12 and 18 %, the as-prepared PLA-Au NCs exhibited brighter red emission with a strong peak centered at ~640 nm than BSA-Au NCs. The fluorescence can be quenched by nitric oxide (NO). A good linear relationship between the relative fluorescence quenching intensity of the as-prepared PLA-Au NCs and the concentration of NO can be obtained in the range of 0.0732 to 0.7320 mM, and the detection limit was 0.0070 mM.

{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.

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).

Structure and shear response of lipid monolayers

International Nuclear Information System (INIS)

Dutta, P.; Ketterson, J.B.

1990-02-01

Organic monolayers and multilayers are both scientifically fascinating and technologically promising; they are, however, both complex systems and relatively inaccessible to experimental probes. In this Progress Report, we describe our X-ray diffraction studies, which have given us substantial new information about the structures and phase transitions in monolayers on the surface of water; our use of these monolayers as a unique probe of the dynamics of wetting and spreading; and our studies of monolayer mechanical properties using a simple but effective technique available to anyone using the Wilhelmy method to measure surface tension

Monolayer Superconductivity in WS2

NARCIS (Netherlands)

Zheliuk, Oleksandr; Lu, Jianming; Yang, Jie; Ye, Jianting

Superconductivity in monolayer tungsten disulfide (2H-WS2) is achieved by strong electrostatic electron doping of an electric double-layer transistor (EDLT). Single crystals of WS2 are grown by a scalable method - chemical vapor deposition (CVD) on standard Si/SiO2 substrate. The monolayers are

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.

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.

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.

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.

Self-organization of nanocluster δ-layers at ion-beam-mixed Si-SiO2 interfaces

International Nuclear Information System (INIS)

Roentzsch, L.

2003-11-01

This diploma thesis presents experimental evidence of a theoretical concept which predicts the self-organization of δ-layers of silicon nanoclusters in the buried oxide of a MOS-like structure. This approach of ''bottom-up'' structuring might be of eminent importance in view of future semiconductor memory devices. Unconventionally, a 15 nm thin SiO 2 layer, which is enclosed by a 50 nm poly-Si capping layer and the Si substrate, is irradiated with Si + ions. Ion impact drives the system to a state far from thermodynamic equilibrium, i.e. the local composition of the target is modified to a degree unattainable in common processes. A region of SiO x (x 2 matrix at a distance of ∼3 nm from the Si substrate. The physical mechanisms of ion mixing of the two Si-SiO 2 interfaces and subsequent phase separation, which result in the desired sample structure, are elucidated from the viewpoint of computer simulations. In addition, experimental evidence is presented based on various methods, including TEM, RBS, and SIMS. A novel method of Si nanocluster decoration is of particular importance which applies Ge as contrast enhancing element in TEM studies of tiny Si nanoclusters. (orig.)

Suitability of using monolayered and multilayered emulsions for microencapsulation of ω-3 fatty acids by spray drying

DEFF Research Database (Denmark)

Jiménez-Martín, Estefanía; Gharsallaoui, Adem; Pérez-Palacios, Trinidad

2015-01-01

Microencapsulation of ω-3 fatty acids by spray drying was studied using both monolayered (lecithin) and multilayered (lecithin-chitosan) fish oil emulsions with maltodextrin as wall material. Stability of the multilayered emulsions was higher than the monolayered ones, and increased...... with the highest concentration of chitosan (1 % w/w), being related with lower detection of TBARS at high storage temperatures. Overall, this study shows the suitability of microencapsulating ω-3 fatty acids by spray drying using both monolayered and multilayered fish oil emulsions with maltodextrin as wall...... material. Multilayered microcapsules prepared with lecithin-chitosan emulsions provide a great protective effect against lipid oxidation of fish oil during storage at moderate to high temperatures (30 °C and 60 °C). These multilayered microcapsules could be therefore successfully used as a fish oil...

Effects of Graphene Monolayer Coating on the Optical Performance of Remote Phosphors

Science.gov (United States)

Yazdan Mehr, M.; Volgbert, S.; van Driel, W. D.; Zhang, G. Q.

2017-10-01

A graphene monolayer has been successfully coated on one side of a bisphenol-A-polycarbonate (BPA-PC) plate, used as a substrate for remote phosphor applications in light-emitting diode (LED)-based products. Using a photoresist transferring method, graphene sheet has been coated on BPA-PC plates. The results show that this graphene monolayer significantly improves the lifetime and performance of LEDs mainly by protecting them against external degradation factors such as moisture and oxygen. Also, LED-based products composed of graphene-coated BPA-PC plates exhibit longer stability with comparatively less loss of luminous efficiency. This method has great potential to significantly improve the reliability of not only LED-based products but also many other microelectronics packaging and components, in which moisture and oxygen are the key causes of failures.

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.

Disorder effect on heat capacity, self-diffusion coefficient, and choosing best potential model for melting temperature, in gold–copper bimetallic nanocluster with 55 atoms

International Nuclear Information System (INIS)

Taherkhani, Farid; Akbarzadeh, Hamed; Feyzi, Mostafa; Rafiee, Hamid Reza

2015-01-01

Molecular dynamics simulation has been implemented for doping effect on melting temperature, heat capacity, self-diffusion coefficient of gold–copper bimetallic nanostructure with 55 total gold and copper atom numbers and its bulk alloy. Trend of melting temperature for gold–copper bimetallic nanocluster is not same as melting temperature copper–gold bulk alloy. Molecular dynamics simulation of our result regarding bulk melting temperature is consistence with available experimental data. Molecular dynamics simulation shows that melting temperature of gold–copper bimetallic nanocluster increases with copper atom fraction. Semi-empirical potential model and quantum Sutton–Chen potential models do not change melting temperature trend with copper doping of gold–copper bimetallic nanocluster. Self-diffusion coefficient of copper atom is greater than gold atom in gold–copper bimetallic nanocluster. Semi-empirical potential within the tight-binding second moment approximation as new application potential model for melting temperature of gold–copper bulk structure shows better result in comparison with EAM, Sutton–Chen potential, and quantum Sutton–Chen potential models

Disorder effect on heat capacity, self-diffusion coefficient, and choosing best potential model for melting temperature, in gold–copper bimetallic nanocluster with 55 atoms

Energy Technology Data Exchange (ETDEWEB)

Taherkhani, Farid, E-mail: faridtaherkhani@gmail.com, E-mail: f.taherkhani@razi.ac.ir [Razi University, Department of Physical Chemistry (Iran, Islamic Republic of); Akbarzadeh, Hamed [Hakim Sabzevari University, Department of Chemistry (Iran, Islamic Republic of); Feyzi, Mostafa; Rafiee, Hamid Reza [Razi University, Department of Physical Chemistry (Iran, Islamic Republic of)

2015-01-15

Molecular dynamics simulation has been implemented for doping effect on melting temperature, heat capacity, self-diffusion coefficient of gold–copper bimetallic nanostructure with 55 total gold and copper atom numbers and its bulk alloy. Trend of melting temperature for gold–copper bimetallic nanocluster is not same as melting temperature copper–gold bulk alloy. Molecular dynamics simulation of our result regarding bulk melting temperature is consistence with available experimental data. Molecular dynamics simulation shows that melting temperature of gold–copper bimetallic nanocluster increases with copper atom fraction. Semi-empirical potential model and quantum Sutton–Chen potential models do not change melting temperature trend with copper doping of gold–copper bimetallic nanocluster. Self-diffusion coefficient of copper atom is greater than gold atom in gold–copper bimetallic nanocluster. Semi-empirical potential within the tight-binding second moment approximation as new application potential model for melting temperature of gold–copper bulk structure shows better result in comparison with EAM, Sutton–Chen potential, and quantum Sutton–Chen potential models.

Monolayer collapse regulating process of adsorption-desorption of palladium nanoparticles at fatty acid monolayers at the air-water interface.

Science.gov (United States)

Goto, Thiago E; Lopez, Ricardo F; Iost, Rodrigo M; Crespilho, Frank N; Caseli, Luciano

2011-03-15

In this paper, we investigate the affinity of palladium nanoparticles, stabilized with glucose oxidase, for fatty acid monolayers at the air-water interface, exploiting the interaction between a planar system and spheroids coming from the aqueous subphase. A decrease of the monolayer collapse pressure in the second cycle of interface compression proved that the presence of the nanoparticles causes destabilization of the monolayer in a mechanism driven by the interpenetration of the enzyme into the bilayer/multilayer structure formed during collapse, which is not immediately reversible after monolayer expansion. Surface pressure and surface potential-area isotherms, as well as infrared spectroscopy [polarization modulation infrared reflection adsorption spectroscopy (PM-IRRAS)] and deposition onto solid plates as Langmuir-Blodgett (LB) films, were employed to construct a model in which the nanoparticle has a high affinity for the hydrophobic core of the structure formed after collapse, which provides a slow desorption rate from the interface after monolayer decompression. This may have important consequences on the interaction between the metallic particles and fatty acid monolayers, which implies the regulation of the multifunctional properties of the hybrid material.

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...

Monolayer MoS2 heterojunction solar cells

KAUST Repository

Tsai, Menglin

2014-08-26

We realized photovoltaic operation in large-scale MoS2 monolayers by the formation of a type-II heterojunction with p-Si. The MoS 2 monolayer introduces a built-in electric field near the interface between MoS2 and p-Si to help photogenerated carrier separation. Such a heterojunction photovoltaic device achieves a power conversion efficiency of 5.23%, which is the highest efficiency among all monolayer transition-metal dichalcogenide-based solar cells. The demonstrated results of monolayer MoS 2/Si-based solar cells hold the promise for integration of 2D materials with commercially available Si-based electronics in highly efficient devices. © 2014 American Chemical Society.

The Relationship between Nanocluster Precipitation and Thermal Conductivity in Si/Ge Amorphous Multilayer Films: Effects of Cu Addition

Directory of Open Access Journals (Sweden)

Ahmad Ehsan Mohd Tamidi

2016-01-01

Full Text Available We have used a molecular dynamics technique to simulate the relationship between nanocluster precipitation and thermal conductivity in Si/Ge amorphous multilayer films, with and without Cu addition. In the study, the Green-Kubo equation was used to calculate thermal conductivity in these materials. Five specimens were prepared: Si/Ge layers, Si/(Ge + Cu layers, (Si + Cu/(Ge + Cu layers, Si/Cu/Ge/Cu layers, and Si/Cu/Ge layers. The number of precipitated nanoclusters in these specimens, which is defined as the number of four-coordinate atoms, was counted along the lateral direction of the specimens. The observed results of precipitate formation were considered in relation to the thermal conductivity results. Enhancement of precipitation of nanoclusters by Cu addition, that is, densification of four-coordinate atoms, can prevent the increment of thermal conductivity. Cu dopant increases the thermal conductivity of these materials. Combining these two points, we concluded that Si/Cu/Ge is the best structure to improve the conversion efficiency of the Si/Ge amorphous multilayer films.

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.

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

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

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

Enhanced charge collection and photocatalysis performance of CdS and PbS nanoclusters co-sensitized TiO{sub 2} porous film

Energy Technology Data Exchange (ETDEWEB)

Zhang, Miao; Xu, Yanyan; Gong, Zezhou; Tao, Jiajia [School of Physics & Material Science, Anhui University, Hefei 230601 (China); Sun, Zhaoqi, E-mail: szq@ahu.edu.cn [School of Physics & Material Science, Anhui University, Hefei 230601 (China); Lv, Jianguo [School of Electronic & Information Engineering, Hefei Normal University, Hefei, 230601 (China); National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Sciences, Shanghai 200083 (China); Chen, Xiaoshuang [National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese Academy of Sciences, Shanghai 200083 (China); Jiang, Xishun [School of Physics & Material Science, Anhui University, Hefei 230601 (China); School of Mechanical & Electronic Engineering, Chuzhou University, Chuzhou, 239000 (China); He, Gang; Wang, Peihong; Meng, Fanming [School of Physics & Material Science, Anhui University, Hefei 230601 (China)

2015-11-15

A novel translucent TiO{sub 2} porous film was prepared through etched method. The CdS, PbS and CdS/PbS nanoclusters were imbedded on TiO{sub 2} porous film by successive ionic layer adsorption and reaction method. Microstructure, morphology, optical and photoelectron-chemical properties of the as-synthesized thin films were investigated systematically. XRD and morphology analysis showed that PbS or CdS nanoclusters have been attached to the TiO{sub 2} porous films. It was found that the energy band gap of TiO{sub 2} porous film decreased from 3.46 to 3.2 eV after sensitized with nanoclusters. The photocurrent density of ITO/TiO{sub 2} photoelectrode increased from 0.017 to 0.28 mA/cm{sup 2} after co-sensitized with CdS and PbS nanoclusters. Besides, the photoelectrode sensitized with two sorts of nanoclusters showed evident higher photocurrent density than which sensitized just one sort of nanoclusters. The photocurrent density of ITO/TiO{sub 2}/PbS and TO/TiO{sub 2}/CdS photoelectrode was 0.11 mA/cm{sup 2} and 0.22 mA/cm{sup 2} respectively. 0.28 mA/cm{sup 2} can be obtained by ITO/TiO{sub 2}/CdS/PbS photoelectrode. The results showed that the optical and photoelectrochemistry properties and phtotcatalysis performance of TiO{sub 2} porous film were greatly improved by co-sensitized with CdS and PbS nanoclusters. - Graphical abstract: When CdS and PbS were brought in the cascade structure, such a Fermi level alignment causes upward and downward shifts of the band edges for PbS and CdS, respectively. Therefore the resulting band edges for the ITO/TiO{sub 2}/CdS/PbS devices are inferred to have a stepwise structure. The elevated conduction band edge of PbS provides a higher driving force for the injection of photogenerated electrons from PbS to CdS as well as the injection of excited holes from CdS to PbS. Such a structure offers efficient separation and transport of the excited electrons and holes. - Highlights: • Ti films were obtained from direct current

Lateral pressure profiles in lipid monolayers

NARCIS (Netherlands)

Baoukina, Svetlana; Marrink, Siewert J.; Tieleman, D. Peter

2010-01-01

We have used molecular dynamics simulations with coarse-grained and atomistic models to study the lateral pressure profiles in lipid monolayers. We first consider simple oil/air and oil/water interfaces, and then proceed to lipid monolayers at air/water and oil/water interfaces. The results are

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.

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.

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.

Phosphate-mediated electrochemical adsorption of cisplatin on gold electrodes

International Nuclear Information System (INIS)

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

2017-01-01

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

Large Friction Anisotropy of a Polydiacetylene Monolayer

International Nuclear Information System (INIS)

Burns, A.R.; Carpick, R.W.; Sasaki, D.Y.

1999-01-01

Friction force microscopy measurements of a polydiacetylene monolayer film reveal a 300% friction anisotropy that is correlated with the film structure. The film consists of a monolayer of the red form of N-(2-ethanol)- 10,12 pentacosadiynamide, prepared on a Langmuir trough and deposited on a mica substrate. As confirmed by atomic force microscopy and fluorescence microscopy, the monolayer consists of domains of linearly oriented conjugated backbones with pendant hydrocarbon side chains above and below the backbones. Maximum friction occurs when the sliding direction is perpendicular to the backbone. We propose that the backbones impose anisotropic packing of the hydrocarbon side chains which leads to the observed friction anisotropy. Friction anisotropy is therefore a sensitive, optically-independent indicator of polymer backbone direction and monolayer structural properties

Faceted titania nanocrystals doped with indium oxide nanoclusters as a superior candidate for sacrificial hydrogen evolution without any noble-metal cocatalyst under solar irradiation.

Science.gov (United States)

Amoli, Vipin; Sibi, Malayil Gopalan; Banerjee, Biplab; Anand, Mohit; Maurya, Abhayankar; Farooqui, Saleem Akhtar; Bhaumik, Asim; Sinha, Anil Kumar

2015-01-14

Development of unique nanoheterostructures consisting of indium oxide nanoclusters like species doped on the TiO2 nanocrystals surfaces with {101} and {001} exposed facets, resulted in unprecedented sacrificial hydrogen production (5.3 mmol h(-1) g(-1)) from water using methanol as a sacrificial agent, under visible light LED source and AM 1.5G solar simulator (10.3 mmol h(-1) g(-1)), which is the highest H2 production rate ever reported for titania based photocatalysts, without using any noble metal cocatalyst. X-ray photoelectron spectroscopy (XPS) analysis of the nanostructures reveals the presence of Ti-O-In and In-O-In like species on the surface of nanostructures. Electron energy-loss spectroscopy (EELS) elemental mapping and EDX spectroscopy techniques combined with transmission electron microscope evidenced the existence of nanoheterostructures. XPS, EELS, EDX, and HAADF-STEM tools collectively suggest the presence of indium oxide nanoclusters like species on the surface of TiO2 nanostructures. These indium oxide nanocluster doped TiO2 (In2O3/T{001}) single crystals with {101} and {001} exposed facets exhibited 1.3 times higher visible light photocatalytic H2 production than indium oxide nanocluster doped TiO2 nanocrystals with only {101}facets (In2O3/T{101}) exposed. The remarkable photocatalytic activity of the obtained nanoheterostructures is attributed to the combined synergetic effect of indium oxide nanoclusters interacting with the titania surface, enhanced visible light response, high crystallinity, and unique structural features.

Thermal conductivity of a h-BCN monolayer.

Science.gov (United States)

Zhang, Ying-Yan; Pei, Qing-Xiang; Liu, Hong-Yuan; Wei, Ning

2017-10-18

A hexagonal graphene-like boron-carbon-nitrogen (h-BCN) monolayer, a new two-dimensional (2D) material, has been synthesized recently. Herein we investigate for the first time the thermal conductivity of this novel 2D material. Using molecular dynamics simulations based on the optimized Tersoff potential, we found that the h-BCN monolayers are isotropic in the basal plane with close thermal conductivity magnitudes. Though h-BCN has the same hexagonal lattice as graphene and hexagonal boron nitride (h-BN), it exhibits a much lower thermal conductivity than the latter two materials. In addition, the thermal conductivity of h-BCN monolayers is found to be size-dependent but less temperature-dependent. Modulation of the thermal conductivity of h-BCN monolayers can also be realized by strain engineering. Compressive strain leads to a monotonic decrease in the thermal conductivity while the tensile strain induces an up-then-down trend in the thermal conductivity. Surprisingly, the small tensile strain can facilitate the heat transport of the h-BCN monolayers.

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.

Nonequilibrium 2-hydroxyoctadecanoic acid monolayers: effect of electrolytes.

Science.gov (United States)

Lendrum, Conrad D; Ingham, Bridget; Lin, Binhua; Meron, Mati; Toney, Michael F; McGrath, Kathryn M

2011-04-19

2-Hydroxyacids display complex monolayer phase behavior due to the additional hydrogen bonding afforded by the presence of the second hydroxy group. The placement of this group at the position α to the carboxylic acid functionality also introduces the possibility of chelation, a utility important in crystallization including biomineralization. Biomineralization, like many biological processes, is inherently a nonequilibrium process. The nonequilibrium monolayer phase behavior of 2-hydroxyoctadecanoic acid was investigated on each of pure water, calcium chloride, sodium bicarbonate and calcium carbonate crystallizing subphases as a precursor study to a model calcium carbonate biomineralizing system, each at a pH of ∼6. The role of the bicarbonate co-ion in manipulating the monolayer structure was determined by comparison with monolayer phase behavior on a sodium chloride subphase. Monolayer phase behavior was probed using surface pressure/area isotherms, surface potential, Brewster angle microscopy, and synchrotron-based grazing incidence X-ray diffraction and X-ray reflectivity. Complex phase behavior was observed for all but the sodium chloride subphase with hydrogen bonding, electrostatic and steric effects defining the symmetry of the monolayer. On a pure water subphase hydrogen bonding dominates with three phases coexisting at low pressures. Introduction of calcium ions into the aqueous subphase ensures strong cation binding to the surfactant head groups through chelation. The monolayer becomes very unstable in the presence of bicarbonate ions within the subphase due to short-range hydrogen bonding interactions between the monolayer and bicarbonate ions facilitated by the sodium cation enhancing surfactant solubility. The combined effects of electrostatics and hydrogen bonding are observed on the calcium carbonate crystallizing subphase. © 2011 American Chemical Society

Zitterbewegung in monolayer silicene in a magnetic field

International Nuclear Information System (INIS)

Romera, E.; Roldán, J.B.; Santos, F. de los

2014-01-01

We study the Zitterbewegung in monolayer silicene under a perpendicular magnetic field. Using an effective Hamiltonian, we have investigated the autocorrelation function and the density currents in this material. Moreover, we have analyzed other types of periodicities of the system (classical and revival times). Finally, the above results are compared with their counterparts in two other monolayer materials subject to a magnetic field: graphene and MoS 2 . - Highlights: • We study Zitterbewegung in monolayer silicene in a magnetic field. • We have analyzed other types of periodicities in silicene. • The above results are compared with other monolayer materials (graphene and MoS 2 )

Zitterbewegung in monolayer silicene in a magnetic field

Energy Technology Data Exchange (ETDEWEB)

Romera, E. [Departamento de Física Atómica, Molecular y Nuclear and Instituto Carlos I de Física Teórica y Computacional, Universidad de Granada, Fuentenueva s/n, 18071 Granada (Spain); Roldán, J.B. [Departamento de Electrónica y Tecnología de Computadores and CITIC, Universidad de Granada, Fuentenueva s/n, 18071 Granada (Spain); Santos, F. de los [Departamento de Electromagnetismo y Física de la Materia, and Instituto Carlos I de Física Teórica y Computacional, Universidad de Granada, Fuentenueva s/n, 18071 Granada (Spain)

2014-07-04

We study the Zitterbewegung in monolayer silicene under a perpendicular magnetic field. Using an effective Hamiltonian, we have investigated the autocorrelation function and the density currents in this material. Moreover, we have analyzed other types of periodicities of the system (classical and revival times). Finally, the above results are compared with their counterparts in two other monolayer materials subject to a magnetic field: graphene and MoS{sub 2}. - Highlights: • We study Zitterbewegung in monolayer silicene in a magnetic field. • We have analyzed other types of periodicities in silicene. • The above results are compared with other monolayer materials (graphene and MoS{sub 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...

Testing the effectiveness of monolayers under wind and wave conditions.

