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Sample records for gold sulfide monolayer

  1. Monolayer Films Prepared by the Spontaneous Self-Assembly of Symmetrical and Unsymmetrical Dialkyl Sulfides from Solution Onto Gold Substrates: Structure, Properties, and Reactivity of Constituent Functional Groups.

    DTIC Science & Technology

    1987-10-01

    adsorption of dialkyl sulfides from alcohol solution onto supported evaporated gold films and examines relations between the molecular structure of the...derivatives. The particular hypothesis used as the basis for this work is summarized in Figure 1. Adsorption of an unsymmetrical dialkyl sulfide, CH3 (CH2...minutes to hours. The adsorption process, and the characteristics of the resulting films, were followed using a number of techniques, of which

  2. Monolayer coated gold nanoparticles for delivery applications

    PubMed Central

    Rana, Subinoy; Bajaj, Avinash; Mout, Rubul; Rotello, Vincent M.

    2011-01-01

    Gold nanoparticles (AuNPs) provide attractive vehicles for delivery of drugs, genetic materials, proteins, and small molecules. AuNPs feature low core toxicity coupled with the ability to parametrically control particle size and surface properties. In this review, we focus on engineering of the AuNP surface monolayer, highlighting recent advances in tuning monolayer structures for efficient delivery of drugs and biomolecules. This review covers two broad categories of particle functionalization, organic monolayers and biomolecule coatings, and discusses their applications in drug, DNA/RNA, protein and small molecule delivery. PMID:21925556

  3. Large excitonic effects in group-IV sulfide monolayers

    NASA Astrophysics Data System (ADS)

    Tuttle, Blair R.; Alhassan, Saeed M.; Pantelides, Sokrates T.

    2015-12-01

    Large exciton binding energies are a distinguishing feature of two-dimensional semiconductors because of reduced screening, potentially leading to unique optoelectronic applications. Here we use electronic structure methods to calculate the properties of a two-dimensional material class: group-IV monosulfides including SiS, GeS, and SnS. Bulk SiS is predicted to be a metastable layered material. Quasiparticle excitations are calculated with the G0W0 method and the Bethe-Salpeter equation is are used to include electron-hole interactions. For monolayers, strongly bound excitons are found below the quasiparticle absorption edge. The predicted excitonic binding energies are as high as 0.7 eV. Due to large excitonic effects, these group-IV sulfide monolayers have great potential for nanoscale optoelectronic applications.

  4. An array of layers in silicon sulfides: Chainlike and monolayer

    NASA Astrophysics Data System (ADS)

    Alonso-Lanza, T.; Ayuela, A.; Aguilera-Granja, F.

    2016-12-01

    While much is known about isoelectronic materials related to carbon nanostructures, such as boron-nitride layers and nanotubes, rather less is known about equivalent silicon-based materials. Following the recent discovery of phosphorene, here we discuss isoelectronic silicon-monosulfide monolayers. We describe a set of anisotropic structures that clearly have a high stability with respect to previously reported silicon-monosulfide monolayers. The source of the layer anisotropy is related to the presence of Si-S double chains linked by some Si-Si covalent bonds together with a remarkable spd hybridization on Si. The increased stability is related to silicon forming four bonds, including an additional double-bond-like Si-Si bond. The involvement of d orbitals brings more variety to silicon-sulfide-based nanostructures that are isoelectronic to phosphorene, which could be relevant for future applications, adding extra degrees of freedom.

  5. Kinetics of alkanethiol monolayer desorption from gold in air.

    PubMed

    Shadnam, Mohammad Reza; Amirfazli, A

    2005-10-14

    Thermal desorption of an alkanethiol monolayer from a gold substrate into a gaseous medium under ambient pressure was investigated using XPS and it was found that there exist 2 consecutive 1st order kinetics mechanisms with activation energies of 29.9 and 32.7 kcal mol(-1), respectively, i.e. on average approximately 15% higher than reports for liquid media desorption.

  6. Pinholes and Defects in Octadecylmercaptan Monolayers on Gold.

    NASA Astrophysics Data System (ADS)

    Snider, Daniel Aaron

    Alkylmercaptan monolayers on gold electrodes have been actively studied since they have potential use as modified electrodes. The amazing thing about these electrodes, is that they survive the electrochemical experiment and are extremely blocking to redox couples in solution. Early attempts to model blocked electrode behavior in terms of electron tunnelling failed. The approximate shape of a Tafel plot at low overpotentials should obey Butler-Volmer kinetics with a slope of 1 order of magnitude current per 120 mV of overpotential. Typical alkylmercaptan-coated electrodes result in Tafel plots with depressed slopes. This phenomena was interpreted in terms of imperfections in the monolayer which allow redox couples to approach the gold surface closer than the full length of the monolayer would allow. We assess imperfections in octadecylmercaptan -coated (OM) gold electrodes by passivating and blocking the pinholes. We passivate pinholes to an inner-sphere redox couple with an adsorbed layer of iodine. We block pinholes with the self-passivating polymer polyphenylene oxide to an outer sphere redox couple. To determine the size and distribution of pinholes in the OM monlayer we study the system with oxide stripping, liner scan voltammetry and AC Impedance Spectroscopy. We have determined that imperfections can be classified as pinholes and defects. Pinholes are areas where a redox couple has direct access to the gold surface. Defects are areas where a redox couple can come closer than the full length of the monolayer but not in direct contact with the monolayer. Both, pinholes and defects result in larger faradaic currents and more non-ideal Tafel plots than would be seen with electron tunnelling. We have determined that pinholes, typically, have radii that are micron size with pinhole separation tens of microns. Additionally, Oxide Stripping experiments are the most damaging way to assess pinhole coverage, with AC impedance spectroscopy providing the most useful