Science.gov (United States)

Palada, C; Schouten, P; Lemckert, C

2012-01-01

Monolayers are highly desirable for their evaporation reducing capabilities due to their relatively minimal cost and ease of application. Despite these positive attributes, monolayers have consistently failed to perform effectively due to the harsh wind and wave conditions prevalent across real-world water reserves. An exhaustive and consistent study testing the influence of wind and wave combinations on monolayer performance has yet to be presented in the literature. To remedy this, the effect of simultaneous wind and wave conditions on a benchmark high-performance monolayer (octadecanol suspension, CH(3)(CH(2))(16)CH(2)OH) has been analysed. Subjected only to waves, the monolayer remained intact due to its innate ability to compress and expand. However, the constant simultaneous application of wind and waves caused the monolayer to break up and gather down-wind where it volatilised over time. At wind speeds above 1.3 m s(-1) the monolayer was completely ineffective. For wind speeds below this threshold, the monolayer had an influence on the evaporation rate dependent on wind speed. From these results a series of application protocols can now be developed for the optimised deployment of monolayers in real-world water reserves. This will be of interest to private, commercial and government organisations involved in the storage and management of water resources.

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

Interfacial synthesis of polyethyleneimine-protected copper nanoclusters: Size-dependent tunable photoluminescence, pH sensor and bioimaging.

Science.gov (United States)

Wang, Chan; Yao, Yagang; Song, Qijun

2016-04-01

The copper nanoclusters (CuNCs) offer excellent potential as functional biological probes due to their unique photoluminescence (PL) properties. Herein, CuNCs capped with hyperbranched polyethylenimine (PEI) were prepared by the interfacial etching approach. The resultant PEI-CuNCs exhibited good dispersion and strong fluorescence with high quantum yields (QYs, up to 7.5%), which would be endowed for bioimaging system. By changing the reaction temperatures from 25 to 150 °C, the size of PEI-CuNCs changed from 1.8 to 3.5 nm, and thus tunable PL were achieved, which was confirmed by transmission electron microscopy (TEM) imagings and PL spectra. Besides, PEI-CuNCs had smart absorption characteristics that the color changes from colorless to blue with changing the pH value from 2.0 to 13.2, and thus they could be used as color indicator for pH detection. In addition, the PEI-CuNCs exhibited good biocompatibility and low cytotoxicity to 293T cells through MTT assay. Owing to the positively charged of PEI-CuNCs surface, they had the ability to capture DNA, and the PEI-CuNCs/DNA complexes could get access to cells for efficient gene expression. Armed with these attractive properties, the synthesized PEI-CuNCs are quite promising in biological applications. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Controlled electrodeposition of Au monolayer film on ionic liquid

Energy Technology Data Exchange (ETDEWEB)

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

2016-05-15

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

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

Evidence of indirect gap in monolayer WSe2

KAUST Repository

Hsu, Wei-Ting

2017-10-09

Monolayer transition metal dichalcogenides, such as MoS2 and WSe2, have been known as direct gap semiconductors and emerged as new optically active materials for novel device applications. Here we reexamine their direct gap properties by investigating the strain effects on the photoluminescence of monolayer MoS2 and WSe2. Instead of applying stress, we investigate the strain effects by imaging the direct exciton populations in monolayer WSe2–MoS2 and MoSe2–WSe2 lateral heterojunctions with inherent strain inhomogeneity. We find that unstrained monolayer WSe2 is actually an indirect gap material, as manifested in the observed photoluminescence intensity–energy correlation, from which the difference between the direct and indirect optical gaps can be extracted by analyzing the exciton thermal populations. Our findings combined with the estimated exciton binding energy further indicate that monolayer WSe2 exhibits an indirect quasiparticle gap, which has to be reconsidered in further studies for its fundamental properties and device applications.

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

Science.gov (United States)

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

2011-04-06

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

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.

Large-area and bright pulsed electroluminescence in monolayer semiconductors

KAUST Repository

Lien, Der-Hsien; Amani, Matin; Desai, Sujay B.; Ahn, Geun Ho; Han, Kevin; He, Jr-Hau; Ager, Joel W.; Wu, Ming C.; Javey, Ali

2018-01-01

Transition-metal dichalcogenide monolayers have naturally terminated surfaces and can exhibit a near-unity photoluminescence quantum yield in the presence of suitable defect passivation. To date, steady-state monolayer light-emitting devices suffer from Schottky contacts or require complex heterostructures. We demonstrate a transient-mode electroluminescent device based on transition-metal dichalcogenide monolayers (MoS, WS, MoSe, and WSe) to overcome these problems. Electroluminescence from this dopant-free two-terminal device is obtained by applying an AC voltage between the gate and the semiconductor. Notably, the electroluminescence intensity is weakly dependent on the Schottky barrier height or polarity of the contact. We fabricate a monolayer seven-segment display and achieve the first transparent and bright millimeter-scale light-emitting monolayer semiconductor device.

Large-area and bright pulsed electroluminescence in monolayer semiconductors

KAUST Repository

Lien, Der-Hsien

2018-04-04

Transition-metal dichalcogenide monolayers have naturally terminated surfaces and can exhibit a near-unity photoluminescence quantum yield in the presence of suitable defect passivation. To date, steady-state monolayer light-emitting devices suffer from Schottky contacts or require complex heterostructures. We demonstrate a transient-mode electroluminescent device based on transition-metal dichalcogenide monolayers (MoS, WS, MoSe, and WSe) to overcome these problems. Electroluminescence from this dopant-free two-terminal device is obtained by applying an AC voltage between the gate and the semiconductor. Notably, the electroluminescence intensity is weakly dependent on the Schottky barrier height or polarity of the contact. We fabricate a monolayer seven-segment display and achieve the first transparent and bright millimeter-scale light-emitting monolayer semiconductor device.

Protonation of octadecylamine Langmuir monolayer by adsorption of halide counterions

Science.gov (United States)

Sung, Woongmo; Avazbaeva, Zaure; Lee, Jonggwan; Kim, Doseok

Langmuir monolayer consisting of octadecylamine (C18H37NH2, ODA) was investigated by heterodyne vibrational sum-frequency generation (HD-VSFG) spectroscopy in conjunction with surface pressure-area (π- A) isotherm, and the result was compared with that from cationic-lipid (DPTAP) Langmuir monolayer. In case of ODA monolayer on pure water, both SF intensity of water OH band and the surface pressure were significantly smaller than those of the DPTAP monolayer implying that only small portion of the amine groups (-NH3+ is protonated in the monolayer. In the presence of sodium halides (NaCl and NaI) in the subphase water, it was found that the sign of Imχ (2) of water OH band remained the same as that of the ODA monolayer on pure water, but there was a substantial increase in the SF amplitude. From this, we propose that surface excess of the halide counterions (Cl- and I-) makes the solution condition near the ODA monolayer/water interface more acidic so that ODA molecules in the monolayer are more positively charged, which works to align the water dipoles at the interface.

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

Defects and oxidation of group-III monochalcogenide monolayers

Science.gov (United States)

Guo, Yu; Zhou, Si; Bai, Yizhen; Zhao, Jijun

2017-09-01

Among various two-dimensional (2D) materials, monolayer group-III monochalcogenides (GaS, GaSe, InS, and InSe) stand out owing to their potential applications in microelectronics and optoelectronics. Devices made of these novel 2D materials are sensitive to environmental gases, especially O2 molecules. To address this critical issue, here we systematically investigate the oxidization behaviors of perfect and defective group-III monochalcogenide monolayers by first-principles calculations. The perfect monolayers show superior oxidation resistance with large barriers of 3.02-3.20 eV for the dissociation and chemisorption of O2 molecules. In contrast, the defective monolayers with single chalcogen vacancy are vulnerable to O2, showing small barriers of only 0.26-0.36 eV for the chemisorption of an O2 molecule. Interestingly, filling an O2 molecule to the chalcogen vacancy of group-III monochalcogenide monolayers could preserve the electronic band structure of the perfect system—the bandgaps are almost intact and the carrier effective masses are only moderately disturbed. On the other hand, the defective monolayers with single vacancies of group-III atoms carry local magnetic moments of 1-2 μB. These results help experimental design and synthesis of group-III monochalcogenides based 2D devices with high performance and stability.

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.

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)

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...

Characterization of iron surface modified by 2-mercaptobenzothiazole self-assembled monolayers

Energy Technology Data Exchange (ETDEWEB)

Feng Yuanyuan [Department of Chemistry, Shandong University, Jinan 250100 (China); Chen Shenhao [Department of Chemistry, Shandong University, Jinan 250100 (China) and State Key Laboratory for Corrosion and Protection, Shenyang 110016 (China)]. E-mail: shchen@sdu.edu.cn; Zhang Honglin [Department of Chemistry, Qufu Normal University, Qufu 273165 (China); Li Ping [Department of Chemistry, Shandong University, Jinan 250100 (China); Wu Ling [Department of Chemistry, Shandong University, Jinan 250100 (China); Guo Wenjuan [Department of Chemistry, Shandong University, Jinan 250100 (China)

2006-12-30

A self-assembled monolayer of 2-mercaptobenzothiazole (MBT) adsorbed on the iron surface was prepared. The films were characterized by electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared reflection spectroscopy (FT-IR) and scanning electron microscopy (SEM). Besides, the microcalorimetry method was utilized to study the self-assembled process on iron surface and the adsorption mechanism was discussed from the power-time curve. The results indicated that MBT was able to form a film spontaneously on iron surface and the presence of it could protect iron from corrosion effectively. However, the assembling time and the concentration influence the protection efficiency. Quantum chemical calculations, according to which adsorption mechanism was discussed, could explain the experimental results to some extent.

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

Science.gov (United States)

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

2013-09-01

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

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

Energy Technology Data Exchange (ETDEWEB)

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

2013-09-15

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

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)

Exploring the atomic structure of 1.8 nm monolayer-protected gold clusters with aberration-corrected STEM

Energy Technology Data Exchange (ETDEWEB)

Liu, Jian; Jian, Nan; Ornelas, Isabel; Pattison, Alexander J. [Nanoscale Physics Research Laboratory, School of Physics and Astronomy, University of Birmingham, Birmingham B15 2TT (United Kingdom); Lahtinen, Tanja; Salorinne, Kirsi [Department of Chemistry, Nanoscience Center, University of Jyväskylä, FI-40014 Jyväskylä (Finland); Häkkinen, Hannu [Department of Chemistry, Nanoscience Center, University of Jyväskylä, FI-40014 Jyväskylä (Finland); Department of Physics, Nanoscience Center, University of Jyväskylä, FI-40014 Jyväskylä (Finland); Palmer, Richard E., E-mail: richardepalmerwork@yahoo.com [Nanoscale Physics Research Laboratory, School of Physics and Astronomy, University of Birmingham, Birmingham B15 2TT (United Kingdom)

2017-05-15

Monolayer-protected (MP) Au clusters present attractive quantum systems with a range of potential applications e.g. in catalysis. Knowledge of the atomic structure is needed to obtain a full understanding of their intriguing physical and chemical properties. Here we employed aberration-corrected scanning transmission electron microscopy (ac-STEM), combined with multislice simulations, to make a round-robin investigation of the atomic structure of chemically synthesised clusters with nominal composition Au{sub 144}(SCH{sub 2}CH{sub 2}Ph){sub 60} provided by two different research groups. The MP Au clusters were “weighed” by the atom counting method, based on their integrated intensities in the high angle annular dark field (HAADF) regime and calibrated exponent of the Z dependence. For atomic structure analysis, we compared experimental images of hundreds of clusters, with atomic resolution, against a variety of structural models. Across the size range 123–151 atoms, only 3% of clusters matched the theoretically predicted Au{sub 144}(SR){sub 60} structure, while a large proportion of the clusters were amorphous (i.e. did not match any model structure). However, a distinct ring-dot feature, characteristic of local icosahedral symmetry, was observed in about 20% of the clusters. - Highlights: • Chemically synthesised gold clusters were “weighed” by atom counting to get true size. • Image simulations show a few percent of clusters have the predicted atomic structure. • But a specific ring-dot feature indicates local icosahedral order in many clusters.

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.

Integrated circuits based on conjugated polymer monolayer.

Science.gov (United States)

Li, Mengmeng; Mangalore, Deepthi Kamath; Zhao, Jingbo; Carpenter, Joshua H; Yan, Hongping; Ade, Harald; Yan, He; Müllen, Klaus; Blom, Paul W M; Pisula, Wojciech; de Leeuw, Dago M; Asadi, Kamal

2018-01-31

It is still a great challenge to fabricate conjugated polymer monolayer field-effect transistors (PoM-FETs) due to intricate crystallization and film formation of conjugated polymers. Here we demonstrate PoM-FETs based on a single monolayer of a conjugated polymer. The resulting PoM-FETs are highly reproducible and exhibit charge carrier mobilities reaching 3 cm 2  V -1  s -1 . The high performance is attributed to the strong interactions of the polymer chains present already in solution leading to pronounced edge-on packing and well-defined microstructure in the monolayer. The high reproducibility enables the integration of discrete unipolar PoM-FETs into inverters and ring oscillators. Real logic functionality has been demonstrated by constructing a 15-bit code generator in which hundreds of self-assembled PoM-FETs are addressed simultaneously. Our results provide the state-of-the-art example of integrated circuits based on a conjugated polymer monolayer, opening prospective pathways for bottom-up organic electronics.

A MOLECULAR-DYNAMICS STUDY OF LECITHIN MONOLAYERS

NARCIS (Netherlands)

AHLSTROM, P; BERENDSEN, HJC

1993-01-01

Two monolayers of didecanoyllecithin at the air-water interface have been studied using molecular dynamics simulations. The model system consisted of two monolayers of 42 lecithin molecules each separated by a roughly 4 nm thick slab of SPC water. The area per lecithin molecule was 0.78 nm(2)

WSe2 Monolayer

KAUST Repository

Zhang, Shuai; Wang, Chen-Guang; Li, Ming-yang; Huang, Di; Li, Lain-Jong; Ji, Wei; Wu, Shiwei

2017-01-01

dichalcogenide materials, intrinsic defects in WSe2 arise surprisingly from single tungsten vacancies, leading to the hole (p-type) doping. Furthermore, we found these defects to dominate the excitonic emission of the WSe2 monolayer at low temperature. Our work

Orientational epitaxy in adsorbed monolayers

International Nuclear Information System (INIS)

Novaco, A.D.; McTague, J.P.

1977-01-01

The ground state for adsorbed monolayers on crystalline substrates is shown to involve a definite relative orientation of the substrate and adsorbate crystal axes, even when the relative lattice parameters are incommensurate. The rotation angle which defines the structure of the monolayer-substrate system is determined by the competition between adsorbate-substrate and adsorbate-adsorbate energy terms, and is generally not a symmetry angle. Numerical predictions are presented for the rare gas-graphite systems, whose interaction potentials are rather well known. Recent LEED data for some of these systems appear to corroborate these predictions

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

Science.gov (United States)

Miura, Manabu; Fujimoto, Keiji

2006-12-01

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

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

Science.gov (United States)

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

2004-06-22

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

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

Metal ion interaction with phosphorylated tyrosine analogue monolayers on gold.

Science.gov (United States)

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

2006-11-23

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

Mechanical and electronic properties of Janus monolayer transition metal dichalcogenides

Science.gov (United States)

Shi, Wenwu; Wang, Zhiguo

2018-05-01

The mechanical and electronic properties of Janus monolayer transition metal dichalcogenides MXY (M  =  Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W; X/Y  =  S, Se, Te) were investigated using density functional theory. Results show that breaking the out-of-plane structural symmetry can be used to tune the electronic and mechanical behavior of monolayer transition metal dichalcogenides. The band gaps of monolayer WXY and MoXY are in the ranges of 0.16–1.91 and 0.94–1.69 eV, respectively. A semiconductor to metallic phase transition occurred in Janus monolayer MXY (M  =  Ti, Zr and Hf). The monolayers MXY (M  =  V, Nb, Ta and Cr) show metallic characteristics, which show no dependence on the structural symmetry breaking. The mechanical properties of MXY depended on the composition. Monolayer MXY (M  =  Mo, Ti, Zr, Hf and W) showed brittle characteristic, whereas monolayer CrXY and VXY are with ductile characteristic. The in-plane stiffness of pristine and Janus monolayer MXY are in the range between 22 and 158 N m‑1. The tunable electronic and mechanical properties of these 2D materials would advance the development of ultra-sensitive detectors, nanogenerators, low-power electronics, and energy harvesting and electromechanical systems.

Hierarchical self-assembly of magnetic nanoclusters for theranostics: Tunable size, enhanced magnetic resonance imagability, and controlled and targeted drug delivery.

Science.gov (United States)

Nguyen, Dai Hai; Lee, Jung Seok; Choi, Jong Hoon; Park, Kyung Min; Lee, Yunki; Park, Ki Dong

2016-04-15

Nanoparticle-based imaging and therapy are of interest for theranostic nanomedicine. In particular, superparamagnetic iron oxide (SPIO) nanoparticles (NPs) have attracted much attention in cancer imaging, diagnostics, and treatment because of their superior imagability and biocompatibility (approved by the Food and Drug Administration). Here, we developed SPIO nanoparticles (NPs) that self-assembled into magnetic nanoclusters (SAMNs) in aqueous environments as a theranostic nano-system. To generate multi-functional SPIO NPs, we covalently conjugated β-cyclodextrin (β-CD) to SPIO NPs using metal-adhesive dopamine groups. Polyethylene glycol (PEG) and paclitaxel (PTX) were hosted in the β-CD cavity through high affinity complexation. The core-shell structure of the magnetic nanoclusters was elucidated based on the condensed SPIO core and a PEG shell using electron microscopy and the composition was analyzed by thermogravimetric analysis (TGA). Our results indicate that nanocluster size could be readily controlled by changing the SPIO/PEG ratio in the assemblies. Interestingly, we observed a significant enhancement in magnetic resonance contrast due to the large cluster size and dense iron oxide core. In addition, tethering a tumor-targeting peptide to the SAMNs enhanced their uptake into tumor cells. PTX was efficiently loaded into β-CDs and released in a controlled manner when exposed to competitive guest molecules. These results strongly indicate that the SAMNs developed in this study possess great potential for application in image-guided cancer chemotherapy. In this study, we developed multi-functional SPIO NPs that self-assembled into magnetic nanoclusters (SAMNs) in aqueous conditions as a theranostic nano-system. The beta-cyclodextrin (β-CD) was immobilized on the surfaces of SPIO NPs and RGD-conjugated polyethylene glycol (PEG) and paclitaxel (PTX) were hosted in the β-CD cavity through high affinity complexation. We found that nanocluster size could be

The comparison of microstructure and nanocluster evolution in proton and neutron irradiated Fe–9%Cr ODS steel to 3 dpa at 500 °C

Energy Technology Data Exchange (ETDEWEB)

Swenson, M.J., E-mail: matthewswenson1@u.boisestate.edu; Wharry, J.P.

2015-12-15

A model Fe–9%Cr oxide dispersion strengthened (ODS) steel was irradiated with protons or neutrons to a dose of 3 displacements per atom (dpa) at a temperature of 500 °C, enabling a direct comparison of ion to neutron irradiation effects at otherwise fixed irradiation conditions. The irradiated microstructures were characterized using transmission electron microscopy and atom probe tomography including cluster analysis. Both proton and neutron irradiations produced a comparable void and dislocation loop microstructure. However, the irradiation response of the Ti–Y–O oxide nanoclusters varied. Oxides remained stable under proton irradiation, but exhibited dissolution and an increase in Y:Ti composition ratio under neutron irradiation. Both proton and neutron irradiation also induced varying extents of Si, Ni, and Mn clustering at existing oxide nanoclusters. Protons are able to reproduce the void and loop microstructure of neutron irradiation carried out to the same dose and temperature. However, since nanocluster evolution is controlled by both diffusion and ballistic impacts, protons are rendered unable to reproduce the nanocluster evolution of neutron irradiation at the same dose and temperature. - Highlights: • Fe–9% Cr ODS was irradiated with protons and neutrons to 3 dpa at 500 °C. • Dislocation loop size and density were similar upon proton and neutron irradiation. • Oxide nanocluster size and density decreased more with neutron irradiation. • Oxide Y:Ti ratio increased from 0.54 to 0.97 upon neutron irradiation. • Irradiation induced enrichment of Si, Mn, and Ni at oxide locations.

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.

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.

Synthesis of ultrasmall CsPbBr3 nanoclusters and their transformation to highly deep-blue-emitting nanoribbons at room temperature.

Science.gov (United States)

Xu, Yibing; Zhang, Qiang; Lv, Longfei; Han, Wenqian; Wu, Guanhong; Yang, Dong; Dong, Angang

2017-11-16

Discretely sized semiconductor clusters have attracted considerable attention due to their intriguing optical properties and self-assembly behaviors. While lead halide perovskite nanostructures have been recently intensively explored, few studies have addressed perovskite clusters and their self-assembled superstructures. Here, we report the room-temperature synthesis of sub-2 nm CsPbBr 3 clusters and present strong evidence that these ultrasmall perovskite species, obtained under a wide range of reaction conditions, possess a specific size, with optical properties and self-assembly characteristics resembling those of well-known II-VI semiconductor magic-sized clusters. Unlike conventional CsPbBr 3 nanocrystals, the as-synthesized CsPbBr 3 nanoclusters spontaneously self-assemble into a hexagonally packed columnar mesophase in solution, which can be further converted to single-crystalline CsPbBr 3 quantum nanoribbons with bright deep-blue emission at room temperature. Such a conversion of CsPbBr 3 nanoclusters to nanoribbons is found to be driven by a ligand-destabilization-induced crystallization and mesophase transition process. Our study will facilitate the investigation of perovskite nanoclusters and offer new possibilities in the low-temperature synthesis of anisotropic perovskite nanostructures.

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

First-principles study of the electronic transport properties in (GaAs)n (n=2–4) nanocluster-based molecular junctions

International Nuclear Information System (INIS)

Zhang, Daoli; Xu, Yuanlan; Zhang, Jianbing; Miao, Xiangshui

2012-01-01

In this program the geometric structures and electronic transport properties of a series of (GaAs) n (n=2,3,4) clusters are comparatively studied using non-equilibrium Green's function (NEGF) combined with density functional theory (DFT). It is find that all the GaAs nanocluster-based molecular junctions show metallic behavior at low biases ([−2 V,2 V]) while negative differential resistance (NDR) appears at a certain high bias range. Our calculation shows that the current of (GaAs) 3 nanocluster-based molecular junction is almost the smallest at any bias. The mechanisms of the current–voltage characteristics of all the three molecular junctions are proposed.

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

International Nuclear Information System (INIS)

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

2011-01-01

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

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.

A pentacene monolayer trapped between graphene and a substrate.

Science.gov (United States)

Zhang, Qicheng; Peng, Boyu; Chan, Paddy Kwok Leung; Luo, Zhengtang

2015-09-21

A self-assembled pentacene monolayer can be fabricated between the solid-solid interface of few-layered graphene (FLG) and the mica substrate, through a diffusion-spreading method. By utilizing a transfer method that allows us to sandwich pentacene between graphene and mica, followed by controlled annealing, we enabled the diffused pentacene to be trapped in the interfaces and led to the formation of a stable monolayer. We found that the formation of a monolayer is kinetically favored by using a 2D Ising lattice gas model for pentacene trapped between the graphene-substrate interfaces. This kinetic Monte Carlo simulation results indicate that, due to the graphene substrate enclosure, the spreading of the first layer proceeds faster than the second layer, as the kinetics favors the filling of voids by molecules from the second layer. This graphene assisted monolayer assembly method provides a new avenue for the fabrication of two-dimensional monolayer structures.

Monolayer atomic crystal molecular superlattices

Science.gov (United States)

Wang, Chen; He, Qiyuan; Halim, Udayabagya; Liu, Yuanyue; Zhu, Enbo; Lin, Zhaoyang; Xiao, Hai; Duan, Xidong; Feng, Ziying; Cheng, Rui; Weiss, Nathan O.; Ye, Guojun; Huang, Yun-Chiao; Wu, Hao; Cheng, Hung-Chieh; Shakir, Imran; Liao, Lei; Chen, Xianhui; Goddard, William A., III; Huang, Yu; Duan, Xiangfeng

2018-03-01

Artificial superlattices, based on van der Waals heterostructures of two-dimensional atomic crystals such as graphene or molybdenum disulfide, offer technological opportunities beyond the reach of existing materials. Typical strategies for creating such artificial superlattices rely on arduous layer-by-layer exfoliation and restacking, with limited yield and reproducibility. The bottom-up approach of using chemical-vapour deposition produces high-quality heterostructures but becomes increasingly difficult for high-order superlattices. The intercalation of selected two-dimensional atomic crystals with alkali metal ions offers an alternative way to superlattice structures, but these usually have poor stability and seriously altered electronic properties. Here we report an electrochemical molecular intercalation approach to a new class of stable superlattices in which monolayer atomic crystals alternate with molecular layers. Using black phosphorus as a model system, we show that intercalation with cetyl-trimethylammonium bromide produces monolayer phosphorene molecular superlattices in which the interlayer distance is more than double that in black phosphorus, effectively isolating the phosphorene monolayers. Electrical transport studies of transistors fabricated from the monolayer phosphorene molecular superlattice show an on/off current ratio exceeding 107, along with excellent mobility and superior stability. We further show that several different two-dimensional atomic crystals, such as molybdenum disulfide and tungsten diselenide, can be intercalated with quaternary ammonium molecules of varying sizes and symmetries to produce a broad class of superlattices with tailored molecular structures, interlayer distances, phase compositions, electronic and optical properties. These studies define a versatile material platform for fundamental studies and potential technological applications.

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

Surface-segregated monolayers: a new type of ordered monolayer for surface modification of organic semiconductors.

Science.gov (United States)

Wei, Qingshuo; Tajima, Keisuke; Tong, Yujin; Ye, Shen; Hashimoto, Kazuhito

2009-12-09

We report a new type of ordered monolayer for the surface modification of organic semiconductors. Fullerene derivatives with fluorocarbon chains ([6,6]-phenyl-C(61)-buryric acid 1H,1H-perfluoro-1-alkyl ester or FC(n)) spontaneously segregated as a monolayer on the surface of a [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) film during a spin-coating process from the mixture solutions, as confirmed by X-ray photoelectron spectroscopy (XPS). Ultraviolet photoelectron spectroscopy (UPS) showed the shift of ionization potentials (IPs) depending on the fluorocarbon chain length, indicating the formation of surface dipole moments. Surface-sensitive vibrational spectroscopy, sum frequency generation (SFG) revealed the ordered molecular orientations of the C(60) moiety in the surface FC(n) layers. The intensity of the SFG signals from FC(n) on the surface showed a clear odd-even effect when the length of the fluorocarbon chain was changed. This new concept of the surface-segregated monolayer provides a facile and versatile approach to modifying the surface of organic semiconductors and is applicable to various organic optoelectronic devices.

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)

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.

Density determination of langmuir-blodgett monolayer films using x-ray reflectivity technique

International Nuclear Information System (INIS)

Damar Yoga Kusuma

2015-01-01

Monolayer deposition by Langmuir-Blodgett technique produces monolayer films that are uniform with controllable thickness down to nanometer scale. To evaluate the quality of the monolayer deposition, X-ray reflectivity technique are employed to monitor the monolayers density. Langmuir-Blodgett monolayer with good coverage and uniformity results in film density close to its macroscopic film counterpart whereas films with presence of air gaps shows lower density compared to its macroscopic film counterpart. (author)

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.

Nonlinear optical characteristics of monolayer MoSe{sub 2}

Energy Technology Data Exchange (ETDEWEB)

Le, Chinh Tam; Ullah, Farman; Senthilkumar, Velusamy; Kim, Yong Soo [Department of Physics and Energy Harvest Storage Research Center, University of Ulsan (Korea, Republic of); Clark, Daniel J.; Jang, Joon I. [Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, NY (United States); Sim, Yumin; Seong, Maeng-Je [Department of Physics, Chung-Ang University, Seoul (Korea, Republic of); Chung, Koo-Hyun [School of Mechanical Engineering, University of Ulsan (Korea, Republic of); Park, Hyoyeol [Electronics, Communication and Semiconductor Applications Department, Ulsan College (Korea, Republic of)

2016-08-15

In this study, we utilized picosecond pulses from an Nd:YAG laser to investigate the nonlinear optical characteristics of monolayer MoSe{sub 2}. Two-step growth involving the selenization of pulsed-laser-deposited MoO{sub 3} film was employed to yield the MoSe{sub 2} monolayer on a SiO{sub 2}/Si substrate. Raman scattering, photoluminescence (PL) spectroscopy, and atomic force microscopy verified the high optical quality of the monolayer. The second-order susceptibility χ{sup (2)} was calculated to be ∝50 pm V{sup -1} at the second harmonic wavelength λ{sub SHG} ∝810 nm, which is near the optical gap of the monolayer. Interestingly, our wavelength-dependent second harmonic scan can identify the bound excitonic states including negatively charged excitons much more efficiently, compared with the PL method at room temperature. Additionally, the MoSe{sub 2} monolayer exhibits a strong laser-induced damage threshold ∝16 GW cm{sup -2} under picosecond-pulse excitation{sub .} Our findings suggest that monolayer MoSe{sub 2} can be considered as a promising candidate for high-power, thin-film-based nonlinear optical devices and applications. (copyright 2016 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

Surface Charge Transfer Doping of Monolayer Phosphorene via Molecular Adsorption.

Science.gov (United States)

He, Yuanyuan; Xia, Feifei; Shao, Zhibin; Zhao, Jianwei; Jie, Jiansheng

2015-12-03

Monolayer phosphorene has attracted much attention owing to its extraordinary electronic, optical, and structural properties. Rationally tuning the electrical transport characteristics of monolayer phosphorene is essential to its applications in electronic and optoelectronic devices. Herein, we study the electronic transport behaviors of monolayer phosphorene with surface charge transfer doping of electrophilic molecules, including 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), NO2, and MoO3, using density functional theory combined with the nonequilibrium Green's function formalism. F4TCNQ shows optimal performance in enhancing the p-type conductance of monolayer phosphorene. Static electronic properties indicate that the enhancement is originated from the charge transfer between adsorbed molecule and phosphorene layer. Dynamic transport behaviors demonstrate that additional channels for hole transport in host monolayer phosphorene were generated upon the adsorption of molecule. Our work unveils the great potential of surface charge transfer doping in tuning the electronic properties of monolayer phosphorene and is of significance to its application in high-performance devices.

Advanced chemistry of monolayers at interfaces trends in methodology and technology

CERN Document Server

Imae, Toyoko

2007-01-01

Advanced Chemistry of Monolayers at Interfaces describes the advanced chemistry of monolayers at interfaces. Focusing on the recent trends of methodology and technology, which are indispensable in monolayer science. They are applied to monolayers of surfactants, amphiphiles, polymers, dendrimers, enzymes, and proteins, which serve many uses.Introduces the methodologies of scanning probe microscopy, surface force instrumentation, surface spectroscopy, surface plasmon optics, reflectometry, and near-field scanning optical microscopy. Modern interface reaction method, lithographic tech

Pressure-dependent optical and vibrational properties of monolayer molybdenum disulfide

KAUST Repository

Nayak, Avinash P.; Pandey, Tribhuwan; Voiry, Damien; Liu, Jin; Moran, Samuel T.; Sharma, Ankit; Tan, Cheng; Chen, Changhsiao; Li, Lain-Jong; Chhowalla, Manish U.; Lin, Jungfu; Singh, Abhishek Kumar; Akinwande, Deji

2015-01-01

vibrational dynamics of the distorted monolayer 1T-MoS2 (1T′) and the monolayer 2H-MoS2 via a diamond anvil cell (DAC) and density functional theory (DFT) calculations. The direct optical band gap of the monolayer 2H-MoS2 increases by 11.7% from 1.85 to 2.08 e

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.

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

Science.gov (United States)

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

2016-05-01

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

Mathematical simulation of the amplification of 1790-nm laser radiation in a nuclear-excited He - Ar plasma containing nanoclusters of uranium compounds

Science.gov (United States)

Kosarev, V. A.; Kuznetsova, E. E.

2014-02-01

The possibility of applying dusty active media in nuclearpumped lasers has been considered. The amplification of 1790-nm radiation in a nuclear-excited dusty He - Ar plasma is studied by mathematical simulation. The influence of nanoclusters on the component composition of the medium and the kinetics of the processes occurring in it is analysed using a specially developed kinetic model, including 72 components and more than 400 reactions. An analysis of the results indicates that amplification can in principle be implemented in an active laser He - Ar medium containing 10-nm nanoclusters of metallic uranium and uranium dioxide.

Enhanced piezoelectricity of monolayer phosphorene oxides: a theoretical study.

Science.gov (United States)

Yin, Huabing; Zheng, Guang-Ping; Gao, Jingwei; Wang, Yuanxu; Ma, Yuchen

2017-10-18

Two-dimensional (2D) piezoelectric materials have potential applications in miniaturized sensors and energy conversion devices. In this work, using first-principles simulations at different scales, we systematically study the electronic structures and piezoelectricity of a series of 2D monolayer phosphorene oxides (POs). Our calculations show that the monolayer POs have tunable band gaps along with remarkable piezoelectric properties. The calculated piezoelectric coefficient d 11 of 54 pm V -1 in POs is much larger than those of 2D transition metal dichalcogenide monolayers and the widely used bulk α-quartz and AlN, and almost reaches the level of the piezoelectric effect in recently discovered 2D GeS. Furthermore, two other considerable piezoelectric coefficients, i.e., d 31 and d 26 with values of -10 pm V -1 and 21 pm V -1 , respectively, are predicted in some monolayer POs. We also examine the correlation between the piezoelectric coefficients and energy stability. The enhancement of piezoelectricity for monolayer phosphorene by oxidation will broaden the applications of phosphorene and phosphorene derivatives in nano-sized electronic and piezotronic devices.

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.

Monolayer arrangement of fatty hydroxystearic acids on graphite: Influence of hydroxyl groups

Energy Technology Data Exchange (ETDEWEB)

Medina, S. [Laboratorio de Rayos-X, Centro de Investigación Tecnología e Innovación, de la Universidad de Sevilla (CITIUS), Universidad de Sevilla, Avenida Reina Mercedes, 4B. 41012, Sevilla (Spain); Benítez, J.J.; Castro, M.A. [Instituto de Ciencia de Materiales de Sevilla, Consejo Superior de Investigaciones Científicas-Universidad de Sevilla, Avenida Américo Vespucio, 49. 41092, Sevilla (Spain); Cerrillos, C. [Servicio de Microscopía, Centro de Investigación Tecnología e Innovación, de la Universidad de Sevilla (CITIUS), Universidad de Sevilla, Avenida Reina Mercedes, 4B. 41012, Sevilla (Spain); Millán, C. [Instituto de Ciencia de Materiales de Sevilla, Consejo Superior de Investigaciones Científicas-Universidad de Sevilla, Avenida Américo Vespucio, 49. 41092, Sevilla (Spain); Alba, M.D., E-mail: alba@icmse.csic.es [Instituto de Ciencia de Materiales de Sevilla, Consejo Superior de Investigaciones Científicas-Universidad de Sevilla, Avenida Américo Vespucio, 49. 41092, Sevilla (Spain)

2013-07-31

Previous studies have indicated that long-chain linear carboxylic acids form commensurate packed crystalline monolayers on graphite even at temperatures above their melting point. This study examines the effect on the monolayer formation and structure of adding one or more secondary hydroxyl, functional groups to the stearic acid skeleton (namely, 12-hydroxystearic and 9,10-dihydroxystearic acid). Moreover, a comparative study of the monolayer formation on recompressed and monocrystalline graphite has been performed through X-ray diffraction (XRD) and Scanning Tunneling Microscopy (STM), respectively. The Differential Scanning Calorimetry (DSC) and XRD data were used to confirm the formation of solid monolayers and XRD data have provided a detailed structural analysis of the monolayers in good correspondence with obtained STM images. DSC and XRD have demonstrated that, in stearic acid and 12-hydroxystearic acid adsorbed onto graphite, the monolayer melted at a higher temperature than the bulk form of the carboxylic acid. However, no difference was observed between the melting point of the monolayer and the bulk form for 9,10-dihydroxystearic acid adsorbed onto graphite. STM results indicated that all acids on the surface have a rectangular p2 monolayer structure, whose lattice parameters were uniaxially commensurate on the a-axis. This structure does not correlate with the initial structure of the pure compounds after dissolving, but it is conditioned to favor a) hydrogen bond formation between the carboxylic groups and b) formation of hydrogen bonds between secondary hydroxyl groups, if spatially permissible. Therefore, the presence of hydroxyl functional groups affects the secondary structure and behavior of stearic acid in the monolayer. - Highlights: • Hydroxyl functional groups affect structure and behavior of acids in the monolayer. • Acids on the surface have a rectangular p2 monolayer structure. • Lattice parameters of acids are uniaxially

Exciton Binding Energy of Monolayer WS2

Science.gov (United States)

Zhu, Bairen; Chen, Xi; Cui, Xiaodong

2015-03-01

The optical properties of monolayer transition metal dichalcogenides (TMDC) feature prominent excitonic natures. Here we report an experimental approach to measuring the exciton binding energy of monolayer WS2 with linear differential transmission spectroscopy and two-photon photoluminescence excitation spectroscopy (TP-PLE). TP-PLE measurements show the exciton binding energy of 0.71 +/- 0.01 eV around K valley in the Brillouin zone.

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

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.

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.

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

Defect-Mediated Lithium Adsorption and Diffusion on Monolayer Molybdenum Disulfide.

Science.gov (United States)

Sun, Xiaoli; Wang, Zhiguo; Fu, Y Q

2015-12-22

Monolayer Molybdenum Disulfide (MoS2) is a promising anode material for lithium ion batteries because of its high capacities. In this work, first principle calculations based on spin density functional theory were performed to investigate adsorption and diffusion of lithium on monolayer MoS2 with defects, such as single- and few-atom vacancies, antisite, and grain boundary. The values of adsorption energies on the monolayer MoS2 with the defects were increased compared to those on the pristine MoS2. The presence of defects causes that the Li is strongly bound to the monolayer MoS2 with adsorption energies in the range between 2.81 and 3.80 eV. The donation of Li 2s electron to the defects causes an enhancement of adsorption of Li on the monolayer MoS2. At the same time, the presence of defects does not apparently affect the diffusion of Li, and the energy barriers are in the range of 0.25-0.42 eV. The presence of the defects can enhance the energy storage capacity, suggesting that the monolayer MoS2 with defects is a suitable anode material for the Li-ion batteries.

Thermal ripples in model molybdenum disulfide monolayers

Energy Technology Data Exchange (ETDEWEB)

Remsing, Richard C.; Klein, Michael L. [Institute for Computational Molecular Science, Center for the Computational, Design of Functional Layered Materials, and Department of Chemistry, Temple University, 1925 N. 12th St., 19122, Philadelphia, PA (United States); Waghmare, Umesh V. [Theoretical Sciences Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, 560 064, Jakkur, Bangalore (India)

2017-01-15

Molybdenum disulfide (MoS{sub 2}) monolayers have the potential to revolutionize nanotechnology. To reach this potential, it will be necessary to understand the behavior of this two-dimensional (2D) material on large length scales and under thermal conditions. Herein, we use molecular dynamics (MD) simulations to investigate the nature of the rippling induced by thermal fluctuations in monolayers of the 2H and 1T phases of MoS{sub 2}. The 1T phase is found to be more rigid than the 2H phase. Both monolayer phases are predicted to follow long wavelength scaling behavior typical of systems with anharmonic coupling between vibrational modes as predicted by classic theories of membrane-like systems. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Passivation of Black Phosphorus via Self-Assembled Organic Monolayers by van der Waals Epitaxy.

Science.gov (United States)

Zhao, Yinghe; Zhou, Qionghua; Li, Qiang; Yao, Xiaojing; Wang, Jinlan

2017-02-01

An effective passivation approach to protect black phosphorus (BP) from degradation based on multi-scale simulations is proposed. The self-assembly of perylene-3,4,9,10-tetracarboxylic dianhydride monolayers via van der Waals epitaxy on BP does not break the original electronic properties of BP. The passivation layer thickness is only 2 nm. This study opens up a new pathway toward fine passivation of BP. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Protecting nickel with graphene spin-filtering membranes: A single layer is enough

Energy Technology Data Exchange (ETDEWEB)

Martin, M.-B.; Dlubak, B.; Piquemal-Banci, M.; Collin, S.; Petroff, F.; Anane, A.; Fert, A.; Seneor, P. [Unité Mixte de Physique CNRS/Thales, 1 Avenue Augustin Fresnel, 91767 Palaiseau, France and Université Paris Sud, 91405 Orsay (France); Weatherup, R. S.; Hofmann, S.; Robertson, J. [Department of Engineering, University of Cambridge, Cambridge CB21PZ (United Kingdom); Yang, H. [IBS Center for Integrated Nanostructure Physics (CINAP), Institute for Basic Science, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Department of Energy Science, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Blume, R. [Helmholtz-Zentrum Berlin fur Materialien und Energie, 12489 Berlin (Germany); Schloegl, R. [Department of Inorganic Chemistry, Fritz Haber Institute of the Max Planck Society, Faradayweg 4-6, 14195 Berlin (Germany)

2015-07-06

We report on the demonstration of ferromagnetic spin injectors for spintronics which are protected against oxidation through passivation by a single layer of graphene. The graphene monolayer is directly grown by catalytic chemical vapor deposition on pre-patterned nickel electrodes. X-ray photoelectron spectroscopy reveals that even with its monoatomic thickness, monolayer graphene still efficiently protects spin sources against oxidation in ambient air. The resulting single layer passivated electrodes are integrated into spin valves and demonstrated to act as spin polarizers. Strikingly, the atom-thick graphene layer is shown to be sufficient to induce a characteristic spin filtering effect evidenced through the sign reversal of the measured magnetoresistance.

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.

Chain Stretching and Order-Disorder Transitions in Block Copolymer Monolayers and Multilayers

Science.gov (United States)

Kramer, Edward J.; Mishra, Vindhya; Stein, Gila E.; Sohn, Karen E.; Hur, Sumi; Fredrickson, Glenn H.; Cochran, Eric W.

2009-03-01

Both monolayers of block copolymer cylinders and spheres undergo order to disorder transitions (ODT) at temperatures well below those of the bulk. Monolayers of PS-b-P2VP cylinders undergo a ``nematic'' to ``isotropic'' transition at temperatures about 20 K below the bulk ODT while monolayers of PS-b-P2VP with P2VP spheres undergo a 2D crystal to hexatic transition at least 10 K below the bulk ODT. Bilayers of each structure disorder at temperatures well above that of the monolayers. While one is tempted to attribute all of the difference to the fact that ordered monolayers are quasi 2 dimensional while bilayers are not, an alternative explanation exists. In the cylinder monolayer the corona PS chains must stretch to fill a nearly square cross-section domain rather than a hexagonal one in the bulk, while the corona PS chains in a sphere monolayer must stretch to fill a hexagonal prism rather than an octahedron in the bulk. The more non-uniform stretching of the chains in the monolayer should increase its free energy and decrease its order-disorder temperature.

The interaction of insulin, glucose, and insulin-glucose mixtures with a phospholipid monolayer.

Science.gov (United States)

Shigenobu, Hayato; McNamee, Cathy E

2012-12-15

We determined how glucose or insulin interacts with a phospholipid monolayer at the air/water interface and explained these mechanisms from a physico-chemical point of view. The 1,2-dipalmitoyl-2-sn-glycero-3-phosphatidylcholine (DPPC) monolayer at an air/water interface acted as a model membrane, which allowed the effect of the molecular packing density in the monolayer on the interactions to be determined. The interaction of glucose, insulin, and a mixture of glucose and insulin to the DPPC monolayer were investigated via surface pressure-area per molecule Langmuir isotherms and fluorescence microscopy. Glucose adsorbed to the underside of the DPPC monolayer, while insulin was able to penetrate through the monolayer when the phospholipid molecules were not densely packed. The presence of a mixture of insulin and glucose affected the molecular packing in the DPPC monolayer differently than the pure insulin or glucose solutions, and the glucose-insulin mixture was seen to be able to penetrate through the monolayer. These results indicated that glucose and insulin interact with one another, giving a material that may then transported through a pore in the monolayer or through the spaces between the molecules of the monolayer. Copyright © 2012 Elsevier Inc. All rights reserved.

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

Science.gov (United States)

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

2016-04-18

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

Electrical-field-induced magnetic Skyrmion ground state in a two-dimensional chromium tri-iodide ferromagnetic monolayer

Science.gov (United States)

Liu, Jie; Shi, Mengchao; Mo, Pinghui; Lu, Jiwu

2018-05-01

Using fully first-principles non-collinear self-consistent field density functional theory (DFT) calculations with relativistic spin-orbital coupling effects, we show that, by applying an out-of-plane electrical field on a free-standing two-dimensional chromium tri-iodide (CrI3) ferromagnetic monolayer, the Néel-type magnetic Skyrmion spin configurations become more energetically-favorable than the ferromagnetic spin configurations. It is revealed that the topologically-protected Skyrmion ground state is caused by the breaking of inversion symmetry, which induces the non-trivial Dzyaloshinskii-Moriya interaction (DMI) and the energetically-favorable spin-canting configuration. Combining the ferromagnetic and the magnetic Skyrmion ground states, it is shown that 4-level data can be stored in a single monolayer-based spintronic device, which is of practical interests to realize the next-generation energy-efficient quaternary logic devices and multilevel memory devices.

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.

Nonlinear optical studies of organic monolayers

International Nuclear Information System (INIS)

Shen, Y.R.