  7. Protein recognition by a self-assembled deep cavitand monolayer on a gold substrate.

    PubMed

    Liu, Ying; Taira, Toshiaki; Young, Michael C; Ajami, Dariush; Rebek, Julius; Cheng, Quan; Hooley, Richard J

    2012-01-17

    This paper details the first use of a self-folding deep cavitand on a gold surface. A sulfide-footed deep, self-folding cavitand has been synthesized, and its attachment to a cleaned gold surface studied by electrochemical and SPR methods. Complete monolayer formation is possible if the cavitand folding is templated by noncovalent binding of choline or by addition of space-filling thiols to cover any gaps in the cavitand adsorption layer. The cavitand is capable of binding trimethylammonium-tagged guests from an aqueous medium and can be deposited in 2 × 2 microarrays on the surface for characterization by SPR imaging techniques. When biotin-labeled guests are used, the cavitand:guest construct can recognize and immobilize streptavidin proteins from aqueous solution, acting as an effective supramolecular biosensor for monitoring protein recognition.

  8. Fluorescent monolayer protected gold nanoparticles - Preparation and structure elucidation

    NASA Astrophysics Data System (ADS)

    Angelova, P.; Kuchukova, N.; Dobrikov, G. M.; Timtcheva, I.; Kostova, K.; Petkova, I.; Vauthey, E.

    2011-05-01

    A novel N-substituted 4-methoxy-1,8-naphthalimide (NAFTA 8) especially designed for fluorescent labeling of gold nanoparticles has been synthesized. NAFTA 8 bears a long methylene chain at the imide N atom and has a terminal SH group, which enables its chemical binding to gold nanostructures. The longest wavelength absorption maximum of NAFTA 8 in chloroform is at 370 nm, the fluorescent maximum is at 430 nm and the fluorescent quantum yield is 0.95. The newly synthesized fluorophore is applied for functionalization of gold nanoparticles with diameter 1.5 ± 0.5 nm prepared through chemical reduction. The obtained Monolayer Protected Clusters are characterized by elemental analysis, TEM, XPS, FT-IR, absorption and fluorescence spectroscopy. The performed investigations provide evidence for the formation of chemical bond between the thiol ligand and the gold surface. They also show that the obtained metal/dielectric 3D structures are highly fluorescent.

  9. Tuning the structure of thermosensitive gold nanoparticle monolayers.

    PubMed

    Rezende, Camila A; Shan, Jun; Lee, Lay-Theng; Zalczer, Gilbert; Tenhu, Heikki

    2009-07-23

    Gold nanoparticles grafted with poly(N-isopropylacrylamide) (PNIPAM) are rendered amphiphilic and thermosensitive. When spread on the surface of water, they form stable Langmuir monolayers that exhibit surface plasmon resonance. Using Langmuir balance and contrast-matched neutron reflectivity, the detailed structural properties of these nanocomposite monolayers are revealed. At low surface coverage, the gold nanoparticles are anchored to the interface by an adsorbed PNIPAM layer that forms a thin and compact pancake structure. Upon isothermal compression (T=20 degrees C), the adsorbed layer thickens with partial desorption of polymer chains to form brush structures. Two distinct polymer conformations thus coexist: an adsorbed conformation that assures stability of the monolayer, and brush structures that dangle in the subphase. An increase in temperature to 30 degrees C results in contractions of both adsorbed and brush layers with a concomitant decrease in interparticle distance, indicating vertical as well as lateral contractions of the graft polymer layer. The reversibility of this thermal response is also shown by the contraction-expansion of the polymer layers in heating-cooling cycles. The structure of the monolayer can thus be tuned by compression and reversibly by temperature. These compression and thermally induced conformational changes are discussed in relation to optical properties.

  10. Structure and function evolution of thiolate monolayers on gold

    SciTech Connect

    Edwards, Grant Alvin

    2006-01-01

    The use of n-alkanethiolate self-assembled monolayers on gold has blossomed in the past few years. These systems have functioned as models for common interfaces. Thiolate monolayers are ideal because they are easily modified before or after deposition. The works contained within this dissertation include interfacial characterization (infrared reflection absorption spectroscopy, ellipsometry, contact angle, scanning probe microscopy, and heterogeneous electron-transfer kinetics) and various modeling scenarios. The results of these characterizations present ground-breaking insights into the structure, function, and reproducible preparation of these monolayers. Surprisingly, three interfacial properties (electron-transfer, contact angle, and ellipsometry) were discovered to depend directly on the odd-even character of the monolayer components. Molecular modeling was utilized to investigate adlayer orientation, and suggests that these effects are adlayer structure specific. Finally, the electric force microscopy and theoretical modeling investigations of monolayer samples are presented, which show that the film dielectric constant, thickness, and dipole moment directly affect image contrast. In addition, the prospects for utilization of this emerging technique are outlined.