1988-02-01

Second-order nonlinear optical effects are forbidden in a medium with inversion symmetry, but are necessarily allowed at a surface where the inversion summary is broken. They are often sufficiently strong so that a submonolayer perturbation of the surface can be readily detected. They can therefore be used as effective tools to study monolayers adsorbed at various interfaces. We discuss here a number of recent experiments in which optical second harmonic generation (SHG) and sum-frequency generation (SFG) are employed to probe and characterize organic monolayers. 15 refs., 5 figs

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

Unanticipated C=C bonds in covalent monolayers on silicon revealed by NEXAFS.

Science.gov (United States)

Lee, Michael V; Lee, Jonathan R I; Brehmer, Daniel E; Linford, Matthew R; Willey, Trevor M

2010-02-02

Interfaces are crucial to material properties. In the case of covalent organic monolayers on silicon, molecular structure at the interface controls the self-assembly of the monolayers, which in turn influences the optical properties and electrical transport. These properties intrinsically affect their application in biology, tribology, optics, and electronics. We use near-edge X-ray absorption fine structure spectroscopy to show that the most basic covalent monolayers formed from 1-alkenes on silicon retain a double bond in one-fifth to two-fifths of the resultant molecules. Unsaturation in the predominantly saturated monolayers will perturb the regular order and affect the dependent properties. The presence of unsaturation in monolayers produced by two different methods also prompts the re-evaluation of other radical-based mechanisms for forming covalent monolayers on silicon.

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

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…

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

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.

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.

Surface-enhanced Raman scattering by colloidal CdSe nanocrystal submonolayers fabricated by the Langmuir–Blodgett technique

Directory of Open Access Journals (Sweden)

Alexander G. Milekhin

2015-12-01

Full Text Available We present the results of an investigation of surface-enhanced Raman scattering (SERS by optical phonons in colloidal CdSe nanocrystals (NCs homogeneously deposited on both arrays of Au nanoclusters and Au dimers using the Langmuir–Blodgett technique. The coverage of the deposited NCs was less than one monolayer, as determined by transmission and scanning electron microscopy. SERS by optical phonons in CdSe nanocrystals showed a significant enhancement that depends resonantly on the Au nanocluster and dimer size, and thus on the localized surface plasmon resonance (LSPR energy. The deposition of CdSe nanocrystals on the Au dimer nanocluster arrays enabled us to study the polarization dependence of SERS. The maximal SERS signal was observed for light polarization parallel to the dimer axis. The polarization ratio of the SERS signal parallel and perpendicular to the dimer axis was 20. The SERS signal intensity was also investigated as a function of the distance between nanoclusters in a dimer. Here the maximal SERS enhancement was observed for the minimal distance studied (about 10 nm, confirming the formation of SERS “hot spots”.

Characterization of self-assembled monolayers on a ruthenium surface

NARCIS (Netherlands)

Shaheen, Amrozia; Sturm, Jacobus Marinus; Ricciardi, R.; Huskens, Jurriaan; Lee, Christopher James; Bijkerk, Frederik

2017-01-01

We have modified and stabilized the ruthenium surface by depositing a self-assembled monolayer (SAM) of 1-hexadecanethiol on a polycrystalline ruthenium thin film. The growth mechanism, dynamics, and stability of these monolayers were studied. SAMs, deposited under ambient conditions, on

Heterointerface Screening Effects between Organic Monolayers and Monolayer Transition Metal Dichalcogenides

KAUST Repository

Zheng, Yu Jie; Huang, Yu Li; Chen, Yifeng; Zhao, Weijie; Eda, Goki; Spataru, Catalin D.; Zhang, Wenjing; Chang, Yung-Huang; Li, Lain-Jong; Chi, Dongzhi; Quek, Su Ying; Wee, Andrew Thye Shen

2016-01-01

© 2016 American Chemical Society. The nature and extent of electronic screening at heterointerfaces and their consequences on energy level alignment are of profound importance in numerous applications, such as solar cells, electronics etc. The increasing availability of two-dimensional (2D) transition metal dichalcogenides (TMDs) brings additional opportunities for them to be used as interlayers in "van der Waals (vdW) heterostructures" and organic/inorganic flexible devices. These innovations raise the question of the extent to which the 2D TMDs participate actively in dielectric screening at the interface. Here we study perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) monolayers adsorbed on single-layer tungsten diselenide (WSe2), bare graphite, and Au(111) surfaces, revealing a strong dependence of the PTCDA HOMO-LUMO gap on the electronic screening effects from the substrate. The monolayer WSe2 interlayer provides substantial, but not complete, screening at the organic/inorganic interface. Our results lay a foundation for the exploitation of the complex interfacial properties of hybrid systems based on TMD materials.

Heterointerface Screening Effects between Organic Monolayers and Monolayer Transition Metal Dichalcogenides

KAUST Repository

Zheng, Yu Jie

2016-01-21

© 2016 American Chemical Society. The nature and extent of electronic screening at heterointerfaces and their consequences on energy level alignment are of profound importance in numerous applications, such as solar cells, electronics etc. The increasing availability of two-dimensional (2D) transition metal dichalcogenides (TMDs) brings additional opportunities for them to be used as interlayers in "van der Waals (vdW) heterostructures" and organic/inorganic flexible devices. These innovations raise the question of the extent to which the 2D TMDs participate actively in dielectric screening at the interface. Here we study perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) monolayers adsorbed on single-layer tungsten diselenide (WSe2), bare graphite, and Au(111) surfaces, revealing a strong dependence of the PTCDA HOMO-LUMO gap on the electronic screening effects from the substrate. The monolayer WSe2 interlayer provides substantial, but not complete, screening at the organic/inorganic interface. Our results lay a foundation for the exploitation of the complex interfacial properties of hybrid systems based on TMD materials.

Template-Directed Self-Assembly of Alkanethiol Monolayers: Selective Growth on Preexisting Monolayer Edges

NARCIS (Netherlands)

Sharpe, R.B.A.; Burdinski, Dirk; Huskens, Jurriaan; Zandvliet, Henricus J.W.; Reinhoudt, David; Poelsema, Bene

2007-01-01

Self-assembled monolayers were investigated for their suitability as two-dimensional scaffolds for the selective growth of alkanethiol edge structures. Heterostructures with chemical contrast could be grown, whose dimensions were governed by both the initial pattern sizes and the process time.

Spatially resolved investigation of competing nanocluster emission in quantum-disks-in-nanowires structure characterized by nanoscale cathodoluminescence

KAUST Repository

Prabaswara, Aditya; Stowe, David J.; Janjua, Bilal; Ng, Tien Khee; Anjum, Dalaver H.; Longo, Paolo; Zhao, Chao; Elafandy, Rami T.; Li, Xiaohang; Alyamani, Ahmed Y.; El-Desouki, Munir M.; Ooi, Boon S.

2017-01-01

We report on the study and characterization of nanoclusters-related recombination centers within quantum-disks-in-nanowires heterostructure by utilizing microphotoluminescence (mu-PL) and cathodoluminescence scanning transmission electron microscopy (CL-STEM). mu-PL measurement shows that the nanoclusters-related recombination center exhibits different temperature-dependent characteristics compared with the surrounding InGaN quantum-disksrelated recombination center. CL-STEM measurements reveal that these recombination centers mainly arise from irregularities within the quantum disks, with a strong, spatially localized emission when measured at low temperature. The spectra obtained from both CL-STEM and mu-PL correlate well with each other. Our work sheds light on the optical and structural properties of simultaneously coexisting recombination centers within nanowires heterostructures. (C) The Authors. Published by SPIE under a Creative Commons Attribution 3.0 Unported License. Distribution or reproduction of this work in whole or in part requires full attribution of the original publication, including its DOI.

Spatially resolved investigation of competing nanocluster emission in quantum-disks-in-nanowires structure characterized by nanoscale cathodoluminescence

KAUST Repository

Prabaswara, Aditya

2017-06-30

We report on the study and characterization of nanoclusters-related recombination centers within quantum-disks-in-nanowires heterostructure by utilizing microphotoluminescence (mu-PL) and cathodoluminescence scanning transmission electron microscopy (CL-STEM). mu-PL measurement shows that the nanoclusters-related recombination center exhibits different temperature-dependent characteristics compared with the surrounding InGaN quantum-disksrelated recombination center. CL-STEM measurements reveal that these recombination centers mainly arise from irregularities within the quantum disks, with a strong, spatially localized emission when measured at low temperature. The spectra obtained from both CL-STEM and mu-PL correlate well with each other. Our work sheds light on the optical and structural properties of simultaneously coexisting recombination centers within nanowires heterostructures. (C) The Authors. Published by SPIE under a Creative Commons Attribution 3.0 Unported License. Distribution or reproduction of this work in whole or in part requires full attribution of the original publication, including its DOI.

Formation and electrochemical investigation of ordered cobalt coordinated peptide monolayers on gold substrates

International Nuclear Information System (INIS)

Wang Xinxin; Nagata, Kenji; Higuchi, Masahiro

2012-01-01

The monolayers composed of cobalt coordinated peptides were prepared on gold substrates by two different approaches. One was the self-assembly method, which was used to prepare a peptide monolayer on the gold substrate via the spontaneous attachment of peptides owing to the interaction between gold and sulfur at the N-terminal of the peptide. The other one was the stepwise polymerization method that was utilized to fabricate the unidirectionally arranged peptide monolayer by the stepwise condensation of amino acids from the initiator fixed on the gold substrate. Leu 2 Ala(4-Pyri)Leu 6 Ala(4-Pyri)Leu 6 sequence was chosen as the cobalt coordinated peptide. The 4-pyridyl alanines, Ala(4-Pyri)s, were introduced as ligands for cobalt to the leucine-rich sequential peptide. The complexation between cobalt and pyridyl groups of the peptide induced the formation of a stable α-helical bundle, which oriented perpendicularly to the substrate surface. In the case of the monolayer fabricated by the stepwise polymerization method, the direction of the peptide macro-dipole moment aligned unidirectionally, and the cobalt complexes were fixed in the monolayer to form the ordered arrangement. On the other hand, the peptides prepared by the self-assembly method formed the mixture of parallel and antiparallel packing owing to the dipole-dipole interaction. The spatial location of the cobalt complexes in the monolayer prepared by the self-assembly method was distorted, compared with that in the monolayer fabricated by the stepwise polymerization method. The vectorial electron flow through the peptide monolayer was achieved by the regular alignment of the peptide macro-dipole moment and the cobalt complexes in the monolayer fabricated by the stepwise polymerization method. - Highlights: ► We fabricated ordered Co coordinated peptide monolayers on the gold substrates. ► The Co complexes in peptide monolayer formed an ordered arrangement of the peptide. ► The peptide macro

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

Energy Technology Data Exchange (ETDEWEB)

Elm, Matthias Thomas

2010-07-01

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

Structural, electronic and magnetic properties of Au-based monolayer derivatives in honeycomb structure

Energy Technology Data Exchange (ETDEWEB)

Kapoor, Pooja, E-mail: pupooja16@gmail.com; Sharma, Munish; Ahluwalia, P. K. [Physics Department, Himachal Pradesh University, Shimla, Himachal Pradesh, India 171005 (India); Kumar, Ashok [Centre for Physical Sciences, School of Basic and Applied Sciences, Central University of Punjab, Bathinda, India, 151001 (India)

2016-05-23

We present electronic properties of atomic layer of Au, Au{sub 2}-N, Au{sub 2}-O and Au{sub 2}-F in graphene-like structure within the framework of density functional theory (DFT). The lattice constant of derived monolayers are found to be higher than the pristine Au monolayer. Au monolayer is metallic in nature with quantum ballistic conductance calculated as 4G{sub 0}. Similarly, Au{sub 2}-N and Au{sub 2}-F monolayers show 4G{sub 0} and 2G{sub 0} quantum conductance respectively while semiconducting nature with calculated band gap of 0.28 eV has been observed for Au{sub 2}-O monolayer. Most interestingly, half metalicity has been predicted for Au{sub 2}-N and Au{sub 2}-F monolayers. Our findings may have importance for the application of these monolayers in nanoelectronic and spintronics.

Sub-THz Characterisation of Monolayer Graphene

Directory of Open Access Journals (Sweden)

Ehsan Dadrasnia

2014-01-01

Full Text Available We explore the optical and electrical characteristics of monolayer graphene by using pulsed optoelectronic terahertz time-domain spectroscopy in the frequency range of 325–500 GHz based on fast direct measurements of phase and amplitude. We also show that these parameters can, however, be measured with higher resolution using a free space continuous wave measurement technique associated with a vector network analyzer that offers a good dynamic range. All the scattering parameters (both magnitude and phase are measured simultaneously. The Nicholson-Ross-Weir method is implemented to extract the monolayer graphene parameters at the aforementioned frequency range.

Piezoelectric effect on the thermal conductivity of monolayer gallium nitride

Science.gov (United States)

Zhang, Jin

2018-01-01

Using molecular dynamics and density functional theory simulations, in this work, we find that the heat transport property of the monolayer gallium nitride (GaN) can be efficiently tailored by external electric field due to its unique piezoelectric characteristic. As the monolayer GaN possesses different piezoelectric properties in armchair and zigzag directions, different effects of the external electric field on thermal conductivity are observed when it is applied in the armchair and zigzag directions. Our further study reveals that due to the elastoelectric effect in the monolayer GaN, the external electric field changes the Young's modulus and therefore changes the phonon group velocity. Also, due to the inverse piezoelectric effect, the applied electric field induces in-plane stress in the monolayer GaN subject to a length constraint, which results in the change in the lattice anharmonicity and therefore affects the phonon mean free path. Furthermore, for relatively long GaN monolayers, the in-plane stress may trigger the buckling instability, which can significantly reduce the phonon mean free path.

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.

Gas sensing with self-assembled monolayer field-effect transistors

NARCIS (Netherlands)

Andringa, Anne-Marije; Spijkman, Mark-Jan; Smits, Edsger C. P.; Mathijssen, Simon G. J.; van Hal, Paul A.; Setayesh, Sepas; Willard, Nico P.; Borshchev, Oleg V.; Ponomarenko, Sergei A.; Blom, Paul W. M.; de Leeuw, Dago M.

A new sensitive gas sensor based on a self-assembled monolayer field-effect transistor (SAMFET) was used to detect the biomarker nitric oxide. A SAMFET based sensor is highly sensitive because the analyte and the active channel are separated by only one monolayer. SAMFETs were functionalised for

One-step synthesis and applications of fluorescent Cu nanoclusters stabilized by L-cysteine in aqueous solution.

Science.gov (United States)

Yang, Xiaoming; Feng, Yuanjiao; Zhu, Shanshan; Luo, Yawen; Zhuo, Yan; Dou, Yao

2014-10-17

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. Copyright © 2014 Elsevier B.V. All rights reserved.

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....

Defect-Mediated Lithium Adsorption and Diffusion on Monolayer Molybdenum Disulfide

OpenAIRE

Sun, Xiaoli; Wang, Zhiguo; Fu, Yong Qing

2015-01-01

Monolayer Molybdenum Disulfide (MoS2) is a promising anode material for lithium ion batteries because of its high capacities. In this work, first principle calculations based on spin density functional theory were performed to investigate adsorption and diffusion of lithium on monolayer MoS2 with defects, such as single- and few-atom vacancies, antisite, and grain boundary. The values of adsorption energies on the monolayer MoS2 with the defects were increased compared to those on the pristin...

Topography and instability of monolayers near domain boundaries

International Nuclear Information System (INIS)

Diamant, H.; Witten, T. A.; Ege, C.; Gopal, A.; Lee, K. Y. C.

2001-01-01

We theoretically study the topography of a biphasic surfactant monolayer in the vicinity of domain boundaries. The differing elastic properties of the two phases generally lead to a nonflat topography of 'mesas,' where domains of one phase are elevated with respect to the other phase. The mesas are steep but low, having heights of up to 10 nm. As the monolayer is laterally compressed, the mesas develop overhangs and eventually become unstable at a surface tension of about K(δc 0 ) 2 (δc 0 being the difference in spontaneous curvature and K a bending modulus). In addition, the boundary is found to undergo a topography-induced rippling instability upon compression, if its line tension is smaller than about Kδc 0 . The effect of diffuse boundaries on these features and the topographic behavior near a critical point are also examined. We discuss the relevance of our findings to several experimental observations related to surfactant monolayers: (i) small topographic features recently found near domain boundaries; (ii) folding behavior observed in mixed phospholipid monolayers and model lung surfactants; (iii) roughening of domain boundaries seen under lateral compression; (iv) the absence of biphasic structures in tensionless surfactant films

Investigating Alkylsilane Monolayer Tribology at a Single-Asperity Contact with Molecular Dynamics Simulation.

Science.gov (United States)

Summers, Andrew Z; Iacovella, Christopher R; Cummings, Peter T; McCabe, Clare

2017-10-24

Chemisorbed monolayer films are known to possess favorable characteristics for nanoscale lubrication of micro- and nanoelectromechanical systems (MEMS/NEMS). Prior studies have shown that the friction observed for monolayer-coated surfaces features a strong dependence on the geometry of contact. Specifically, tip-like geometries have been shown to penetrate into monolayer films, inducing defects in the monolayer chains and leading to plowing mechanisms during shear, which result in higher coefficients of friction (COF) than those observed for planar geometries. In this work, we use molecular dynamics simulations to examine the tribology of model silica single-asperity contacts under shear with monolayer-coated substrates featuring various film densities. It is observed that lower monolayer densities lead to reduced COFs, in contrast to results for planar systems where COF is found to be nearly independent of monolayer density. This is attributed to a liquid-like response to shear, whereby fewer defects are imparted in monolayer chains from the asperity, and chains are easily displaced by the tip as a result of the higher free volume. This transition in the mechanism of molecular plowing suggests that liquid-like films should provide favorable lubrication at single-asperity contacts.

DPPC Monolayers Exhibit an Additional Phase Transition at High Surface Pressure

DEFF Research Database (Denmark)

Shen, Chen; de la Serna, Jorge B.; Struth, Bernd

2015-01-01

Pulmonary surfactant forms a monolayer at the air/aqueous interface within the lung. During the breath process, the surface pressure (Π) periodically varies from ~40mN/m up to ~70mN/m. The film is mechanically stable during this rapid and reversible expansion. Pulmonary surfactant consists of ~90......% of lipid with 10% integrated proteins. Among its lipid compounds, di-palmitoyl-phosphatidylcholine (DPPC) dominates (~45wt%). DPPC is the only known lipid that can be compressed to very high surface pressure (~70mN/m) before its monolayer collapses. Most probably, this feature contributes to the mechanical...... stability of the alveoli monolayer. Still, to the best of our knowledge, some details of the compression isotherm presented here and the related structures of the DPPC monolayer were not studied so far. The liquid-expanded/liquid-condensed phase transition of the DPPC monolayer at ~10mN/m is well known...

Collapse of Langmuir monolayer at lower surface pressure: Effect of hydrophobic chain length

Energy Technology Data Exchange (ETDEWEB)

Das, Kaushik, E-mail: kaushikdas2089@gmail.com; Kundu, Sarathi [Physical Sciences Division, Institute of Advanced Study in Science and Technology, Vigyan Path, Paschim Boragaon, Garchuk, Guwahati, Assam 781035 (India)

2016-05-23

Long chain fatty acid molecules (e.g., stearic and behenic acids) form a monolayer on water surface in the presence of Ba{sup 2+} ions at low subphase pH (≈ 5.5) and remain as a monolayer before collapse generally occurs at higher surface pressure (π{sub c} > 50 mN/m). Monolayer formation is verified from the surface pressure vs. area per molecule (π-A) isotherms and also from the atomic force microscopy (AFM) analysis of the films deposited by single upstroke of hydrophilic Si (001) substrate through the monolayer covered water surface. At high subphase pH (≈ 9.5), barium stearate molecules form multilayer structure at lower surface pressure which is verified from the π-A isotherms and AFM analysis of the film deposited at 25 mN/m. Such monolayer to multilayer structure formation or monolayer collapse at lower surface pressure is unusual as at this surface pressure generally fatty acid salt molecules form a monolayer on the water surface. Formation of bidentate chelate coordination in the metal containing headgroups is the reason for such monolayer to multilayer transition. However, for longer chain barium behenate molecules only monolayer structure is maintained at that high subphase pH (≈ 9.5) due to the presence of relatively more tail-tail hydrophobic interaction.

A molecular beacon based on DNA-templated silver nanoclusters for the highly sensitive and selective multiplexed detection of virulence genes.

Science.gov (United States)

Han, Dan; Wei, Chunying

2018-05-01

In this work, we develop a fluorescent molecular beacon based on the DNA-templated silver nanoclusters (DNA-Ag NCs). The skillfully designed molecular beacon can be conveniently used for detection of diverse virulence genes as long as the corresponding recognition sequences are embedded. Importantly, the constructed detection system allows simultaneous detection of multiple nucleic acids, which is attributed to non-overlapping emission spectra of the as-synthesized silver nanoclusters. Based on the target-induced fluorescence enhancement, three infectious disease-related genes HIV, H1N1, and H5N1 are detected, and the corresponding detection limits are 3.53, 0.12 and 3.95nM, respectively. This design allows specific, versatile and simultaneous detection of diverse targets with easy operation and low cost. Copyright © 2017 Elsevier B.V. All rights reserved.

Transfer matrix theory of monolayer graphene/bilayer graphene heterostructure superlattice

International Nuclear Information System (INIS)

Wang, Yu

2014-01-01

We have formulated a transfer matrix method to investigate electronic properties of graphene heterostructure consisting of monolayer graphene and bilayer counterpart. By evaluating transmission, conductance, and band dispersion, we show that, irrespective of the different carrier chiralities in monolayer graphene and bilayer graphene, superlattice consisting of biased bilayer graphene barrier and monolayer graphene well can mimic the electronic properties of conventional semiconductor superlattice, displaying the extended subbands in the quantum tunneling regime and producing anisotropic minigaps for the classically allowed transport. Due to the lateral confinement, the lowest mode has shifted away from the charge neutral point of monolayer graphene component, opening a sizeable gap in concerned structure. Following the gate-field and geometry modulation, all electronic states and gaps between them can be externally engineered in an electric-controllable strategy.

Exploring atomic defects in molybdenum disulphide monolayers

KAUST Repository

Hong, Jinhua; Hu, Zhixin; Probert, Matt; Li, Kun; Lv, Danhui; Yang, Xinan; Gu, Lin; Mao, Nannan; Feng, Qingliang; Xie, Liming; Zhang, Jin; Wu, Dianzhong; Zhang, Zhiyong; Jin, Chuanhong; Ji, Wei; Zhang, Xixiang; Yuan, Jun; Zhang, Ze

2015-01-01

Defects usually play an important role in tailoring various properties of two-dimensional materials. Defects in two-dimensional monolayer molybdenum disulphide may be responsible for large variation of electric and optical properties. Here we present a comprehensive joint experiment-theory investigation of point defects in monolayer molybdenum disulphide prepared by mechanical exfoliation, physical and chemical vapour deposition. Defect species are systematically identified and their concentrations determined by aberration-corrected scanning transmission electron microscopy, and also studied by ab-initio calculation. Defect density up to 3.5 × 10 13 cm '2 is found and the dominant category of defects changes from sulphur vacancy in mechanical exfoliation and chemical vapour deposition samples to molybdenum antisite in physical vapour deposition samples. Influence of defects on electronic structure and charge-carrier mobility are predicted by calculation and observed by electric transport measurement. In light of these results, the growth of ultra-high-quality monolayer molybdenum disulphide appears a primary task for the community pursuing high-performance electronic devices.