  11. Structure and Function Evolution of Thiolate Monolayers on Gold

    SciTech Connect

    Edwards, Grant Alvin

    2006-01-01

    The use of n-alkanethiolate self-assembled monolayers on gold has blossomed in the past few years. These systems have functioned as models for common interfaces. Thiolate monolayers are ideal because they are easily modified before or after deposition. The works contained within this dissertation include interfacial characterization (inbred reflection absorption spectroscopy, ellipsometry, contact angle, scanning probe microscopy, and heterogeneous electron-transfer kinetics) and various modeling scenarios. The results of these characterizations present ground-breaking insights into the structure, function, and reproducible preparation of these monolayers. Surprisingly, three interfacial properties (electron-transfer, contact angle, and ellipsometry) were discovered to depend directly on the odd-even character of the monolayer components. Molecular modeling was utilized to investigate adlayer orientation, and suggests that these effects are adlayer structure specific. Finally, the electric force microscopy and theoretical modeling investigations of monolayer samples are presented, which show that the film dielectric constant, thickness, and dipole moment directly affect image contrast. In addition, the prospects for utilization of this emerging technique are outlined.

  12. On the characteristics of mixed Langmuir monolayer templates containing dipalmitoyl phosphatidylcholine for gold nanoparticle formation.

    PubMed

    Hsiao, Fang-Wei; Lee, Yuh-Lang; Chang, Chien-Hsiang

    2009-10-01

    Mixed Langmuir monolayers containing dipalmitoyl phosphatidylcholine (DPPC) were applied as two-dimensional templates to incorporate with gold precursor AuCl4- in the subphases. The organic monolayer templates were then transferred onto solid substrates to form ultra-thin films by the Langmuir-Blodgett (LB) deposition technique. With an UV irradiation approach, gold nanoparticles were thus fabricated in the LB films of monolayer templates. Characteristics of the monolayer templates were studied by the surface pressure-area isotherm measurements and Brewster angle microscopy (BAM) observation. The factors affecting the formation of gold nanoparticle structures in the LB films of organic monolayer templates were elucidated by the atomic force microscopy (AFM). The monolayer isotherms and BAM images suggested that by changing the gold precursor concentration in the subphase, one could control the adsorption behavior of the gold precursor onto the monolayer templates. It was found that the association of the gold precursor with a pure DPPC monolayer template resulted in an unstable Langmuir monolayer, which was inappropriate for the following LB deposition. With the presence of n-hexadecanol in a DPPC monolayer, the monolayer template stability and corresponding LB deposition quality could be tremendously improved. Moreover, the distribution of DPPC molecules in the monolayer templates was possible to be regulated by the addition of n-hexadecanol, and the association behavior of the gold precursor with the monolayer templates was thus controlled. The AFM analysis then indicated that the number and size of gold nanoparticles fabricated in the LB films of the mixed DPPC/n-hexadecanol monolayer templates by a photoreduction reaction could be manipulated by the mole fraction of n-hexadecanol and UV irradiation time.

  13. Dendritic functionalization of monolayer-protected gold nanoparticles

    SciTech Connect

    Cutler, Erin C.; Lundin, Erik; Garabato, B. Davis; Choi, Daeock; Shon, Young-Seok . E-mail: young.shon@wku.edu

    2007-06-05

    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. {sup 1}H NMR spectroscopy, FT-IR spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) were used for the characterization of these hybrid nanoparticles.

  14. Assembly of citrate gold nanoparticles on hydrophilic monolayers

    NASA Astrophysics Data System (ADS)

    Vikholm-Lundin, Inger; Rosqvist, Emil; Ihalainen, Petri; Munter, Tony; Honkimaa, Anni; Marjomäki, Varpu; Albers, Willem M.; Peltonen, Jouko

    2016-08-01

    Self-assembled monolayers (SAMs) as model surfaces were linked onto planar gold films thorough lipoic acid or disulfide groups. The molecules used were polyethylene glycol (EG-S-S), N-[tris-(hydroxymethyl)methyl]acrylamide polymers with and without lipoic acid (Lipa-pTHMMAA and pTHMMAA) and a lipoic acid triazine derivative (Lipa-MF). All the layers, but Lipa-MF with a primary amino group were hydroxyl terminated. The layers were characterized by contact angle measurements and atomic force microscopy, AFM. Citrate stabilized nanoparticles, AuNPs in water and phosphate buffer were allowed to assemble on the layers for 10 min and the binding was followed in real-time with surface plasmon resonance, SPR. The SPR resonance curves were observed to shift to higher angles and become increasingly damped, while also the peaks strongly broaden when large nanoparticles assembled on the surface. Both the angular shift and the damping of the curve was largest for nanoparticles assembling on the EG-S-S monolayer. High amounts of particles were also assembled on the pTHMMAA layer without the lipoic acid group, but the damping of the curve was considerably lower with a more even distribution of the particles. Topographical images confirmed that the highest number of particles were assembled on the polyethylene glycol monolayer. By increasing the interaction time more particles could be assembled on the surface.

  15. Influences of the adsorption of different elements on the electronic structures of a tin sulfide monolayer.

    PubMed

    Li, Yang; Xia, Congxin; Du, Juan; Xiong, Wenqi; Li, Xueping; Wei, Shuyi

    2017-02-15

    Based on first-principles calculations, we investigated the adsorption energy, structural parameters, and electronic and magnetic properties for the adsorption of different atoms, including light metals, hydrogen, oxygen, and 3D transition metals (TM) adatoms, on a tin sulfide (SnS) monolayer. The results showed that Li- and Al-atom adsorption can effectively induce n-type carriers, whereas O atom adsorption can produce p-type doping in the SnS monolayer. In addition, except for Ni atoms, the other adatoms can induce magnetism in the SnS monolayer. Moreover, for Fe- and Co-atom adsorption, the occupied and unoccupied states belong to the same spin-channel. These results indicate that surface adsorption is an effective method to tune the electronic structures of the SnS monolayer.

  16. Molecular Beam Optical Study of Gold Sulfide and Gold Oxide

    NASA Astrophysics Data System (ADS)

    Zhang, Ruohan; Yu, Yuanqin; Steimle, Timothy

    2016-06-01

    Gold-sulfur and gold-oxygen bonds are key components to numerous established and emerging technologies that have applications as far ranging as medical imaging, catalysis, electronics, and material science. A major theoretical challenge for describing this bonding is correctly accounting for the large relativistic and electron correlation effects. Such effects are best studied in diatomic, AuX, molecules. Recently, the observed AuS electronic state energy ordering was measured and compared to a simple molecular orbital diagram prediction. Here we more thoroughly investigate the nature of the electronic states of both AuS and AuO from the analysis of high-resolution (FWHM\\cong35MHz) optical Zeeman spectroscopy of the (0,0){B}2Σ--{X}2Π3/2 bands. The determined fine and hyperfine parameters for the {B}2Σ- state of AuO differ from those extracted from the analysis of a hot, Doppler-limited, spectrum. It is demonstrated that the nature of the {B}2Σ- states of AuO and AuS are radically different. The magnetic tuning of AuO and AuS indicates that the {B}2Σ- states are heavily contaminated. Supported by the National Science Foundation under Grant No.1265885. D. L. Kokkin, R. Zhang, T. C. Steimle, I. A. Wyse, B. W. Pearlman and T. D. Varberg, J. Phys. Chem. A., 119(48), 4412, 2015. L. C. O'Brien, B. A. Borchert, A. Farquhar, S. Shaji, J. J. O'Brien and R. W. Field, J. Mol. Spectrosc., 252(2), 136, 2008

  17. The gold content of volcanogenic massive sulfide deposits

    NASA Astrophysics Data System (ADS)

    Mercier-Langevin, Patrick; Hannington, Mark D.; Dubé, Benoît; Bécu, Valérie

    2011-07-01

    Volcanogenic massive sulfide deposits contain variable amounts of gold, both in terms of average grade and total gold content, with some VMS deposits hosting world-class gold mines with more than 100 t Au. Previous studies have identified gold-rich VMS as having an average gold grade, expressed in g/t, exceeding the total abundance of base metals, expressed in wt.%. However, statistically meaningful criteria for the identification of truly anomalous deposits have not been established. This paper presents a more extensive analysis of gold grades and tonnages of 513 VMS deposits worldwide, revealing a number of important features in the distribution of the data. A large proportion of deposits are characterized by a relatively low gold grade (<2 g/t), with a gradual decrease in frequency towards maximum gold grades, defining a log-normal distribution. In the analysis presented in this paper, the geometric mean and geometric standard deviation appear to be the simplest metric for identifying subclasses of VMS deposits based on gold grade, especially when comparing deposits within individual belts and districts. The geometric mean gold grade of 513 VMS deposits worldwide is 0.76 g/t; the geometric standard deviation is +2.70 g/t Au. In this analysis, deposits with more than 3.46 g/t Au (geometric mean plus one geometric standard deviation) are considered auriferous. The geometric mean gold content is 4.7 t Au, with a geometric standard deviation of +26.3 t Au. Deposits containing 31 t Au or more (geometric mean plus one geometric standard deviation) are also considered to be anomalous in terms of gold content, irrespective of the gold grade. Deposits with more than 3.46 g/t Au and 31 t Au are considered gold-rich VMS. A large proportion of the total gold hosted in VMS worldwide is found in a relatively small number of such deposits. The identification of these truly anomalous systems helps shed light on the geological parameters that control unusual enrichment of gold

  18. Vibrational properties of an adamantane monolayer on a gold surface

    NASA Astrophysics Data System (ADS)

    Sakai, Yuki; Nguyen, Giang D.; Capaz, Rodrigo B.; Coh, Sinisa; Pechenezhskiy, Ivan V.; Hong, Xiaoping; Crommie, Michael F.; Wang, Feng; Saito, Susumu; Louie, Steven G.; Cohen, Marvin L.

    2014-03-01

    We study the vibrational properties of an adamantane monolayer on a Au(111) surface. The IR spectrum of a self-assembled monolayer of adamantane on Au(111) is measured by a newly developed infrared scanning tunneling microscopy (IRSTM) technique. We analyze the IR spectrum of this system by a density functional theory and find that the IR spectrum is severely modified by both adamantane-gold and adamantane-adamantane interactions. One of three gas-phase C-H bond stretching modes is significantly red-shifted due to the molecule-substrate interactions. The intermolecular interactions cause a suppression of the IR intensity of another gas-phase IR peak. The techniques used in this work can be applied for an independent estimate of molecule-substrate and intermolecular interactions in related diamondoid/metal-substrate systems. This work was supported by NSF grant No. DMR10-1006184 and U.S. DOE under Contract No. DE-AC02-05CH11231.