Exploring atomic defects in molybdenum disulphide monolayers

KAUST Repository

Hong, Jinhua

2015-02-19

Defects usually play an important role in tailoring various properties of two-dimensional materials. Defects in two-dimensional monolayer molybdenum disulphide may be responsible for large variation of electric and optical properties. Here we present a comprehensive joint experiment-theory investigation of point defects in monolayer molybdenum disulphide prepared by mechanical exfoliation, physical and chemical vapour deposition. Defect species are systematically identified and their concentrations determined by aberration-corrected scanning transmission electron microscopy, and also studied by ab-initio calculation. Defect density up to 3.5 × 10 13 cm \\'2 is found and the dominant category of defects changes from sulphur vacancy in mechanical exfoliation and chemical vapour deposition samples to molybdenum antisite in physical vapour deposition samples. Influence of defects on electronic structure and charge-carrier mobility are predicted by calculation and observed by electric transport measurement. In light of these results, the growth of ultra-high-quality monolayer molybdenum disulphide appears a primary task for the community pursuing high-performance electronic devices.

Affinity of serum apolipoproteins for lipid monolayers

International Nuclear Information System (INIS)

Ibdah, J.A.

1987-01-01

The effects of lipid composition and packing as well as the structure of the protein on the affinities of apolipoproteins for lipid monolayers have been investigated. The adsorption of 14 C-reductively methylated human apolipoproteins A-I and A-II at saturating subphase concentrations to monolayers prepared with synthetic lipids or lipoprotein surface lipids spread at various initial surface pressures has been studied. The adsorption of apolipoproteins is monitored by following the surface radioactivity using a gas flow counter and Wilhelmy plate, respectively. The physical states of the lipid monolayers are evaluated by measurement of the surface pressure-molecular area isotherms using a Langmuir-Adam surface balance. The probable helical regions in various apolipoproteins have been predicted using a secondary structure analysis computer program. The mean residue hydrophobicity and mean residue hydrophobic moment for the predicted helical segments have been calculated. The surface properties of synthetic peptides which are amphipathic helix analogs have been investigated at the air-water and lipid-water interfaces

Janus monolayers of transition metal dichalcogenides

KAUST Repository

Lu, Ang-Yu

2017-05-15

Structural symmetry-breaking plays a crucial role in determining the electronic band structures of two-dimensional materials. Tremendous efforts have been devoted to breaking the in-plane symmetry of graphene with electric fields on AB-stacked bilayers or stacked van der Waals heterostructures. In contrast, transition metal dichalcogenide monolayers are semiconductors with intrinsic in-plane asymmetry, leading to direct electronic bandgaps, distinctive optical properties and great potential in optoelectronics. Apart from their in-plane inversion asymmetry, an additional degree of freedom allowing spin manipulation can be induced by breaking the out-of-plane mirror symmetry with external electric fields or, as theoretically proposed, with an asymmetric out-of-plane structural configuration. Here, we report a synthetic strategy to grow Janus monolayers of transition metal dichalcogenides breaking the out-of-plane structural symmetry. In particular, based on a MoS2 monolayer, we fully replace the top-layer S with Se atoms. We confirm the Janus structure of MoSSe directly by means of scanning transmission electron microscopy and energy-dependent X-ray photoelectron spectroscopy, and prove the existence of vertical dipoles by second harmonic generation and piezoresponse force microscopy measurements.

Mixed DPPC/POPC Monolayers: All-atom Molecular Dynamics Simulations and Langmuir Monolayer Experiments

Czech Academy of Sciences Publication Activity Database

Olžyńska, Agnieszka; Zubek, M.; Roeselová, Martina; Korchowiec, J.; Cwiklik, Lukasz

2016-01-01

Roč. 1858, č. 12 (2016), s. 3120-3130 ISSN 0005-2736 R&D Projects: GA ČR GA15-14292S Institutional support: RVO:61388955 ; RVO:61388963 Keywords : phospholipid monolayers * Lung surfactant * molecular dynamics Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.498, year: 2016

Self assembled monolayers of octadecyltrichlorosilane for dielectric materials

Energy Technology Data Exchange (ETDEWEB)

Kumar, Vijay, E-mail: cirivijaypilani@gmail.com [Centre for Nanoscience and Engineering, Indian Institute of Science-Bangalore (India); Mechanical Engineering Department, Birla Institute of Technology and Science-Pilani (India); Puri, Paridhi; Nain, Shivani [Mechanical Engineering Department, Birla Institute of Technology and Science-Pilani (India); Bhat, K. N. [Centre for Nanoscience and Engineering, Indian Institute of Science-Bangalore (India); Sharma, N. N. [Mechanical Engineering Department, Birla Institute of Technology and Science-Pilani (India); School of Automobile, Mechanical & Mechatronics, Manipal University-Jaipur (India)

2016-04-13

Treatment of surfaces to change the interaction of fluids with them is a critical step in constructing useful microfluidics devices, especially those used in biological applications. Selective modification of inorganic materials such as Si, SiO{sub 2} and Si{sub 3}N{sub 4} is of great interest in research and technology. We evaluated the chemical formation of OTS self-assembled monolayers on silicon substrates with different dielectric materials. Our investigations were focused on surface modification of formerly used common dielectric materials SiO{sub 2}, Si{sub 3}N{sub 4} and a-poly. The improvement of wetting behaviour and quality of monolayer films were characterized using Atomic force microscope, Scanning electron microscope, Contact angle goniometer, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) monolayer deposited oxide surface.

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.

X-Ray Reflectometry of DMPS Monolayers on a Water Substrate

Science.gov (United States)

Tikhonov, A. M.; Asadchikov, V. E.; Volkov, Yu. O.; Roshchin, B. S.; Ermakov, Yu. A.

2017-12-01

The molecular structure of dimyristoyl phosphatidylserine (DMPS) monolayers on a water substrate in different phase states has been investigated by X-ray reflectometry with a photon energy of 8 keV. According to the experimental data, the transition from a two-dimensional expanded liquid state to a solid gel state (liquid crystal) accompanied by the ordering of the hydrocarbon tails C14H27 of the DMPS molecule occurs in the monolayer as the surface pressure rises. The monolayer thickness is 20 ± 3 and 28 ± 2 Å in the liquid and solid phases, respectively, with the deflection angle of the molecular tail axis from the normal to the surface in the gel phase being 26° ± 8°. At least a twofold decrease in the degree of hydration of the polar lipid groups also occurs under two-dimensional monolayer compression. The reflectometry data have been analyzed using two approaches: under the assumption about the presence of two layers with different electron densities in the monolayer and without any assumptions about the transverse surface structure. Both approaches demonstrate satisfactory agreement between themselves in describing the experimental results.

Electronic characteristics of p-type transparent SnO monolayer with high carrier mobility

International Nuclear Information System (INIS)

Du, Juan; Xia, Congxin; Liu, Yaming; Li, Xueping; Peng, Yuting; Wei, Shuyi

2017-01-01

Graphical abstract: SnO monolayer is a p-type transparent semiconducting oxide with high hole mobility (∼641 cm 2 V −1 s −1 ), which is much higher than that of MoS 2 monolayer, which indicate that it can be a promising candidate for high-performance nanoelectronic devices. Display Omitted - Highlights: • SnO monolayer is a p-type transparent semiconducting oxide. • The transparent properties can be still maintained under the strain 8%. • It has a high hole mobility (∼641 cm 2 V −1 s −1 ), which is higher than that of MoS 2 monolayer. - Abstract: More recently, two-dimensional (2D) SnO nanosheets are attaching great attention due to its excellent carrier mobility and transparent characteristics. Here, the stability, electronic structures and carrier mobility of SnO monolayer are investigated by using first-principles calculations. The calculations of the phonon dispersion spectra indicate that SnO monolayer is dynamically stable. Moreover, the band gap values are decreased from 3.93 eV to 2.75 eV when the tensile strain is applied from 0% to 12%. Interestingly, SnO monolayer is a p-type transparent semiconducting oxide with hole mobility of 641 cm 2 V −1 s −1 , which is much higher than that of MoS 2 monolayer. These findings make SnO monolayer becomes a promising 2D material for applications in nanoelectronic devices.

A new s-adenosylhomocysteine hydrolase-linked method for adenosine detection based on DNA-templated fluorescent Cu/Ag nanoclusters.

Science.gov (United States)

Ahn, Jun Ki; Kim, Hyo Yong; Baek, Songyi; Park, Hyun Gyu

2017-07-15

We herein describe a novel fluorescent method for the rapid and selective detection of adenosine by utilizing DNA-templated Cu/Ag nanoclusters (NCs) and employing s-adenosylhomocysteine hydrolase (SAHH). SAHH is allowed to promote hydrolysis reaction of s-adenosylhomocysteine (SAH) and consequently produces homocysteine, which would quench the fluorescence signal from DNA-templated Cu/Ag nanoclusters employed as a signaling probe in this study. On the other hand, adenosine significantly inhibits the hydrolysis reaction and prevent the formation of homocysteine. Consequently, highly enhanced fluorescence signal from DNA-Cu/Ag NCs is retained, which could be used to identify the presence of adenosine. By employing this design principle, adenosine was sensitively detected down to 19nM with high specificity over other adenosine analogs such as AMP, ADP, ATP, cAMP, guanosine, cytidine, and urine. Finally, the diagnostic capability of this method was successfully verified by reliably detecting adenosine present in a real human serum sample. Copyright © 2016 Elsevier B.V. All rights reserved.

Strain-mediated electronic properties of pristine and Mn-doped GaN monolayers

Science.gov (United States)

Sharma, Venus; Srivastava, Sunita

2018-04-01

Graphene-like two-dimensional (2D) monolayer structures GaN has gained enormous amount of interest due to high thermal stability and inherent energy band gap for practical applications. First principles calculations are performed to investigate the electronic structure and strain-mediated electronic properties of pristine and Mn-doped GaN monolayer. Binding energy of Mn dopant at various adsorption site is found to be nearly same indicating these sites to be equally favorable for adsorption of foreign atom. Depending on the adsorption site, GaN monolayer can act as p-type or n-type magnetic semiconductor. The tensile strength of both pristine and doped GaN monolayer (∼24 GPa) at ultimate tensile strain of 34% is comparable with the tensile strength of graphene. The in-plane biaxial strain modulate the energy band gap of both pristine and doped-monolayer from direct to indirect gap semiconductor and finally retendered theme into metal at critical value of applied strain. These characteristics make GaN monolayer to be potential candidate for the future applications in tunable optoelectronics.

Monolayer MoSe 2 Grown by Chemical Vapor Deposition for Fast Photodetection

KAUST Repository

Chang, Yung-Huang

2014-08-26

Monolayer molybdenum disulfide (MoS2) has become a promising building block in optoelectronics for its high photosensitivity. However, sulfur vacancies and other defects significantly affect the electrical and optoelectronic properties of monolayer MoS2 devices. Here, highly crystalline molybdenum diselenide (MoSe2) monolayers have been successfully synthesized by the chemical vapor deposition (CVD) method. Low-temperature photoluminescence comparison for MoS2 and MoSe 2 monolayers reveals that the MoSe2 monolayer shows a much weaker bound exciton peak; hence, the phototransistor based on MoSe2 presents a much faster response time (<25 ms) than the corresponding 30 s for the CVD MoS2 monolayer at room temperature in ambient conditions. The images obtained from transmission electron microscopy indicate that the MoSe exhibits fewer defects than MoS2. This work provides the fundamental understanding for the differences in optoelectronic behaviors between MoSe2 and MoS2 and is useful for guiding future designs in 2D material-based optoelectronic devices. © 2014 American Chemical Society.

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.

Neutrophil-endothelial cell interactions on endothelial monolayers grown on micropore filters.

Science.gov (United States)

Taylor, R F; Price, T H; Schwartz, S M; Dale, D C

1981-01-01

We have developed a technique for growing endothelial monolayers on micropore filters. These monolayers demonstrate confluence by phase and electron microscopy and provide a functional barrier to passage of radiolabeled albumin. Neutrophils readily penetrate the monolayer in response to chemotaxin, whereas there is little movement in the absence of chemotaxin. This system offers unique advantages over available chemotaxis assays and may have wider applications in the study of endothelial function. Images PMID:7007441

Proton and hydrogen transport through two-dimensional monolayers

International Nuclear Information System (INIS)

Seel, Max; Pandey, Ravindra

2016-01-01

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

Proton and hydrogen transport through two-dimensional monolayers

Science.gov (United States)

Seel, Max; Pandey, Ravindra

2016-06-01

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

The influence of chromatin structure on the frequency of radiation-induced DNA strand breaks: a study using nuclear and nucleoid monolayers

International Nuclear Information System (INIS)

Ljungman, M.

1991-01-01

To assess the influence of chromatin structure on the frequency of radiation-induced DNA strand breaks, the alkaline unwinding technique was applied to nuclear and nucleoid monolayers. These chromatin substrates were prepared by treating human fibroblasts grown as monolayers with the nonionic detergent Triton X-100 and varying concentrations of cations. The chromatin structure was modified either by a stepwise removal of DNA-bound proteins by extraction in increasing concentrations of monovalent salt, or by the addition or deletion of mono- and divalent cations to condense or decondense the chromatin, respectively. It was found that the stepwise removal of DNA-bound proteins from the chromatin dramatically increased the frequency of radiation-induced DNA strand breaks. The DNA-bound proteins showed a qualitative difference in their ability to protect the DNA where proteins removed by salt concentrations above 1.0 M exerted the greatest protection. Furthermore, the frequency of radiation-induced DNA strand breaks was found to be 6 times lower in condensed chromatin than in decondensed chromatin and about 80 times lower than in protein-depleted chromatin. It is concluded that the presence of DNA-bound proteins and the folding of the chromatin into higher-order structures protect the DNA against radiation-induced strand breaks

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

Studies of the structure and properties of organic monolayers, multilayers and superlattices

International Nuclear Information System (INIS)

Dutta, P.; Ketterson, J.B.

1990-01-01

Organic monolayers and multilayers are both scientifically fascinating and technologically promising; they are, however, both complex systems and relatively inaccessible to experimental probes. In this progress report, we describe our x-ray diffraction studies, which have given us substantial new information about the structures and phase transitions in monolayers on the surface of water; our use of these monolayers as a unique probe of the dynamics of wetting and spreading; and our studies of monolayer mechanical properties using a simple but effective technique available to anyone using the Wilhelmy method to measure surface tension. 20 refs., 11 figs

Langmuir monolayer formation of metal complexes from polymerizable amphiphilic ligands

NARCIS (Netherlands)

Werkman, P.J; Schouten, A.J.

1996-01-01

The monolayer behaviour of 4-(10,12-pentacosadiynoicamidomethyl)-pyridine at the air-water interface was studied by measuring the surface pressure-area isotherms. The amphiphile formed stable monolayers with a clear liquid-expanded (LE) to liquid-condensed phase transition at various temperatures.

Bioimaging of metallothioneins in ocular tissue sections by laser ablation-ICP-MS using bioconjugated gold nanoclusters as specific tags.

Science.gov (United States)

Cruz-Alonso, María; Fernandez, Beatriz; Álvarez, Lydia; González-Iglesias, Héctor; Traub, Heike; Jakubowski, Norbert; Pereiro, Rosario

2017-12-18

An immunohistochemical method is described to visualize the distribution of metallothioneins 1/2 (MT 1/2) and metallothionein 3 (MT 3) in human ocular tissue. It is making use of (a) antibodies conjugated to gold nanoclusters (AuNCs) acting as labels, and (b) laser ablation (LA) coupled to inductively coupled plasma - mass spectrometry (ICP-MS). Water-soluble fluorescent AuNCs (with an average size of 2.7 nm) were synthesized and then conjugated to antibody by carbodiimide coupling. The surface of the modified AuNCs was then blocked with hydroxylamine to avoid nonspecific interactions with biological tissue. Immunoassays for MT 1/2 and MT 3 in ocular tissue sections (5 μm thick) from two post mortem human donors were performed. Imaging studies were then performed by fluorescence using confocal microscopy, and LA-ICP-MS was performed in the retina to measure the signal for gold. Signal amplification by the >500 gold atoms in each nanocluster allowed the antigens (MT 1/2 and MT 3) to be imaged by LA-ICP-MS using a laser spot size as small as 4 μm. The image patterns found in retina are in good agreement with those obtained by conventional fluorescence immunohistochemistry which was used as an established reference method. Graphical abstract Gold nanoclusters (AuNCs) conjugated to a primary specific antibody serve as a label for amplified bioimaging of metallothioneins (MTs) by laser ablation coupled to inductively coupled plasma - mass spectrometry (ICP-MS) in human ocular tissue sections.

Factors responsible for the stability and the existence of a clean energy gap of a silicon nanocluster

International Nuclear Information System (INIS)

Liu, Lei; Jayanthi, C. S.; Wu, Shi-Yu

2001-01-01

We present a critical theoretical study of electronic properties of silicon nanoclusters, in particular the roles played by symmetry, relaxation, and hydrogen passivation on the stability, the gap states and the energy gap of the system using the order N [O(N)] nonorthogonal tight-binding molecular dynamics and the local analysis of electronic structure. We find that for an unrelaxed cluster with its atoms occupying the regular tetrahedral network, the presence of undistorted local bonding configuration is sufficient for the appearance of a small clean energy gap. However, the energy gap of the unrelaxed cluster does not start at the highest occupied molecular orbital (HOMO). In fact, between the HOMO and the lower edge of the energy gap, localized dangling bond states are found. With hydrogen passivation, the localized dangling bond states are eliminated, resulting in a wider and clean energy gap. Relaxation of these hydrogen passivated clusters does not alter either the structure or the energy gap appreciably. However, if the silicon clusters are allowed to relax first, the majority of the dangling bonds are eliminated but additional defect states due to bond distortion appear, making the energy gap dirty. Hydrogen passivation of these relaxed clusters will further eliminate most of the remnant dangling bonds but no appreciable effect on the defect states associated with bond distortions will take place, thus still resulting in a dirty gap. For the hydrogen-passivated Si N nanoclusters with no bond distortion and no overall symmetry, we have studied the variation of the energy gap as a function of size of the cluster for N in the range of 80< N<6000. The dependence of the energy gap on the size shows similar behavior to that for silicon nanoclusters with no bond distortion but possessing overall symmetry

Synthesis of highly dispersed Pt nanoclusters anchored graphene composites and their application for non-enzymatic glucose sensing

International Nuclear Information System (INIS)

Chang, Gang; Shu, Honghui; Huang, Qiwei; Oyama, Munetaka; Ji, Kai; Liu, Xiong; He, Yunbin

2015-01-01

Highlights: • PtNCs/graphene (PVP) composites were obtained by a clean and facile method. • The addition of graphene effectively promotes the catalytic performance of composites. • The highly dispersed PtNCs show superior electrocatalytic activity to glucose oxidation. • PtNCs/graphene (PVP) composites exhibit excellent stability and selectivity for nonenzymatic glucose detection. - Abstract: A facile and clean method by using ascorbic acid as mild reductant was developed to synthesize nanocomposites of graphene and platinum nanoclusters (PtNCs/graphene), in which Polyvinyl-Pyrrolidone (PVP) was added during the one-step reductive process so as to improve the dispersity of PtNCs on the graphene and decrease the size of PtNCs. By several characterization methods such as X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS), we demonstrated that Pt nanoclusters have successfully anchored on the surface of graphene sheets with average diameter of 22 nm. It was found that with the assistant of PVP, Pt nanoclusters appeared with smaller particle size and narrower particle size distribution. Cyclic voltammetry and amperometric methods were used to evaluate the electro-catalytic activity of the synthesized nanocomposites toward the oxidation of glucose in neutral media (0.1 M PBS, pH 7.4). The PtNCs/graphene exhibited a rapid response time (about 3 s), a broad linear range (1 mM to 25 mM), good stability, and sensitivity estimated to be 1.21 μA cm −2 mM −1 (R = 0.995, 71.9 μA cm −2 mM −1 vs. geometric area). Additionally, the impact from the oxidation of interferences can be effectively limited by choosing the appropriate detection potential. These results indicated a great potential of PtNCs/graphene in fabricating novel non-enzymatic glucose sensors with high performance

Wavepacket revivals in monolayer and bilayer graphene rings.

Science.gov (United States)

García, Trinidad; Rodríguez-Bolívar, Salvador; Cordero, Nicolás A; Romera, Elvira

2013-06-12

We have studied the existence of quantum revivals in graphene quantum rings within a simplified model. The time evolution of a Gaussian-populated wavepacket shows revivals in monolayer and bilayer graphene rings. We have also studied this behavior for quantum rings in a perpendicular magnetic field. We have found that revival time is an observable that shows different values for monolayer and bilayer graphene quantum rings. In addition, the revival time shows valley degeneracy breaking.

Electronic characteristics of p-type transparent SnO monolayer with high carrier mobility

Energy Technology Data Exchange (ETDEWEB)

Du, Juan [College of Physics and Materials Science, Henan Normal University, Xinxiang, Henan 453007 (China); Xia, Congxin, E-mail: xiacongxin@htu.edu.cn [College of Physics and Materials Science, Henan Normal University, Xinxiang, Henan 453007 (China); Liu, Yaming [Henan Institute of Science and Technology, Xinxiang 453003 (China); Li, Xueping [College of Physics and Materials Science, Henan Normal University, Xinxiang, Henan 453007 (China); Peng, Yuting [Department of Physics, University of Texas at Arlington, TX 76019 (United States); Wei, Shuyi [College of Physics and Materials Science, Henan Normal University, Xinxiang, Henan 453007 (China)

2017-04-15

Graphical abstract: SnO monolayer is a p-type transparent semiconducting oxide with high hole mobility (∼641 cm{sup 2} V{sup −1} s{sup −1}), which is much higher than that of MoS{sub 2} monolayer, which indicate that it can be a promising candidate for high-performance nanoelectronic devices. Display Omitted - Highlights: • SnO monolayer is a p-type transparent semiconducting oxide. • The transparent properties can be still maintained under the strain 8%. • It has a high hole mobility (∼641 cm{sup 2} V{sup −1} s{sup −1}), which is higher than that of MoS{sub 2} monolayer. - Abstract: More recently, two-dimensional (2D) SnO nanosheets are attaching great attention due to its excellent carrier mobility and transparent characteristics. Here, the stability, electronic structures and carrier mobility of SnO monolayer are investigated by using first-principles calculations. The calculations of the phonon dispersion spectra indicate that SnO monolayer is dynamically stable. Moreover, the band gap values are decreased from 3.93 eV to 2.75 eV when the tensile strain is applied from 0% to 12%. Interestingly, SnO monolayer is a p-type transparent semiconducting oxide with hole mobility of 641 cm{sup 2} V{sup −1} s{sup −1}, which is much higher than that of MoS{sub 2} monolayer. These findings make SnO monolayer becomes a promising 2D material for applications in nanoelectronic devices.