  19. Near Infrared Resonant Gold / Gold Sulfide Nanoparticles as a Photothermal Cancer Therapeutic Agent

    PubMed Central

    Gobin, André M.; Watkins, Emily M.; Quevedo, Elizabeth; Colvin, Vicki L.; West, Jennifer L.

    2010-01-01

    The development and optimization of near-infrared (nIR) absorbing nanoparticles for use as photothermal cancer therapeutic agents has been ongoing. We have previously reported on larger layered gold / silica nanoshells (~140 nm) for combined therapy and imaging applications. This work exploits the properties of smaller gold / gold sulfide (GGS) nIR absorbing nanoparticles (~35–55 nm) that provide higher absorption (98% absorption & 2% scattering for GGS versus 70% absorption & 30% scattering for gold/silica nanoshells) as well as potentially better tumor penetration. In this work we demonstrate ability to ablate tumor cells in vitro, and efficacy for photothermal cancer therapy, where in an in vivo model we show significantly increased long-term, tumor-free survival. Further, enhanced circulation and bio-distribution is observed in vivo. This class of nIR absorbing nanoparticles has potential to improve upon photothermal tumor ablation for cancer therapy. PMID:20183810

  20. Electron-Impurity Interactions in the Relaxation of Hot Electrons in Gold-Gold Sulfide Nanoshells

    NASA Astrophysics Data System (ADS)

    Westcott, Sarah; Wolfgang, John; Nordlander, Peter; Halas, Naomi

    2000-10-01

    Hot electron dynamics can be modified in metallic nanostructures compared to bulk metals. In this experiment, ultrafast pump-probe spectroscopy permits observation of the effects of the local environment on hot electron relaxation in gold nanoshell particles. These nanoparticles consist of spherical (40 nm diameter) gold sulfide cores surrounded by ultrathin (5 nm) gold shells and possess a structure-dependent plasmon resonance.^1 Following excitation by a pump pulse at the plasmon resonance, the relaxation of the hot electrons in the nanoparticle's shell layer was observed. When molecules were adsorbed onto the nanoshell surface, increased electronic relaxation rates were observed for those molecular species with the greatest induced dipole moments near the nanoparticle surface. The effect of impurity adsorbates on the nanoparticle's electron dynamics is attributed to a perturbation in the electronic potential in the metal by the presence of the nearby impurities. ^1 R. D. Averitt, D. Sarkar, and N. J. Halas, Phys. Rev. Lett. 78, 4217 (1997).

  1. Platinum monolayer electrocatalyst on gold nanostructures on silicon for photoelectrochemical hydrogen evolution.

    PubMed

    Kye, Joohong; Shin, Muncheol; Lim, Bora; Jang, Jae-Won; Oh, Ilwhan; Hwang, Seongpil

    2013-07-23

    Pt monolayer decorated gold nanostructured film on planar p-type silicon is utilized for photoelectrochemical H2 generation in this work. First, gold nanostructured film on silicon was spontaneously produced by galvanic displacement of the reduction of gold ion and the oxidation of silicon in the presence of fluoride anion. Second, underpotential deposition (UPD) of copper under illumination produced Cu monolayer on gold nanostructured film followed by galvanic exchange of less-noble Cu monolayer with more-noble PtCl6(2-). Pt(shell)/Au(core) on p-type silicon showed the similar activity with platinum nanoparticle on silicon for photoelectrochemical hydrogen evolution reaction in spite of low platinum loading. From Tafel analysis, Pt(shell)/Au(core) electrocatalyst shows the higher area-specific activity than platinum nanoparticle on silicon demonstrating the significant role of underlying gold for charge transfer reaction from silicon to H(+) through platinum catalyst.

  2. Self-assembled monolayers of phosphorylcholine alkylthiols on gold

    NASA Astrophysics Data System (ADS)

    Tegoulia, Vassiliki; Rao, Weisun; Cooper, Stuart

    2000-03-01

    One of the most intriguing developments in biomaterials science in the past decade has been the observation that membrane-mimetic systems based on the phosphorylcholine head group limit the adsorption of proteins and cells on surfaces. This phenomenon may be related to the zwitterionic nature of the phosphorylcholine moiety and the tendency for a large amount of bound water to be associated with this structure. In this work, we have prepared and studied single and mixed self-assembled monolayers (SAMs) of phoshorylcholine (PC) and hydroxyl (OH) or methyl (CH3) terminated thiols on gold-coated substrates in order to create surfaces that resist protein adsorption and cell adhesion. The direct organization of monomolecular assemblies on solid surfaces provided a convenient method for fabricating substrates with well-defined compositions and structures. The surfaces have been characterized by means of contact angle measurements, ellipsometry, X-ray photoelectron spectroscopy and grazing angle-FTIR. The resulting surfaces exhibited good resistance to the adsorption of a variety of proteins such as fibrinogen, fibronectin and albumin. Results evaluating bacterial and leukocyte adhesion under flow on these surfaces will be discussed.

  3. Electronic and optical properties of beryllium sulfide monolayer: Under stress and strain conditions

    NASA Astrophysics Data System (ADS)

    Jalilian, Jaafar; Safari, Mandana

    2016-10-01

    Electronic and optical properties of two-dimensional graphene-like structure of beryllium sulfide (BeS) have been studied in the framework of the density functional theory. Different values of stress and strain are exerted for tuning electronic and optical parameters. The electronic results show that both biaxial stress and strain effects cause band gap reduction with different rates. Also, we have red and blue shifts in the optical absorption spectrum peaks by applying strain and stress, respectively. Our results express that BeS monolayer can be the promising candidate for the future nano-devices.

  4. Organo-Soluble Porphyrin Mixed Monolayer-Protected Gold Nanorods with Intercalated Fullerenes

    DTIC Science & Technology

    2012-03-16

    Plasmon Electronic Oscillations in Gold and Silver Nanodots and Nanorods . J. Phys. Chem. B 1999, 103, 8410- 8426. (7) Yu, C.; Irudayaraj, J...Mixed Monolayer- Protected Gold Nanorods with Intercalated Fullerenes Chenming Xue, Yongqian Xu, Yi Pang, Dingshan Yu, Liming Dai, Min Gao, Augustine...Protected Gold Nanorods with Intercalated Fullerenes 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT

  5. Electrochemical and scanning probe microscopic characterization of spontaneously adsorbed organothiolate monolayers at gold

    SciTech Connect

    Wong, Sze-Shun Season

    1999-12-10

    This dissertation presented several results which add to the general knowledge base regarding organothiolates monolayer spontaneously adsorbed at gold films. Common to the body of this work is the use of voltammetric reductive resorption and variants of scanning probe microscopy to gain insight into the nature of the monolayer formation process as well as the resulting interface. The most significant result from this work is the success of using friction force microscopy to discriminate the end group orientation of monolayer chemisorbed at smooth gold surfaces with micrometer resolution (Chapter 4). The ability to detect the differences in the orientational disposition is demonstrated by the use PDMS polymer stamp to microcontact print an adlayer of n-alkanethiolate of length n in a predefine pattern onto a gold surface, followed by the solution deposition of a n-alkanethiol of n ± 1 to fill in the areas on the gold surface intentionally not coated by the stamping process. These two-component monolayers can be discriminated by using friction force microscopy which detects differences in friction contributed by the differences in the orientation of the terminal groups at surfaces. This success has recently led to the detection of the orientation differences at nanometer scale. Although the substrates examined in this work consisted entirely of smooth gold films, the same test can be performed on other smooth substrates and monolayer materials.

  6. Molecular structure of cysteamine monolayers on silver and gold substrates. Comparative studies by surface-enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Michota, Agnieszka; Kudelski, Andrzej; Bukowska, Jolanta

    2002-04-01

    Monolayers of cysteamine (2-aminoethanethiol) frequently work as linkage layers for adsorption of other molecules on metal surfaces. We compared the structure of cysteamine monolayers formed on gold and silver and the influence of various electrolytes on the structure of monolayers formed on both substrates. The monolayers formed on silver contain significantly higher portion of a trans conformer than monolayers on gold. Probably monolayers on silver are self-assembled in such a way that higher portion of the amino groups is unbonded to the surface, thus being available for attaching other molecules. The structure of cysteamine monolayers formed on gold is considerably more stable and resistive to the influence of electrolytes as compared to the silver substrate. The greater stability of the monolayers on Au surface was ascribed to the strong affinity of the amine groups toward this metal.

  7. Synthesis and characterization of mixed monolayer protected gold nanorods and their Raman activities

    SciTech Connect

    Mlambo, Mbuso; Mdluli, Phumlani S.; Shumbula, Poslet; Mpelane, Siyasanga; Moloto, Nosipho; Skepu, Amanda; Tshikhudo, Robert

    2013-10-15

    Graphical abstract: Gold nanorods surface functionalization. - Highlights: • Mixed monolayer protected gold nanorods. • Surface enhanced Raman spectroscopy. • HS-(CH{sub 2}){sub 11}-NHCO-coumarin as a Raman active compound. - Abstract: The cetyltrimethylammonium bromide (CTAB) gold nanorods (AuNRs) were prepared by seed-mediated route followed by the addition of a Raman active compound (HS-(CH{sub 2}){sub 11}-NHCO-coumarin) on the gold nanorods surfaces. Different stoichiometric mixtures of HS-(CH{sub 2}){sub 11}-NHCO-coumarin and HS-PEG-(CH{sub 2}){sub 11}COOH were evaluated for their Raman activities. The lowest stoichiometric ratio HS-(CH{sub 2}){sub 11}-NHCO-coumarin adsorbed on gold nanorods surface was detected and enhanced by Raman spectroscopy. The produced mixed monolayer protected gold nanorods were characterized by UV-vis spectrometer for optical properties, transmission electron microscope (TEM) for structural properties (shape and aspect ratio) and their zeta potentials (charges) were obtained from ZetaSizer to determine the stability of the produced mixed monolayer protected gold nanorods. The Raman results showed a surface enhanced Raman scattering (SERS) enhancement at the lowest stoichiometric ratio of 1% HS-(CH{sub 2}){sub 11}-NHCO-coumarin compared to high ratio of 50% HS-(CH{sub 2}){sub 11}-NHCO-coumarin on the surface of gold nanorods.