Lower lattice thermal conductivity in SbAs than As or Sb monolayers: a first-principles study.

Science.gov (United States)

Guo, San-Dong; Liu, Jiang-Tao

2017-12-06

Phonon transport in group-VA element (As, Sb and Bi) monolayer semiconductors has been widely investigated in theory, and, of them, monolayer Sb (antimonene) has recently been synthesized. In this work, phonon transport in monolayer SbAs is investigated with a combination of first-principles calculations and the linearized phonon Boltzmann equation. It is found that the lattice thermal conductivity of monolayer SbAs is lower than those of both monolayer As and Sb, and the corresponding sheet thermal conductance is 28.8 W K -1 at room temperature. To understand the lower lattice thermal conductivity in monolayer SbAs than those in monolayer As and Sb, the group velocities and phonon lifetimes of monolayer As, SbAs and Sb are calculated. The calculated results show that the group velocities of monolayer SbAs are between those of monolayer As and Sb, but that the phonon lifetimes of SbAs are smaller than those of both monolayer As and Sb. Hence, the low lattice thermal conductivity in monolayer SbAs is attributed to very small phonon lifetimes. Unexpectedly, the ZA branch has very little contribution to the total thermal conductivity, only 2.4%, which is obviously different from those of monolayer As and Sb with very large contributions. This can be explained by very small phonon lifetimes for the ZA branch of monolayer SbAs. The lower lattice thermal conductivity of monolayer SbAs compared to that of monolayer As or Sb can be understood by the alloying of As (Sb) with Sb (As), which should introduce phonon point defect scattering. We also consider the isotope and size effects on the lattice thermal conductivity. It is found that isotope scattering produces a neglectful effect, and the lattice thermal conductivity with a characteristic length smaller than 30 nm can reach a decrease of about 47%. These results may offer perspectives on tuning the lattice thermal conductivity by the mixture of multiple elements for applications of thermal management and

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

KAUST Repository

Chen, Chang-Hsiao

2014-10-28

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

Emergence of Dirac and quantum spin Hall states in fluorinated monolayer As and AsSb

KAUST Repository

Zhang, Qingyun

2016-01-21

Using first-principles calculations, we investigate the electronic and vibrational properties of monolayer As and AsSb. While the pristine monolayers are semiconductors (direct band gap at the Γ point), fluorination results in Dirac cones at the K points. Fluorinated monolayer As shows a band gap of 0.16 eV due to spin-orbit coupling, and fluorinated monolayer AsSb a larger band gap of 0.37 eV due to inversion symmetry breaking. Spin-orbit coupling induces spin splitting similar to monolayer MoS2. Phonon calculations confirm that both materials are dynamically stable. Calculations of the edge states of nanoribbons by the tight-binding method demonstrate that fluorinated monolayer As is topologically nontrivial in contrast to fluorinated monolayer AsSb.

Surface chemistry of lipid raft and amyloid Aβ (1-40) Langmuir monolayer.

Science.gov (United States)

Thakur, Garima; Pao, Christine; Micic, Miodrag; Johnson, Sheba; Leblanc, Roger M

2011-10-15

Lipid rafts being rich in cholesterol and sphingolipids are considered to provide ordered lipid environment in the neuronal membranes, where it is hypothesized that the cleavage of amyloid precursor protein (APP) to Aβ (1-40) and Aβ (1-42) takes place. It is highly likely that the interaction of lipid raft components like cholesterol, sphingomylein or GM1 leads to nucleation of Aβ and results in aggregation or accumulation of amyloid plaques. One has investigated surface pressure-area isotherms of the lipid raft and Aβ (1-40) Langmuir monolayer. The compression-decompression cycles and the stability of the lipid raft Langmuir monolayer are crucial parameters for the investigation of interaction of Aβ (1-40) with the lipid raft Langmuir monolayer. It was revealed that GM1 provides instability to the lipid raft Langmuir monolayer. Adsorption of Aβ (1-40) onto the lipid raft Langmuir monolayer containing neutral (POPC) or negatively charged phospholipid (DPPG) was examined. The adsorption isotherms revealed that the concentration of cholesterol was important for adsorption of Aβ (1-40) onto the lipid raft Langmuir monolayer containing POPC whereas for the lipid raft Langmuir monolayer containing DPPG:cholesterol or GM1 did not play any role. In situ UV-vis absorption spectroscopy supported the interpretation of results for the adsorption isotherms. Copyright © 2011 Elsevier B.V. All rights reserved.

Ni-Nanocluster Modified Black TiO2 with Dual Active Sites for Selective Photocatalytic CO2 Reduction.

Science.gov (United States)

Billo, Tadesse; Fu, Fang-Yu; Raghunath, Putikam; Shown, Indrajit; Chen, Wei-Fu; Lien, Hsiang-Ting; Shen, Tzu-Hsien; Lee, Jyh-Fu; Chan, Ting-Shan; Huang, Kuo-You; Wu, Chih-I; Lin, M C; Hwang, Jih-Shang; Lee, Chih-Hao; Chen, Li-Chyong; Chen, Kuei-Hsien

2018-01-01

One of the key challenges in artificial photosynthesis is to design a photocatalyst that can bind and activate the CO 2 molecule with the smallest possible activation energy and produce selective hydrocarbon products. In this contribution, a combined experimental and computational study on Ni-nanocluster loaded black TiO 2 (Ni/TiO 2[Vo] ) with built-in dual active sites for selective photocatalytic CO 2 conversion is reported. The findings reveal that the synergistic effects of deliberately induced Ni nanoclusters and oxygen vacancies provide (1) energetically stable CO 2 binding sites with the lowest activation energy (0.08 eV), (2) highly reactive sites, (3) a fast electron transfer pathway, and (4) enhanced light harvesting by lowering the bandgap. The Ni/TiO 2[Vo] photocatalyst has demonstrated highly selective and enhanced photocatalytic activity of more than 18 times higher solar fuel production than the commercial TiO 2 (P-25). An insight into the mechanisms of interfacial charge transfer and product formation is explored. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical Properties of Alkanethiol Monolayers Adsorbed on Nanoporous Au Surfaces

International Nuclear Information System (INIS)

Chu, Yeon Yi; Seo, Bora; Kim, Jong Won

2010-01-01

We investigated the electrochemical properties of alkanethiol monolayers adsorbed on NPG surfaces by cyclic voltammetry and electrochemical impedance spectroscopy, and the results are compared to those on flat Au surfaces. The reductive desorption of alkanethiols on NPG surfaces is observed in more negative potential regions than that on flat Au surfaces due the stronger S-Au interaction on NPG surfaces. While the electron transfer through alkanethiol monolayers on flat Au surfaces occurs via a tunneling process through the monolayer films, the redox species can permeate through the monolayers on NPG surfaces to transfer the electrons to the Au surfaces. The results presented here will help to elucidate the intrinsic electrochemical properties of alkanethiol monolayers adsorbed on curved Au surfaces, particularly on the surface of AuNPs. Self-assembled monolayers (SAMs) of thiolate molecules on Au surfaces have been the subject of intensive research for the last few decades due to their unique physical and chemical properties. The well-organized surface structures of thiolate SAMs with various end-group functionalities can be further utilized for many applications in biology and nanotechnology. In addition to the practical applications, SAMs of thiolate molecules on Au surfaces also provide unique opportunities to address fundamental issues in surface chemistry such as self-organized surface structures, electron transfer behaviors, and moleculesubstrate interactions. Although there have been numerous reports on the fundamental physical and chemical properties of thiolate SAMs on Au surfaces, most of them were investigated on flat Au surfaces, typically on well-defined Au(111) surfaces

Disorder-derived, strong tunneling attenuation in bis-phosphonate monolayers

Science.gov (United States)

Pathak, Anshuma; Bora, Achyut; Liao, Kung-Ching; Schmolke, Hannah; Jung, Antje; Klages, Claus-Peter; Schwartz, Jeffrey; Tornow, Marc

2016-03-01

Monolayers of alkyl bisphosphonic acids (bisPAs) of various carbon chain lengths (C4, C8, C10, C12) were grown on aluminum oxide (AlO x ) surfaces from solution. The structural and electrical properties of these self-assembled monolayers (SAMs) were compared with those of alkyl monophosphonic acids (monoPAs). Through contact angle (CA) and Kelvin-probe (KP) measurements, ellipsometry, and infrared (IR) and x-ray photoelectron (XPS) spectroscopies, it was found that bisPAs form monolayers that are relatively disordered compared to their monoPA analogs. Current-voltage (J-V) measurements made with a hanging Hg drop top contact show tunneling to be the prevailing transport mechanism. However, while the monoPAs have an observed decay constant within the typical range for dense monolayers, β mono  =  0.85  ±  0.03 per carbon atom, a surprisingly high value, β bis  =  1.40  ±  0.05 per carbon atom, was measured for the bisPAs. We attribute this to a strong contribution of ‘through-space’ tunneling, which derives from conformational disorder in the monolayer due to strong interactions of the distal phosphonic acid groups; they likely form a hydrogen-bonding network that largely determines the molecular layer structure. Since bisPA SAMs attenuate tunnel currents more effectively than do the corresponding monoPA SAMs, they may find future application as gate dielectric modification in organic thin film devices.

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.

Synthesis and stability of monolayer-protected Au38 clusters

NARCIS (Netherlands)

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

2008-01-01

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

Landau levels in biased graphene structures with monolayer-bilayer interfaces

Science.gov (United States)

Mirzakhani, M.; Zarenia, M.; Vasilopoulos, P.; Ketabi, S. A.; Peeters, F. M.

2017-09-01

The electron energy spectrum in monolayer-bilayer-monolayer and in bilayer-monolayer-bilayer graphene structures is investigated and the effects of a perpendicular magnetic field and electric bias are studied. Different types of monolayer-bilayer interfaces are considered as zigzag (ZZ) or armchair (AC) junctions which modify considerably the bulk Landau levels (LLs) when the spectra are plotted as a function of the center coordinate of the cyclotron orbit. Far away from the two interfaces, one obtains the well-known LLs for extended monolayer or bilayer graphene. The LL structure changes significantly at the two interfaces or junctions where the valley degeneracy is lifted for both types of junctions, especially when the distance between them is approximately equal to the magnetic length. Varying the nonuniform bias and the width of this junction-to-junction region in either structure strongly influence the resulting spectra. Significant differences exist between ZZ and AC junctions in both structures. The densities of states (DOSs) for unbiased structures are symmetric in energy whereas those for biased structures are asymmetric. An external bias creates interface LLs in the gaps between the LLs of the unbiased system in which the DOS can be quite small. Such a pattern of LLs can be probed by scanning tunneling microscopy.

Wavepacket revivals in monolayer and bilayer graphene rings

International Nuclear Information System (INIS)

García, Trinidad; Rodríguez-Bolívar, Salvador; Cordero, Nicolás A; Romera, Elvira

2013-01-01

We have studied the existence of quantum revivals in graphene quantum rings within a simplified model. The time evolution of a Gaussian-populated wavepacket shows revivals in monolayer and bilayer graphene rings. We have also studied this behavior for quantum rings in a perpendicular magnetic field. We have found that revival time is an observable that shows different values for monolayer and bilayer graphene quantum rings. In addition, the revival time shows valley degeneracy breaking. (paper)

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

NARCIS (Netherlands)

Onclin, S.; Mulder, A.; Huskens, Jurriaan; Ravoo, B.J.; Reinhoudt, David

2004-01-01

Monolayers of β-cyclodextrin host molecules have been prepared on SiO2 surfaces. An ordered and stable cyano-terminated monolayer was modified in three consecutive surface reactions. First, the cyanide groups were reduced to their corresponding free amines using Red Al as a reducing agent. Second,

A self-assembled monolayer-assisted surface microfabrication and release technique

NARCIS (Netherlands)

Kim, B.J.; Liebau, M.; Huskens, Jurriaan; Reinhoudt, David; Brugger, J.P.

2001-01-01

This paper describes a method of thin film and MEMS processing which uses self-assembled monolayers as ultra-thin organic surface coating to enable a simple removal of microfabricated devices off the surface without wet chemical etching. A 1.5-nm thick self-assembled monolayer of

Infrared spectroscopy of self-assembled monolayer films on silicon

Science.gov (United States)

Rowell, N. L.; Tay, Lilin; Boukherroub, R.; Lockwood, D. J.

2007-07-01

Infrared vibrational spectroscopy in an attenuated total reflection (ATR) geometry has been employed to investigate the presence of organic thin layers on Si-wafer surfaces. The phenomena have been simulated to show there can be a field enhancement with the presented single-reflection ATR (SR-ATR) approach which is substantially larger than for conventional ATR or specular reflection. In SR-ATR, a discontinuity of the field normal to the film contributes a field enhancement in the lower index thin film causing a two order of magnitude increase in sensitivity. SR-ATR was employed to characterize a single monolayer of undecylenic acid self-assembled on Si(1 1 1) and to investigate a two monolayer system obtained by adding a monolayer of bovine serum albumin protein.

Triptycene-terminated thiolate and selenolate monolayers on Au(111

Directory of Open Access Journals (Sweden)

Jinxuan Liu

2017-04-01

Full Text Available To study the implications of highly space-demanding organic moieties on the properties of self-assembled monolayers (SAMs, triptycyl thiolates and selenolates with and without methylene spacers on Au(111 surfaces were comprehensively studied using ultra-high vacuum infrared reflection absorption spectroscopy, X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy and thermal desorption spectroscopy. Due to packing effects, the molecules in all monolayers are substantially tilted. In the presence of a methylene spacer the tilt is slightly less pronounced. The selenolate monolayers exhibit smaller defect densities and therefore are more densely packed than their thiolate analogues. The Se–Au binding energy in the investigated SAMs was found to be higher than the S–Au binding energy.

Controlled electrodeposition of Au monolayer film on ionic liquid

Science.gov (United States)

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

2016-05-01

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

Active cell-matrix coupling regulates cellular force landscapes of cohesive epithelial monolayers

Science.gov (United States)

Zhao, Tiankai; Zhang, Yao; Wei, Qiong; Shi, Xuechen; Zhao, Peng; Chen, Long-Qing; Zhang, Sulin

2018-03-01

Epithelial cells can assemble into cohesive monolayers with rich morphologies on substrates due to competition between elastic, edge, and interfacial effects. Here we present a molecularly based thermodynamic model, integrating monolayer and substrate elasticity, and force-mediated focal adhesion formation, to elucidate the active biochemical regulation over the cellular force landscapes in cohesive epithelial monolayers, corroborated by microscopy and immunofluorescence studies. The predicted extracellular traction and intercellular tension are both monolayer size and substrate stiffness dependent, suggestive of cross-talks between intercellular and extracellular activities. Our model sets a firm ground toward a versatile computational framework to uncover the molecular origins of morphogenesis and disease in multicellular epithelia.

Producing air-stable monolayers of phosphorene and their defect engineering.

Science.gov (United States)

Pei, Jiajie; Gai, Xin; Yang, Jiong; Wang, Xibin; Yu, Zongfu; Choi, Duk-Yong; Luther-Davies, Barry; Lu, Yuerui

2016-01-22

It has been a long-standing challenge to produce air-stable few- or monolayer samples of phosphorene because thin phosphorene films degrade rapidly in ambient conditions. Here we demonstrate a new highly controllable method for fabricating high quality, air-stable phosphorene films with a designated number of layers ranging from a few down to monolayer. Our approach involves the use of oxygen plasma dry etching to thin down thick-exfoliated phosphorene flakes, layer by layer with atomic precision. Moreover, in a stabilized phosphorene monolayer, we were able to precisely engineer defects for the first time, which led to efficient emission of photons at new frequencies in the near infrared at room temperature. In addition, we demonstrate the use of an electrostatic gate to tune the photon emission from the defects in a monolayer phosphorene. This could lead to new electronic and optoelectronic devices, such as electrically tunable, broadband near infrared lighting devices operating at room temperature.

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.

Monolayer II-VI semiconductors: A first-principles prediction

Science.gov (United States)

Zheng, Hui; Chen, Nian-Ke; Zhang, S. B.; Li, Xian-Bin

A systematic study of 32 honeycomb monolayer II-VI semiconductors is carried out by first-principles methods. It appears that BeO, MgO, CaO, ZnO, CdO, CaS, SrS, SrSe, BaTe, and HgTe honeycomb monolayers have a good dynamic stability which is revealed by phonon calculations. In addition, from the molecular dynamic (MD) simulation of other unstable candidates, we also find two extra monolayers dynamically stable, which are tetragonal BaS and orthorhombic HgS. The honeycomb monolayers exist in form of either a planar perfect honeycomb or a low-buckled 2D layer, all of which possess a band gap and most of them are in the ultraviolet region. Interestingly, the dynamically stable SrSe has a gap near visible light, and displays exotic electronic properties with a flat top of the valence band, and hence has a strong spin polarization upon hole doping. The honeycomb HgTe has been reported to achieve a topological nontrivial phase under appropriate in-plane tensile strain and spin-orbital coupling (SOC). Some II-VI partners with less than 5% lattice mismatch may be used to design novel 2D heterojunction devices. If synthesized, potential applications of these 2D II-VI families could include optoelectronics, spintronics, and strong correlated electronics. Distinguished Student (DS) Program of APS FIP travel funds.

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.

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.

Liquid-Phase Exfoliation into Monolayered BiOBr Nanosheets for Photocatalytic Oxidation and Reduction

Energy Technology Data Exchange (ETDEWEB)

Yu, Hongjian [Beijing; Huang, Hongwei [Beijing; Xu, Kang [Center; Hao, Weichang [Center; Guo, Yuxi [Beijing; Wang, Shuobo [Beijing; Shen, Xiulin [Beijing; Pan, Shaofeng [Beijing; Zhang, Yihe [Beijing

2017-09-26

Monolayered photocatalytic materials have attracted huge research interests in terms of their large specific surface area and ample active sites. Sillén-structured layered BiOX (X = Cl, Br, I) casts great prospects owing to their strong photo-oxidation ability and high stability. Fabrication of monolayered BiOX by a facile, low-cost, and scalable approach is highly challenging and anticipated. Herein, we describe the large-scale preparation of monolayered BiOBr nanosheets with a thickness of ~0.85 nm via a readily achievable liquid-phase exfoliation strategy with assistance of formamide at ambient conditions. The as-obtained monolayered BiOBr nanosheets are allowed diverse superiorities, such as enhanced specific surface area, promoted band structure, and strengthened charge separation. Profiting from these benefits, the advanced BiOBr monolayers not only show excellent adsorption and photodegradation performance for treating contaminants, but also demonstrate a greatly promoted photocatalytic activity for CO2 reduction into CO and CH4. Additionally, monolayered BiOI nanosheets have also been obtained by the same synthetic approach. Our work offers a mild and general approach for preparation of monolayered BiOX, and may have huge potential to be extended to the synthesis of other single-layer two-dimensional materials.

Label-free turn-on fluorescent detection of melamine based on the anti-quenching ability of Hg 2+ to gold nanoclusters.

Science.gov (United States)

Dai, Haichao; Shi, Yan; Wang, Yilin; Sun, Yujing; Hu, Jingting; Ni, Pengjuan; Li, Zhuang

2014-03-15

In this work, we proposed a facile, environmentally friendly and cost-effective assay for melamine with BSA-stabilized gold nanoclusters (AuNCs) as a fluorescence reader. Melamine, which has a multi-nitrogen heterocyclic ring, is prone to coordinate with Hg(2+). This property causes the anti-quenching ability of Hg(2+) to AuNCs through decreasing the metallophilic interaction between Hg(2+) and Au(+). By this method, detection limit down to 0.15 µM is obtained, which is approximately 130 times lower than that of the US food and Drug Administration estimated melamine safety limit of 20 µM. Furthermore, several real samples spiked with melamine, including raw milk and milk powder, are analyzed using the sensing system with excellent recoveries. This gold-nanocluster-based fluorescent method could find applications in highly sensitive detection of melamine in real samples. © 2013 Elsevier B.V. All rights reserved.

Strongly bound excitons in monolayer PtS2 and PtSe2

KAUST Repository

Sajjad, M.

2018-01-22

Based on first-principles calculations, the structural, electronic, and optical properties of monolayers PtS2 and PtSe2 are investigated. The bond stiffnesses and elastic moduli are determined by means of the spring constants and strain-energy relations, respectively. Dynamic stability is confirmed by calculating the phonon spectra, which shows excellent agreement with experimental reports for the frequencies of the Raman-active modes. The Heyd-Scuseria-Ernzerhof functional results in electronic bandgaps of 2.66 eV for monolayer PtS2 and 1.74 eV for monolayer PtSe2. G0W0 calculations combined with the Bethe-Salpeter equation are used to predict the optical spectra and exciton binding energies (0.78 eV for monolayer PtS2 and 0.60 eV for monolayer PtSe2). It turns out that the excitons are strongly bound and therefore very stable against external perturbations.

Disorder-derived, strong tunneling attenuation in bis-phosphonate monolayers

International Nuclear Information System (INIS)

Pathak, Anshuma; Bora, Achyut; Tornow, Marc; Liao, Kung-Ching; Schwartz, Jeffrey; Schmolke, Hannah; Jung, Antje; Klages, Claus-Peter

2016-01-01

Monolayers of alkyl bisphosphonic acids (bisPAs) of various carbon chain lengths (C4, C8, C10, C12) were grown on aluminum oxide (AlO x ) surfaces from solution. The structural and electrical properties of these self-assembled monolayers (SAMs) were compared with those of alkyl monophosphonic acids (monoPAs). Through contact angle (CA) and Kelvin-probe (KP) measurements, ellipsometry, and infrared (IR) and x-ray photoelectron (XPS) spectroscopies, it was found that bisPAs form monolayers that are relatively disordered compared to their monoPA analogs. Current–voltage (J–V) measurements made with a hanging Hg drop top contact show tunneling to be the prevailing transport mechanism. However, while the monoPAs have an observed decay constant within the typical range for dense monolayers, β mono   =  0.85  ±  0.03 per carbon atom, a surprisingly high value, β bis   =  1.40  ±  0.05 per carbon atom, was measured for the bisPAs. We attribute this to a strong contribution of ‘through-space’ tunneling, which derives from conformational disorder in the monolayer due to strong interactions of the distal phosphonic acid groups; they likely form a hydrogen-bonding network that largely determines the molecular layer structure. Since bisPA SAMs attenuate tunnel currents more effectively than do the corresponding monoPA SAMs, they may find future application as gate dielectric modification in organic thin film devices. (paper)

Defect Structure of Localized Excitons in a WSe2 Monolayer

KAUST Repository

Zhang, Shuai

2017-07-26

The atomic and electronic structure of intrinsic defects in a WSe2 monolayer grown on graphite was revealed by low temperature scanning tunneling microscopy and spectroscopy. Instead of chalcogen vacancies that prevail in other transition metal dichalcogenide materials, intrinsic defects in WSe2 arise surprisingly from single tungsten vacancies, leading to the hole (p-type) doping. Furthermore, we found these defects to dominate the excitonic emission of the WSe2 monolayer at low temperature. Our work provided the first atomic-scale understanding of defect excitons and paved the way toward deciphering the defect structure of single quantum emitters previously discovered in the WSe2 monolayer.