  8. Two-laser mass spectrometry of thiolate, disulfide, and sulfide self-assembled monolayers.

    SciTech Connect

    Trevor, J. L.; Lykke, K. R.; Chemistry; Univ. of Illinois at Chicago

    1998-03-31

    Self-assembled monolayers (SAMs) of thiolates, disulfides (RSSR+), and sulfides were studied on Au by N2 laser desorption followed by vacuum ultraviolet (VUV) (118-nm) photoionization of secondary neutrals in a time-of-flight mass spectrometer. Dimers (RSSR+) dominated the photoionization mass spectrum from all chain lengths of alkanethiolates and disulfides studied. Nonmethyl-terminated alkanethiolates with X = (OH and COOH) were detected as dimers without loss of the terminal group. Phenyl-SAMs with X = (H, OH, OCH3, Cl, and NO2) were detected as both monomers and dimers. Thiocholesterol SAMs were detected solely as monomers. The data suggest that dimerization occurs as a result of the recombination of surface thiolates during desorption. The alkane sulfides were detected intact, but with additional monomer and dimer species present in the spectra. The appearance of dimers is not a strong function of adsorbate structure or ordering and therefore cannot be taken as evidence for or against the recently proposed model of thiolate dimers on Au surfaces. Two receptor adsorbates, resorcin[4]arene tetrasulfide and {beta}-cyclodextrin sulfide were examined by two-laser mass spectrometry (L2MS), but only the former gave identifiable high mass peaks. Mixed thiolate and disulfide monolayers generated both pure and mixed dimers, providing information on nearest neighbor interactions. The mixed disulfide results indicate there is a common adsorption state for thiolates and disulfides. The laser desorption and VUV photoionization cross sections for these various organosulfur SAMs were found to be similar. L2MS with VUV photoionization was nonselective in its detection of these organosulfur species and produced mass spectra with little fragmentation.

  9. [Biooxidation of a Double-Refractory Gold-Bearing Sulfide Ore Concentrate].

    PubMed

    Bulaev, A G; Kanaeva, Z K; Kanaev, A T; Kondrat'eva, T F

    2015-01-01

    The efficiency of biooxidation for treatment of a double-refractory gold-bearing sulfide ore concentrate from the Bakyrchik deposit (East Kazakhstan) was defined. The experiments were conducted in two different modes, i.e., with the standard liquid medium and the medium imitating the chemical composition of the Bakyrchik deposit groundwater and containing high concentrations of sodium, magnesium, and chloride. The concentrate contained 17.5% of organic carbon, 6% of pyrite and 13% arsenopyrite. Gold content was 57.5 g t@-1@. Direct gold recovery by cyanidation was very low (2.8%). While biooxidation was efficient in both cases (approximately 90% of sulfide sulfur was oxidized), the efficiency of cyanidation was low (39 and 32%, respectively). This fact suggests high efficiency of biooxidation is insufficient for efficient treatment of double-refractory gold-bearing sulfide ore concentrates.

  10. Solvent-mediated conductance increase of dodecanethiol-stabilized gold nanoparticle monolayers

    PubMed Central

    Tisserant, Jean-Nicolas; Sánchez-Ferrer, Antoni; Mezzenga, Raffaele

    2016-01-01

    Gold nanoparticle monolayers provide convenient templates to study charge transport in organic molecules beyond single junction techniques. Conductance is reported to increase by several orders of magnitude following immersion of alkanethiol-stabilized gold nanoparticle monolayers in a solution containing conjugated thiol-functionalized molecules. Typically, this observation is attributed to molecular exchange. Less attention has been paid to the role of the solvent alone. Here, we report on an increase in conductance of dodecanethiol-stabilized gold nanoparticle monolayers on Si/SiO2 by an average factor of 36 and 22 after immersion in pure ethanol (EtOH) and tetrahydrofuran (THF), respectively. Analysis by scanning electron microscopy (SEM) and small-angle X-ray scattering (SAXS) reveals a solvent-induced decrease in lattice constant of close-packed monolayers. We compare the conductance of the monolayer after molecular exchange with two different oligophenylenes to shed light on the respective contribution of the solvent-induced structural change and the molecular exchange itself on the conductance increase. PMID:28144553

  11. Solvent-mediated conductance increase of dodecanethiol-stabilized gold nanoparticle monolayers.

    PubMed

    Reissner, Patrick A; Tisserant, Jean-Nicolas; Sánchez-Ferrer, Antoni; Mezzenga, Raffaele; Stemmer, Andreas

    2016-01-01

    Gold nanoparticle monolayers provide convenient templates to study charge transport in organic molecules beyond single junction techniques. Conductance is reported to increase by several orders of magnitude following immersion of alkanethiol-stabilized gold nanoparticle monolayers in a solution containing conjugated thiol-functionalized molecules. Typically, this observation is attributed to molecular exchange. Less attention has been paid to the role of the solvent alone. Here, we report on an increase in conductance of dodecanethiol-stabilized gold nanoparticle monolayers on Si/SiO2 by an average factor of 36 and 22 after immersion in pure ethanol (EtOH) and tetrahydrofuran (THF), respectively. Analysis by scanning electron microscopy (SEM) and small-angle X-ray scattering (SAXS) reveals a solvent-induced decrease in lattice constant of close-packed monolayers. We compare the conductance of the monolayer after molecular exchange with two different oligophenylenes to shed light on the respective contribution of the solvent-induced structural change and the molecular exchange itself on the conductance increase.