Methods for top-down fabrication of wafer scale TMDC monolayers

Science.gov (United States)

Das, Saptarshi; Bera, Mrinal K.; Roelofs, Andreas K; Antonio, Mark

2017-11-07

A method of forming a TMDC monolayer comprises providing a multi-layer transition metal dichalcogenide (TMDC) film. The multi-layer TMDC film comprises a plurality of layers of the TMDC. The multi-layer TMDC film is positioned on a conducting substrate. The conducting substrate is contacted with an electrolyte solution. A predetermined electrode potential is applied on the conducting substrate and the TMDC monolayer for a predetermined time. A portion of the plurality of layers of the TMDC included in the multi-layer TMDC film is removed by application of the predetermined electrode potential, thereby leaving a TMDC monolayer film positioned on the conducting substrate.

Current Transport Properties of Monolayer Graphene/n-Si Schottky Diodes

Science.gov (United States)

Pathak, C. S.; Garg, Manjari; Singh, J. P.; Singh, R.

2018-05-01

The present work reports on the fabrication and the detailed macroscopic and nanoscale electrical characteristics of monolayer graphene/n-Si Schottky diodes. The temperature dependent electrical transport properties of monolayer graphene/n-Si Schottky diodes were investigated. Nanoscale electrical characterizations were carried out using Kelvin probe force microscopy and conducting atomic force microscopy. Most the values of ideality factor and barrier height are found to be in the range of 2.0–4.4 and 0.50–0.70 eV for monolayer graphene/n-Si nanoscale Schottky contacts. The tunneling of electrons is found to be responsible for the high value of ideality factor for nanoscale Schottky contacts.

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

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.

SYNCHROTRON X-RAY OBSERVATIONS OF A MONOLAYER TEMPLATE FOR MINERALIZATION

International Nuclear Information System (INIS)

Dimasi, E.; Gower, L.B.

2000-01-01

Mineral nucleation at a Langmuir film interface has been studied by synchrotron x-ray scattering. Diluted calcium bicarbonate solutions were used as subphases for arachidic and stearic acid monolayers, compressed in a Langmuir trough. Self-assembly of the monolayer template is observed directly, and subsequent crystal growth monitored in-situ

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...

Self-renewing Monolayer of Primary Colonic or Rectal Epithelial CellsSummary

Directory of Open Access Journals (Sweden)

Yuli Wang

2017-07-01

Full Text Available Background & Aims: Three-dimensional organoid culture has fundamentally changed the in vitro study of intestinal biology enabling novel assays; however, its use is limited because of an inaccessible luminal compartment and challenges to data gathering in a three-dimensional hydrogel matrix. Long-lived, self-renewing 2-dimensional (2-D tissue cultured from primary colon cells has not been accomplished. Methods: The surface matrix and chemical factors that sustain 2-D mouse colonic and human rectal epithelial cell monolayers with cell repertoires comparable to that in vivo were identified. Results: The monolayers formed organoids or colonoids when placed in standard Matrigel culture. As with the colonoids, the monolayers exhibited compartmentalization of proliferative and differentiated cells, with proliferative cells located near the peripheral edges of growing monolayers and differentiated cells predominated in the central regions. Screening of 77 dietary compounds and metabolites revealed altered proliferation or differentiation of the murine colonic epithelium. When exposed to a subset of the compound library, murine organoids exhibited similar responses to that of the monolayer but with differences that were likely attributable to the inaccessible organoid lumen. The response of the human primary epithelium to a compound subset was distinct from that of both the murine primary epithelium and human tumor cells. Conclusions: This study demonstrates that a self-renewing 2-D murine and human monolayer derived from primary cells can serve as a physiologically relevant assay system for study of stem cell renewal and differentiation and for compound screening. The platform holds transformative potential for personalized and precision medicine and can be applied to emerging areas of disease modeling and microbiome studies. Keywords: Colonic Epithelial Cells, Monolayer, Organoids, Compound Screening

Conformations and orientations of a signal peptide interacting with phospholipid monolayers

International Nuclear Information System (INIS)

Cornell, D.G.; Dluhy, R.A.; Briggs, M.S.; McKnight, C.J.; Gierasch, L.M.

1989-01-01

The interaction of a chemically synthesized 25-residue signal peptide of LamB protein from Escherichia coli with phospholipids has been studied with a film balance technique. The conformation, orientation, and concentration of the peptides in lipid monolayers have been determined from polarized infrared spectroscopy, ultraviolet spectroscopy, and assay of 14 C-labeled peptide in transferred films. When the LamB signal peptide in injected into the subphase under a phosphatidylethanolamine-phosphatidylglycerol monolayer at low initial pressure, insertion of a portion of the peptide into the lipid film is evidenced by a rapid rise in film pressure. Spectroscopic results obtained on films transferred to quartz plates and Ge crystals show that the peptide is a mixture of α-helix and β-conformation where the long axis of the α-helix penetrates the monolayer plane and the β-structure which is coplanar with the film. By contrast, when peptide is injected under lipid at high initial pressure, no pressure rise is observed, and the spectroscopic results show the presence of only β-structure which is coplanar with the monolayer. The spectroscopic and radioassay results are all consistent with the picture of a peptide anchored to the monolayer through electrostatic binding with a helical portion inserted into the lipid region of the monolayer and a β-structure portion resident in the aqueous phase. The negative charges on the lipid molecules are roughly neutralized by the positive charges of the peptide

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.

InSe monolayer: synthesis, structure and ultra-high second-harmonic generation

Science.gov (United States)

Zhou, Jiadong; Shi, Jia; Zeng, Qingsheng; Chen, Yu; Niu, Lin; Liu, Fucai; Yu, Ting; Suenaga, Kazu; Liu, Xinfeng; Lin, Junhao; Liu, Zheng

2018-04-01

III–IV layered materials such as indium selenide have excellent photoelectronic properties. However, synthesis of materials in such group, especially with a controlled thickness down to monolayer, still remains challenging. Herein, we demonstrate the successful synthesis of monolayer InSe by physical vapor deposition (PVD) method. The high quality of the sample was confirmed by complementary characterization techniques such as Raman spectroscopy, atomic force microscopy (AFM) and high resolution annular dark field scanning transmission electron microscopy (ADF-STEM). We found the co-existence of different stacking sequence (β- and γ-InSe) in the same flake with a sharp grain boundary in few-layered InSe. Edge reconstruction is also observed in monolayer InSe, which has a distinct atomic structure from the bulk lattice. Moreover, we discovered that the second-harmonic generation (SHG) signal from monolayer InSe shows large optical second-order susceptibility that is 1–2 orders of magnitude higher than MoS2, and even 3 times of the largest value reported in monolayer GaSe. These results make atom-thin InSe a promising candidate for optoelectronic and photosensitive device applications.

Platinum Monolayer Electrocatalysts for Anodic Oxidation of Alcohols.

Science.gov (United States)

Li, Meng; Liu, Ping; Adzic, Radoslav R

2012-12-06

The slow, incomplete oxidation of methanol and ethanol on platinum-based anodes as well as the high price and limited reserves of Pt has hampered the practical application of direct alcohol fuel cells. We describe the electrocatalysts consisting of one Pt monolayer (one atom thick layer) placed on extended or nanoparticle surfaces having the activity and selectivity for the oxidation of alcohol molecules that can be controlled with platinum-support interaction. The suitably expanded Pt monolayer (i.e., Pt/Au(111)) exhibits a factor of 7 activity increase in catalyzing methanol electrooxidation relative to Pt(111). Sizable enhancement is also observed for ethanol electrooxidation. Furthermore, a correlation between substrate-induced lateral strain in a Pt monolayer and its activity/selectivity is established and rationalized by experimental and theoretical studies. The knowledge we gained with single-crystal model catalysts was successfully applied in designing real nanocatalysts. These findings for alcohols are likely to be applicable for the oxidation of other classes of organic molecules.

Measuring the Edge Recombination Velocity of Monolayer Semiconductors.

Science.gov (United States)

Zhao, Peida; Amani, Matin; Lien, Der-Hsien; Ahn, Geun Ho; Kiriya, Daisuke; Mastandrea, James P; Ager, Joel W; Yablonovitch, Eli; Chrzan, Daryl C; Javey, Ali

2017-09-13

Understanding edge effects and quantifying their impact on the carrier properties of two-dimensional (2D) semiconductors is an essential step toward utilizing this material for high performance electronic and optoelectronic devices. WS 2 monolayers patterned into disks of varying diameters are used to experimentally explore the influence of edges on the material's optical properties. Carrier lifetime measurements show a decrease in the effective lifetime, τ effective , as a function of decreasing diameter, suggesting that the edges are active sites for carrier recombination. Accordingly, we introduce a metric called edge recombination velocity (ERV) to characterize the impact of 2D material edges on nonradiative carrier recombination. The unpassivated WS 2 monolayer disks yield an ERV ∼ 4 × 10 4 cm/s. This work quantifies the nonradiative recombination edge effects in monolayer semiconductors, while simultaneously establishing a practical characterization approach that can be used to experimentally explore edge passivation methods for 2D materials.

Photo-induced travelling waves in condensed Langmuir monolayers

Energy Technology Data Exchange (ETDEWEB)

Tabe, Y [Yokoyama Nano-Structured Liquid Crystal Project, ERATO, Japan Science and Technology Corporation, 5-9-9 Tokodai, Tsukuba, Ibaraki 300-2635, Japan (Japan); Yamamoto, T [Yokoyama Nano-Structured Liquid Crystal Project, ERATO, Japan Science and Technology Corporation, 5-9-9 Tokodai, Tsukuba, Ibaraki 300-2635, Japan (Japan); Yokoyama, H [Yokoyama Nano-Structured Liquid Crystal Project, ERATO, Japan Science and Technology Corporation, 5-9-9 Tokodai, Tsukuba, Ibaraki 300-2635, Japan (Japan)

2003-06-01

We report the detailed properties of photo-induced travelling waves in liquid crystalline Langmuir monolayers composed of azobenzene derivatives. When the monolayer, in which the constituent rodlike molecules are coherently tilted from the layer normal, is weakly illuminated to undergo the trans-cis photo-isomerization, spatio-temporal periodic oscillations of the molecular azimuth begin over the entire excited area and propagate as a two-dimensional orientational wave. The wave formation takes place only when the film is formed at an asymmetric interface with broken up-down symmetry and when the chromophores are continuously excited near the long-wavelength edge of absorption to induce repeated photo-isomerizations between the trans and cis forms. Under proper illumination conditions, Langmuir monolayers composed of a wide variety of azobenzene derivatives have been confirmed to exhibit similar travelling waves with velocity proportional to the excitation power irrespective of the degree of amphiphilicity. The dynamics can be qualitatively explained by the modified reaction-diffusion model proposed by Reigada, Sagues and Mikhailov.

Pressure-dependent optical and vibrational properties of monolayer molybdenum disulfide

KAUST Repository

Nayak, Avinash P.

2015-01-14

Controlling the band gap by tuning the lattice structure through pressure engineering is a relatively new route for tailoring the optoelectronic properties of two-dimensional (2D) materials. Here, we investigate the electronic structure and lattice vibrational dynamics of the distorted monolayer 1T-MoS2 (1T′) and the monolayer 2H-MoS2 via a diamond anvil cell (DAC) and density functional theory (DFT) calculations. The direct optical band gap of the monolayer 2H-MoS2 increases by 11.7% from 1.85 to 2.08 eV, which is the highest reported for a 2D transition metal dichalcogenide (TMD) material. DFT calculations reveal a subsequent decrease in the band gap with eventual metallization of the monolayer 2H-MoS2, an overall complex structure-property relation due to the rich band structure of MoS2. Remarkably, the metastable 1T′-MoS2 metallic state remains invariant with pressure, with the J2, A1g, and E2g modes becoming dominant at high pressures. This substantial reversible tunability of the electronic and vibrational properties of the MoS2 family can be extended to other 2D TMDs. These results present an important advance toward controlling the band structure and optoelectronic properties of monolayer MoS2 via pressure, which has vital implications for enhanced device applications.

Growth of cells superinoculated onto irradiated and nonirradiated confluent monolayers

International Nuclear Information System (INIS)

Matsuoka, H.; Ueo, H.; Sugimachi, K.

1990-01-01

We prepared confluent monolayers of normal BALB/c 3T3 cells and compared differences in the growth of four types of cells superinoculated onto these nonirradiated and irradiated monolayers. The test cells were normal BALB/c 3T3 A31 cells, a squamous cell carcinoma from a human esophageal cancer (KSE-1), human fetal fibroblasts, and V-79 cells from Chinese hamster lung fibroblasts. Cell growth was checked by counting the cell number, determining [3H]thymidine incorporation and assessing colony formation. We found that on nonirradiated monolayers, colony formation of human fetal fibroblasts and normal BALB/c 3T3 cells was completely inhibited. On irradiated cells, test cells did exhibit some growth. KSE-1 cells, which had a low clonogenic efficiency on plastic surfaces, formed colonies on both irradiated and nonirradiated cells. On these monolayers, the clonogenic efficiency of V-79 cells was also higher than that on plastic surfaces. We conclude that the nonirradiated monolayer of BALB/c 3T3 cells completely inhibits the growth of superinoculated normal BALB/c 3T3 and human fetal fibroblasts, while on the other hand, they facilitate the growth of neoplastic KSE-1 and V-79 cells by providing a surface for cell adherence and growth, without affecting the presence of normal cells in co-cultures

Controlled synthesis of high-quality crystals of monolayer MoS2 for nanoelectronic device application

DEFF Research Database (Denmark)

Yang, Xiaonian; Li, Qiang; Hu, Guofeng

2016-01-01

. Monolayer MoS2 so far can be obtained by mechanical exfoliation or chemical vapor deposition (CVD). However, controllable synthesis of large area monolayer MoS2 with high quality needs to be improved and their growth mechanism requires more studies. Here we report a systematical study on controlled...... synthesis of high-quality monolayer MoS2 single crystals using low pressure CVD. Large-size monolayer MoS2 triangles with an edge length up to 405 mu m were successfully synthesized. The Raman and photoluminescence spectroscopy studies indicate high homogenous optical characteristic of the synthesized...... monolayer MoS2 triangles. The transmission electron microscopy results demonstrate that monolayer MoS2 triangles are single crystals. The back-gated field effect transistors (FETs) fabricated using the as-grown monolayer MoS2 show typical n-type semiconductor behaviors with carrier mobility up to 21.8 cm(2...

A simple method to tune graphene growth between monolayer and bilayer

Directory of Open Access Journals (Sweden)

Xiaozhi Xu

2016-02-01

Full Text Available Selective growth of either monolayer or bilayer graphene is of great importance. We developed a method to readily tune large area graphene growth from complete monolayer to complete bilayer. In an ambient pressure chemical vapor deposition process, we used the sample temperature at which to start the H2 flow as the control parameter and realized the change from monolayer to bilayer growth of graphene on Cu foil. When the H2 starting temperature was above 700°C, continuous monolayer graphene films were obtained. When the H2 starting temperature was below 350°C, continuous bilayer films were obtained. Detailed characterization of the samples treated under various conditions revealed that heating without the H2 flow caused Cu oxidation. The more the Cu substrate oxidized, the less graphene bilayer could form.

Penetration of Milk-Derived Antimicrobial Peptides into Phospholipid Monolayers as Model Biomembranes

Directory of Open Access Journals (Sweden)

Wanda Barzyk

2013-01-01

Full Text Available Three antimicrobial peptides derived from bovine milk proteins were examined with regard to penetration into insoluble monolayers formed with 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC or 1,2-dipalmitoyl-sn-glycero-3-phospho-rac-(1-glycerol sodium salt (DPPG. Effects on surface pressure (Π and electric surface potential (ΔV were measured, Π with a platinum Wilhelmy plate and ΔV with a vibrating plate. The penetration measurements were performed under stationary diffusion conditions and upon the compression of the monolayers. The two type measurements showed greatly different effects of the peptide-lipid interactions. Results of the stationary penetration show that the peptide interactions with DPPC monolayer are weak, repulsive, and nonspecific while the interactions with DPPG monolayer are significant, attractive, and specific. These results are in accord with the fact that antimicrobial peptides disrupt bacteria membranes (negative while no significant effect on the host membranes (neutral is observed. No such discrimination was revealed from the compression isotherms. The latter indicate that squeezing the penetrant out of the monolayer upon compression does not allow for establishing the penetration equilibrium, so the monolayer remains supersaturated with the penetrant and shows an under-equilibrium orientation within the entire compression range, practically.

Pressure-area isotherm of a lipid monolayer from molecular dynamics simulations

NARCIS (Netherlands)

Baoukina, Svetlana; Monticelli, Luca; Marrink, Siewert J.; Tieleman, D. Peter

2007-01-01

We calculated the pressure-area isotherm of a dipalmitoyl-phosphatidylcholine (DPPC) lipid monolayer from molecular dynamics simulations using a coarse-grained molecular model. We characterized the monolayer structure, geometry, and phases directly from the simulations and compared the calculated

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.

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.

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

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

International Nuclear Information System (INIS)

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

2014-01-01

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

Epitaxially Grown Ultra-Flat Self-Assembling Monolayers with Dendrimers

Directory of Open Access Journals (Sweden)

Takane Imaoka

2018-02-01

Full Text Available Mono-molecular films formed by physical adsorption and dendrimer self-assembly were prepared on various substrate surfaces. It was demonstrated that a uniform dendrimer-based monolayer on the subnanometer scale can be easily constructed via simple dip coating. Furthermore, it was shown that an epitaxially grown monolayer film reflecting the crystal structure of the substrate (highly ordered pyrolytic graphite (HOPG can also be formed by aligning specific conditions.

Atomic defects and doping of monolayer NbSe2

OpenAIRE

Nguyen, Lan; Komsa, Hannu-Pekka; Khestanova, Ekaterina; Kashtiban, Reza J; Peters, Jonathan J.P.; Lawlor, Sean; Sanchez, Ana M.; Sloan, Jeremy; Gorbachev, Roman; Grigorieva, Irina; Krasheninnikov, Arkady V.; Haigh, Sarah

2017-01-01

We have investigated the structure of atomic defects within monolayer NbSe2 encapsulated in graphene by combining atomic resolution transmission electron microscope imaging, density functional theory (DFT) calculations, and strain mapping using geometric phase analysis. We demonstrate the presence of stable Nb and Se monovacancies in monolayer material and reveal that Se monovacancies are the most frequently observed defects, consistent with DFT calculations of their formation energy. We reve...

Effect of lipid composition and packing on the adsorption of apolipoproteins to lipid monolayers

International Nuclear Information System (INIS)

Ibdah, J.A.; Lund-Katz, S.; Phillips, M.C.

1987-01-01

The monolayer system has been used to study the effects of lipoprotein surface lipid composition and packing on the affinities of apolipoproteins for the surfaces of lipoprotein particles. The adsorption of apolipoproteins injected beneath lipid monolayers prepared with pure lipids or lipoprotein surface lipids is evaluated by monitoring the surface pressure of the film and the surface concentration (Gamma) of 14 C-labelled apolipoprotein. At a given initial film pressure (π/sub i/) there is a higher adsorption of human apo A-I to unsaturated phosphatidylcholine (PC) monolayers compared to saturated PC monolayers (e.g., at π/sub i/ = 10 mN/m, Gamma = 0.35 and 0.06 mg/m 2 for egg PC and distearoyl PC, respectively, with 3 x 10 -4 mg/ml apo A-I in the subphase). In addition, adsorption of apo A-I is less to an egg sphingomyelin monolayer than to an egg PC monolayer. The adsorption of apo A-I to PC monolayers is decreased by addition of cholesterol. Generally, apo A-I adsorption diminishes as the lipid molecular area decreases. Apo A-I adsorbs more to monolayers prepared with HDL 3 surface lipids than with LDL surface lipids. These studies suggest that lipoprotein surface lipid composition and packing are crucial factors influencing the transfer and exchange of apolipoproteins among various lipoprotein classes during metabolism of lipoprotein particles

Electrochemical behavior of monolayer and bilayer graphene.

Science.gov (United States)

Valota, Anna T; Kinloch, Ian A; Novoselov, Kostya S; Casiraghi, Cinzia; Eckmann, Axel; Hill, Ernie W; Dryfe, Robert A W

2011-11-22

Results of a study on the electrochemical properties of exfoliated single and multilayer graphene flakes are presented. Graphene flakes were deposited on silicon/silicon oxide wafers to enable fast and accurate characterization by optical microscopy and Raman spectroscopy. Conductive silver paint and silver wires were used to fabricate contacts; epoxy resin was employed as a masking coating in order to expose a stable, well-defined area of graphene. Both multilayer and monolayer graphene microelectrodes showed quasi-reversible behavior during voltammetric measurements in potassium ferricyanide. However, the standard heterogeneous charge transfer rate constant, k°, was estimated to be higher for monolayer graphene flakes. © 2011 American Chemical Society

Low temperature photoresponse of monolayer tungsten disulphide

Directory of Open Access Journals (Sweden)

Bingchen Cao

2014-11-01

Full Text Available High photoresponse can be achieved in monolayers of transition metal dichalcogenides. However, the response times are inconveniently limited by defects. Here, we report low temperature photoresponse of monolayer tungsten disulphide prepared by exfoliation and chemical vapour deposition (CVD method. The exfoliated device exhibits n-type behaviour; while the CVD device exhibits intrinsic behaviour. In off state, the CVD device has four times larger ratio of photoresponse for laser on/off and photoresponse decay–rise times are 0.1 s (limited by our setup, while the exfoliated device has few seconds. These findings are discussed in terms of charge trapping and localization.

Electrically tunable magnetic configuration on vacancy-doped GaSe monolayer

Science.gov (United States)

Tang, Weiqing; Ke, Congming; Fu, Mingming; Wu, Yaping; Zhang, Chunmiao; Lin, Wei; Lu, Shiqiang; Wu, Zhiming; Yang, Weihuang; Kang, Junyong

2018-03-01

Group-IIIA metal-monochalcogenides with the enticing properties have attracted tremendous attention across various scientific disciplines. With the aim to satisfy the multiple demands of device applications, here we report a design framework on GaSe monolayer in an effort to tune the electronic and magnetic properties through a dual modulation of vacancy doping and electric field. A half-metallicity with a 100% spin polarization is generated in a Ga vacancy doped GaSe monolayer due to the nonbonding 4p electronic orbital of the surrounding Se atoms. The stability of magnetic moment is found to be determined by the direction of applied electric field. A switchable magnetic configuration in Ga vacancy doped GaSe monolayer is achieved under a critical electric field of 0.6 V/Å. Electric field induces redistribution of the electronic states. Finally, charge transfers are found to be responsible for the controllable magnetic structure in this system. The magnetic modulation on GaSe monolayer in this work offers some references for the design and fabrication of tunable two-dimensional spintronic device.

Theory of lithium islands and monolayers: Electronic structure and stability

International Nuclear Information System (INIS)

Quassowski, S.; Hermann, K.

1995-01-01

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

Nanotubes based on monolayer blue phosphorus

KAUST Repository

Montes Muñ oz, Enrique; Schwingenschlö gl, Udo

2016-01-01

We demonstrate structural stability of monolayer zigzag and armchair blue phosphorus nanotubes by means of molecular dynamics simulations. The vibrational spectrum and electronic band structure are determined and analyzed as functions of the tube

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

Science.gov (United States)

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

2008-09-01

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

Overcrowding drives the unjamming transition of gap-free monolayers

Science.gov (United States)

Lan, Ganhui; Su, Tao

Collective cell motility plays central roles in various biological phenomena such as wound healing, cancer metastasis and embryogenesis. These are demonstrations of the unjamming transition in biology. However, contradictory to the typical density-driven jamming in particulate assemblies, cellular systems often get unjammed in highly packed, sometimes overcrowding environments. Here, we investigate monolayers' collective behaviors when cell number changes under the gap-free constraint. We report that overcrowding can unjam gap-free monolayers through increasing isotropic compression. We show that the transition boundary is determined by the isotropic compression and the cell-cell adhesion. Furthermore, we construct the free energy landscape for the T1 topological transition during monolayer rearrangement, and discover that the landscape evolves from single-barrier W shape to double-barrier M shape during the unjamming process. We also discover a distributed-to-disordered morphological transition of cells' geometry, coinciding with the unjamming transition. Our analyses reveal that the overcrowding and adhesion induced unjamming reflects the mechanical yielding of the highly deformable monolayer, suggesting an alternative mechanism that cells may robustly gain collective mobility through proliferation in confined environments, which differs from those caused by loosing up a packed particulate assembly. This work is supported by the GWU College Facilitating Funds.

Vertical uniformity of cells and nuclei in epithelial monolayers.

Science.gov (United States)

Neelam, Srujana; Hayes, Peter Robert; Zhang, Qiao; Dickinson, Richard B; Lele, Tanmay P

2016-01-22

Morphological variability in cytoskeletal organization, organelle position and cell boundaries is a common feature of cultured cells. Remarkable uniformity and reproducibility in structure can be accomplished by providing cells with defined geometric cues. Cells in tissues can also self-organize in the absence of directing extracellular cues; however the mechanical principles for such self-organization are not understood. We report that unlike horizontal shapes, the vertical shapes of the cell and nucleus in the z-dimension are uniform in cells in cultured monolayers compared to isolated cells. Apical surfaces of cells and their nuclei in monolayers were flat and heights were uniform. In contrast, isolated cells, or cells with disrupted cell-cell adhesions had nuclei with curved apical surfaces and variable heights. Isolated cells cultured within micron-sized square wells displayed flat cell and nuclear shapes similar to cells in monolayers. Local disruption of nuclear-cytoskeletal linkages resulted in spatial variation in vertical uniformity. These results suggest that competition between cell-cell pulling forces that expand and shorten the vertical cell cross-section, thereby widening and flattening the nucleus, and the resistance of the nucleus to further flattening results in uniform cell and nuclear cross-sections. Our results reveal the mechanical principles of self-organized vertical uniformity in cell monolayers.

Phase transitions in polymer monolayers

NARCIS (Netherlands)

Deschênes, Louise; Lyklema, J.; Danis, Claude; Saint-Germain, François

2015-01-01

In this paper we investigate the application of the two-dimensional Clapeyron law to polymer monolayers. This is a largely unexplored area of research. The main problems are (1) establishing if equilibrium is reached and (2) if so, identifying and defining phases as functions of the temperature.

Direct immobilization of antibodies on Zn-doped Fe_3O_4 nanoclusters for detection of pathogenic bacteria

International Nuclear Information System (INIS)

Pal, Monalisa; Lee, Sanghee; Kwon, Donghoon; Hwang, Jeongin; Lee, Hyeonjeong; Hwang, Seokyung; Jeon, Sangmin

2017-01-01

Zinc-doped magnetic nanoclusters (Zn-MNCs) were synthesized and used to detect pathogenic bacteria in milk. Hydrothermally synthesized Zn-MNCs exhibited stronger magnetic properties than pure MNCs, which facilitated the magnetic separation from the sample using a permanent magnet. The presence of accessible Zn sites allows the direct immobilization of half-fragmented antibodies over Zn-MNCs through strong Zn−S bonds and prevents the tedious multiple steps of molecular functionalization or coating with costly noble metals prior to conjugation with an antibody. After the capture and magnetic separation of Salmonella in milk using the antibody-functionalized Zn-MNCs, the concentration of bacteria was determined with a portable ATP luminometer and the detection limit was found to be 10 CFU/mL. - Highlights: • Zn-doped Fe_3O_4 nanoclusters (Zn-MNCs) were synthesized by hydrothermal method. • Antibodies were directly immobilized over Zn-MNCs through strong Zn–S_t_h_i_o_l bonds. • Higher magnetization of Zn-MNCs than pure MNCs facilitates the magnetic separation. • Detection limit of pathogenic bacteria in milk was found to be 10 cfu/mL. • Cost effective, sensitive and selective detection of bacteria.

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.

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

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.

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.

Interactions of phospholipid monolayer with single-walled carbon nanotube wrapped by lysophospholipid

Energy Technology Data Exchange (ETDEWEB)

Lim, Siwool; Kim, Hyungsu, E-mail: hkim@dku.edu

2012-10-01

In this study, we prepared single-walled carbon nanotubes (SWNTs) wrapped by 1-stearoyl-2-hydroxy-sn-glycero-3-phospho-(1 Prime -rac-glycerol) (LPG), leading to a complex of SWNT-LPG. In an attempt to investigate the interactions of SWNT-LPG with a mimicked cell surface, SWNT-LPG solution was injected into the sub-phase of Langmuir trough to form a mixed monolayer with dipalmitoylphosphatidylcholine (DPPC) and dipalmitoylphosphatidylglycerol (DPPG), respectively. In addition to the measurement of typical surface pressure-area isotherms under compression mode, area changes occurring during insertion of SWNT-LPG into the monolayer were recorded at various surface pressures. Changes in surface potential were also measured for evident tracing of the degree of interactions between sub-phase and monolayer. A systematic comparison of relaxation patterns and insertion behavior along with surface potential data provided a rational basis to distinguish the degree of interactions between SWNT-LPG and the designated monolayer. The observed tendencies were found to be in accordance with the surface topography as revealed by the tapping mode atomic force microscopy. It was consistently observed that SWNT-LPG interacted with DPPC to a greater extent than with DPPG, when the sufficient coverage of nanotube surface by LPG molecules was assured. - Highlights: Black-Right-Pointing-Pointer Complex of single-walled carbon nanotubes and lysophospholipid (SWNT-LPG) is formed. Black-Right-Pointing-Pointer Composite monolayer is formed by inserting SWNT-LPG into the phospholipid monolayer. Black-Right-Pointing-Pointer We measure area-pressure responses and dipole potentials during the insertion process. Black-Right-Pointing-Pointer Properties of composite monolayer depend on the kind of phospholipid and LPG content.

The langmuir monolayer: an efficient model for studying interfacial properties of biomembranes

International Nuclear Information System (INIS)

Cirak, J.; Sokolsky, M.; Dobrocka, E.; Weis, M.

2012-01-01

In this communication, we describe aspects of monolayer technology by focusing on effects of calcium ions on physical properties of phospholipid monolayers using results of measurements of surface pressure, x-ray reflectivity and AFM. These experiments are motivated by the search for lipid-DNA complexes with high transfection efficiency but without toxicity which might be a promising tool in gene therapy. In each part methodological importance is stressed and its specificity for studying molecular interactions at a lipid monolayer. (authors)

Quantification of stromal vascular cell mechanics with a linear cell monolayer rheometer

Energy Technology Data Exchange (ETDEWEB)

Elkins, Claire M., E-mail: cma9@stanford.edu; Fuller, Gerald G. [Department of Chemical Engineering, Stanford University, Stanford, California 94305 (United States); Shen, Wen-Jun; Khor, Victor K.; Kraemer, Fredric B. [Division of Endocrinology, Gerontology and Metabolism, Stanford University, Stanford, California 94305 and Veterans Affairs Palo Alto Health Care System, Palo Alto, California 94304 (United States)

2015-01-15

Over the past few decades researchers have developed a variety of methods for measuring the mechanical properties of whole cells, including traction force microscopy, atomic force microscopy (AFM), and single-cell tensile testing. Though each of these techniques provides insight into cell mechanics, most also involve some nonideal conditions for acquiring live cell data, such as probing only one portion of a cell at a time, or placing the cell in a nonrepresentative geometry during testing. In the present work, we describe the development of a linear cell monolayer rheometer (LCMR) and its application to measure the mechanics of a live, confluent monolayer of stromal vascular cells. In the LCMR, a monolayer of cells is contacted on both top and bottom by two collagen-coated plates and allowed to adhere. The top plate then shears the monolayer by stepping forward to induce a predetermined step strain, while a force transducer attached to the top plate collects stress information. The stress and strain data are then used to determine the maximum relaxation modulus recorded after step-strain, G{sub r}{sup 0}, referred to as the zero-time relaxation modulus of the cell monolayer. The present study validates the ability of the LCMR to quantify cell mechanics by measuring the change in G{sub r}{sup 0} of a confluent cell monolayer upon the selective inhibition of three major cytoskeletal components (actin microfilaments, vimentin intermediate filaments, and microtubules). The LCMR results indicate that both actin- and vimentin-deficient cells had ∼50% lower G{sub r}{sup 0} values than wild-type, whereas tubulin deficiency resulted in ∼100% higher G{sub r}{sup 0} values. These findings constitute the first use of a cell monolayer rheometer to quantitatively distinguish the roles of different cytoskeletal elements in maintaining cell stiffness and structure. Significantly, they are consistent with results obtained using single-cell mechanical testing methods

Tuning Ag29 nanocluster light emission from red to blue with one and two-photon excitation.

Science.gov (United States)

Russier-Antoine, Isabelle; Bertorelle, Franck; Hamouda, Ramzi; Rayane, Driss; Dugourd, Philippe; Sanader, Željka; Bonačić-Koutecký, Vlasta; Brevet, Pierre-François; Antoine, Rodolphe

2016-02-07

We demonstrate that the tuning of the light emission from red to blue in dihydrolipoic acid (DHLA) capped Ag29 nanoclusters can be trigged with one and two photon excitations. The cluster stoichiometry was determined with mass spectrometry and found to be Ag29(DHLA)12. In a detailed optical investigation, we show that these silver nanoclusters exhibit a strong red photoluminescence visible to the naked eye and characterized by a quantum yield of nearly ∼2% upon one-photon excitation. In the nonlinear optical (NLO) study of the properties of the clusters, the two-photon excited fluorescence spectra were recorded and their first hyperpolarizability obtained. The two-photon absorption cross-section at ∼800 nm for Ag29(DHLA)12 is higher than 10(4) GM and the hyperpolarizability is 106 × 10(-30) esu at the same excitation wavelength. The two-photon excited fluorescence spectrum appears strongly blue-shifted as compared to the one-photon excited spectrum, displaying a broad band between 400 and 700 nm. The density functional theory (DFT) provides insight into the structural and electronic properties of Ag29(DHLA)12 as well as into interplay between metallic subunit or core and ligands which is responsible for unique optical properties.

Simulation studies of pore and domain formation in a phospholipid monolayer

NARCIS (Netherlands)

Knecht, Volker; Muller, M; Bonn, M; Marrink, SJ; Mark, AE

2005-01-01

Despite extensive study the phase behavior of phospholipid monolayers at an air-water interface is still not fully understood. In particular recent vibrational sum-frequency generation (VSFG) spectra of DPPC monolayers as a function of area density show a sharp transition in the order of the lipid

Conformation, orientation and interaction in molecular monolayers

International Nuclear Information System (INIS)

Superfine, R.; Huang, J.Y.; Shen, Y.R.

1989-01-01

Knowledge of the conformation and ordering of molecular monolayers is essential for a detailed understanding of a wide variety of surface and interfacial phenomena. Over the past several years, surface second harmonic generation (SHG) has proven to be a valuable and versatile probe of monolayer systems. Our group has recently extended the technique to infrared-visible sum frequency generation (SFG) which has unique capabilities for surface vibrational spectroscopy. Like second harmonic generation, SFG is highly surface specific with submonolayer sensitivity at all interfaces accessible by light. The orientation of individual groups within an adsorbate molecule can be deduced by a polarization analysis of the SFG signal from the vibrational modes of the groups. The authors have used SHG and SFG to study orientations and conformations of surfactant and liquid crystal (LC) monolayers and their interaction on a substrate. The interfacial properties of LC are of great interest to many researchers for both basic science understanding and practical application to LC devices. It is well known that the bulk alignment of a liquid crystal in a cell is strongly affected by the surface treatment of the cell walls. The reason behind it is not yet clear. The theoretical background and experimental arrangement of SHG and SFG have been described elsewhere. In the setup, a 30 psec. Nd:YAG mode-locked laser system together with nonlinear accessories generates a visible beam at .532μm and an infrared beam tunable about 3.4μm. Both beams are focused to a common spot of 300μm dia. The typical signal off the surface from a compact ordered alkyl chain monolayer is ∼500 photons per pulse, easily detected with a photomultiplier tube

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.

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.

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.

Fluorescent probe for turn-on sensing of L-cysteine by ensemble of AuNCs and polymer protected AuNPs.

Science.gov (United States)

Xu, Xiaozhe; Qiao, Juan; Li, Nan; Qi, Li; Zhang, Shufeng

2015-06-16

A new fluorescent probe based on ensemble of gold nanoclusters (AuNCs) and polymer protected gold nanoparticles (AuNPs) for turn-on sensing of L-cysteine was designed and prepared. The AuNCs were protected by bovine serum albumin and had strong fluorescence. The polymer protected AuNPs were synthesized by a facile in situ strategy at room temperature and could quench the fluorescence of AuNCs due to the Förster resonance energy transfer. Interestingly, it has been observed that the quenched fluorescence of AuNCs was recovered by L-cysteine, which could induce the aggregation of polymer protected AuNPs by sulfur group. Then the prepared fluorescent probe was successfully used for determination of L-Cys in human urines, which would have an evolving aspect and promote the subsequent exploration. Copyright © 2015 Elsevier B.V. All rights reserved.

Microchannel-flowed-plasma modification of octadecyltrichlorosilane self-assembled-monolayers for liquid crystal alignment

International Nuclear Information System (INIS)

Zheng, W.; Chiang, C.-Y.; Underwood, I.

2013-01-01

We report that a chemical patterning technique based on local plasma modification of self-assembled monolayers has been utilized to fabricate surfaces for domain liquid crystal alignment. Highly hydrophobic octadecyltrichlorosilane monolayers deposited on glass substrates coated with Indium-Tin-Oxide were brought into contact with elastomeric stamps comprising trenches on a micro scale, and then exposed to an oxygen plasma. In the regions exposed to the plasma the monolayer was etched away leaving a patterned surface that exhibited surface energy differences between surface domains. The surfaces that bear the micropatterns have been shown to be capable of producing patterned alignment of nematic liquid crystal. - Highlights: • Chemical surface-patterning is used to fabricate liquid crystal alignment surface. • Highly hydrophobic octadecyltrichlorosilane monolayer is deposited on substrate. • O 2 plasma flow is used to etch the monolayer to form patterned surface. • The patterned surface exhibits surface energy differences between surface domains. • The surface borne the micropatterns is capable of domain liquid crystal alignment

Lateral electron transport in monolayers of short chains at interfaces: A Monte Carlo study

International Nuclear Information System (INIS)

George, Christopher B.; Szleifer, Igal; Ratner, Mark A.

2010-01-01

Graphical abstract: Electron hopping between electroactive sites in a monolayer composed of redox-active and redox-passive molecules. - Abstract: Using Monte Carlo simulations, we study lateral electronic diffusion in dense monolayers composed of a mixture of redox-active and redox-passive chains tethered to a surface. Two charge transport mechanisms are considered: the physical diffusion of electroactive chains and electron hopping between redox-active sites. Results indicate that by varying the monolayer density, the mole fraction of electroactive chains, and the electron hopping range, the dominant charge transport mechanism can be changed. For high density monolayers in a semi-crystalline phase, electron diffusion proceeds via electron hopping almost exclusively, leading to static percolation behavior. In fluid monolayers, the diffusion of chains may contribute more to the overall electronic diffusion, reducing the observed static percolation effects.

Interferon induction in bovine and feline monolayer cultures by four bluetongue virus serotypes.

OpenAIRE

Fulton, R W; Pearson, N J

1982-01-01

The interferon inducing ability of bluetongue viruses was studied in bovine and feline monolayer cultures inoculated with each of four bluetongue virus serotypes. Interferon was assayed by a plaque reduction method in monolayer cultures with vesicular stomatitis virus as challenge virus. Interferon was produced by bovine turbinate, Georgia bovine kidney, and Crandell feline kidney monolayer cultures in response to bluetongue virus serotypes 10, 11, 13 and 17. The antiviral substances produced...

Investigation on gallium ions impacting monolayer graphene

Energy Technology Data Exchange (ETDEWEB)

Wu, Xin; Zhao, Haiyan, E-mail: hyzhao@tsinghua.edu.cn; Yan, Dong; Pei, Jiayun [State Key Laboratory of Tribology, Tsinghua University, Beijing 100084, P. R. Chinaand Department of Mechanical Engineering, Tsinghua University, Beijing 100084 (China)

2015-06-15

In this paper, the physical phenomena of gallium (Ga{sup +}) ion impacting monolayer graphene in the nanosculpting process are investigated experimentally, and the mechanisms are explained by using Monte Carlo (MC) and molecular dynamics (MD) simulations. Firstly, the MC method is employed to clarify the phenomena happened to the monolayer graphene target under Ga{sup +} ion irradiation. It is found that substrate has strong influence on the damage mode of graphene. The mean sputtering yield of graphene under 30 keV Ga{sup +} ion irradiation is 1.77 and the least ion dose to completely remove carbon atoms in graphene is 21.6 ion/nm{sup 2}. Afterwards, the focused ion beam over 21.6 ion/nm{sup 2} is used for the irradiation on a monolayer graphene supported by SiO2 experimentally, resulting in the nanostructures, i.e., nanodot and nanowire array on the graphene. The performances of the nanostructures are characterized by atomic force microscopy and Raman spectrum. A plasma plume shielding model is put forward to explain the nanosculpting results of graphene under different irradiation parameters. In addition, two damage mechanisms are found existing in the fabrication process of the nanostructures by using empirical MD simulations. The results can help us open the possibilities for better control of nanocarbon devices.

Electric field effect of GaAs monolayer from first principles

Directory of Open Access Journals (Sweden)

Jiongyao Wu

2017-03-01

Full Text Available Using first-principle calculations, we investigate two-dimensional (2D honeycomb monolayer structures composed of group III-V binary elements. It is found that such compound like GaAs should have a buckled structure which is more stable than graphene-like flat structure. This results a polar system with out-of-plane dipoles arising from the non-planar structure. Here, we optimized GaAs monolayer structure, then calculated the electronic band structure and the change of buckling height under external electric field within density functional theory using generalized gradient approximation method. We found that the band gap would change proportionally with the electric field magnitude. When the spin-orbit coupling (SOC is considered, we revealed fine spin-splitting at different points in the reciprocal space. Furthermore, the valence and conduction bands spin-splitting energies due to SOC at the K point of buckled GaAs monolayers are found to be weakly dependent on the electric field strength. Finally electric field effects on the spin texture and second harmonic generation are discussed. The present work sheds light on the control of physical properties of GaAs monolayer by the applied electric field.

Interfacial and thermal energy driven growth and evolution of Langmuir-Schaefer monolayers of Au-nanoparticles.

Science.gov (United States)

Mukhopadhyay, Mala; Hazra, S

2018-01-03

Structures of Langmuir-Schaefer (LS) monolayers of thiol-coated Au-nanoparticles (DT-AuNPs) deposited on H-terminated and OTS self-assembled Si substrates (of different hydrophobic strength and stability) and their evolution with time under ambient conditions, which plays an important role for their practical use as 2D-nanostructures over large areas, were investigated using the X-ray reflectivity technique. The strong effect of substrate surface energy (γ) on the initial structures and the competitive role of room temperature thermal energy (kT) and the change in interfacial energy (Δγ) at ambient conditions on the evolution and final structures of the DT-AuNP LS monolayers are evident. The strong-hydrophobic OTS-Si substrate, during transfer, seems to induce strong attraction towards hydrophobic DT-AuNPs on hydrophilic (repulsive) water to form vertically compact partially covered (with voids) monolayer structures (of perfect monolayer thickness) at low pressure and nearly covered buckled monolayer structures (of enhanced monolayer thickness) at high pressure. After transfer, the small kT-energy (in absence of repulsive water) probably fluctuates the DT-AuNPs to form vertically expanded monolayer structures, through systematic exponential growth with time. The effect is prominent for the film deposited at low pressure, where the initial film-coverage and film-thickness are low. On the other hand, the weak-hydrophobic H-Si substrate, during transfer, appears to induce optimum attraction towards DT-AuNPs to better mimic the Langmuir monolayer structures on it. After transfer, the change in the substrate surface nature, from weak-hydrophobic to weak-hydrophilic with time (i.e. Δγ-energy, apart from the kT-energy), enhances the size of the voids and weakens the monolayer/bilayer structure to form a similar expanded monolayer structure, the thickness of which is probably optimized by the available thermal energy.