  12. Comparison of Self-Assembled Monolayers on Gold: Coadsorption of Thiols and Disulfides

    DTIC Science & Technology

    1989-02-15

    self-assembled monolayers of thiols and disulfides. Previous studies by Dubois et alt t of the adsorption of dimethyl disulfide and methanethiol on...with an activation energy of desorption of 28 kcal/mol of disulfide, but the methanethiol was only physisorbed on the gold surface and desorbed intact

  13. Ordering and defects in self-assembled monolayers on nanoporous gold

    NASA Astrophysics Data System (ADS)

    Patel, Dipna A.; Weller, Andrew M.; Chevalier, Robert B.; Karos, Constantine A.; Landis, Elizabeth C.

    2016-11-01

    Self-assembled monolayers are commonly used to tailor nanoporous structures for applications, and they also provide a model system for determining the effects of nanoscale structure on self-assembly. We have investigated the ordering and defects in alkanethiol self-assembled monolayers on nanoporous gold, a high surface area mesoporous material. Infrared reflection absorption spectroscopy was used to characterize the effects of alkyl chain length and nanoporous gold pore size on molecular layer ordering. Cyclic voltammetry was used to characterize the monolayer density and ordering, with ferrocenylalkylthiolates used to quantify and characterize defect sites. We find that dense and well-ordered molecular layers form quickly with low defect levels. However, we do not observe differences in molecular layer ordering or defects with changes in pore size.

  14. Mechanism for femtosecond laser pulse patterning of self-assembled monolayers on gold-coated substrates

    NASA Astrophysics Data System (ADS)

    Kirkwood, S. E.; Shadnam, M. R.; Amirfazli, A.; Fedosejevs, R.

    2007-04-01

    Self-assembled monolayer (SAM) patterning on gold thin films was performed using 800 nm, 118 fs laser pulses. SAM removal was ablative and was observed at fluences near the multishot ablation threshold for the thin gold film. Line widths six times smaller than the 2 e-folding intensity beam diameter were observed demonstrating sub-diffraction limited patterning with femtosecond lasers. Similar experimental results in air and N2 indicated that the removal process does not involve oxidation of the gold-sulfur bond as was claimed in the literature.

  15. Self-Assembled Monolayers of Dithiophosphinic Acids on Gold

    NASA Astrophysics Data System (ADS)

    San Juan, Ronan Roca

    This dissertation reports the synthesis of derivatives of dithiophosphinic acids (R1R2DTPAs), and the formation and characterization of DTPA SAMs on gold to build a knowledge base on their nature of binding, organization of the alkyl chains and electrochemical barrier properties. The binding of DTPA molecules on gold depends on the morphology of the gold film: They bind in a mixed monodentate and bidentate modes on standard as-deposited (As-Dep) gold, while they fully chelate on smoother template-stripped (TS) gold. Chapter 2 focuses on van der Waals interactions of various alkyl chain lengths of symmetrical R2DTPA SAMs, which increase with increasing chain lengths similar to those of the analogous n-alkanethiol SAMs, but with alkyl chains that are generally less dense than those of n-alkanethiol SAMs. Chapter 3 addresses why the DTPA compounds do not chelate on the standard As-Dep gold by comparing (C16)2DTPA SAM to (C16 )2DDP SAM. Here, side chain crystallinity stabilizes DTPA SAM structure at the expense of chelation of the DTPA molecules, which leads to a mixture of bidentate and monodentate DTPA molecules, whereas the increased flexibility of the chains in DDP due to the oxygen atoms retains chelation of the DDP molecules. Chapter 4 focuses on the SAMs formed from RlongRshort DTPAs, which shows that the length of the short chain spacer affects SAM packing density and thickness. The SAMs of these molecules also show homogeneous mixing of Rlong and Rshort chains. Chapter 5 investigates PhRDTPA SAMs in preparation for molecular junction studies. The chelation of PhRDTPA molecules on TS gold allows the PhRDTPAs to act as molecular alligator clips. The length of the alkyl chains controls the density of the phenyl group and they fill in the voids between adsorbates to prevent electrical shorting. Finally, Chapter 6 incorporates OH tail group(s) to control the wettability of DTPA SAMs. The presence of OH groups in DTPAs forms hydrophilic SAMs. The symmetrical OH

  16. Amperometric inhibitive biosensor based on horseradish peroxidase-nanoporous gold for sulfide determination

    NASA Astrophysics Data System (ADS)

    Sun, Huihui; Liu, Zhuang; Wu, Chao; Xu, Ping; Wang, Xia

    2016-08-01

    As a well-known toxic pollutant, sulfide is harmful to human health. In this study, a simple and sensitive amperometric inhibitive biosensor was developed for the determination of sulfide in the environment. By immobilizing nanoporous gold (NPG) on glassy carbon electrode (GCE), and encapsulating horseradish peroxidase (HRP) onto NPG, a HRP/NPG/GCE bioelectrode for sulfide detection was successfully constructed based on the inhibition of sulfide on HRP activity with o-Phenylenediamine (OPD) as a substrate. The resulted HRP/NPG/GCE bioelectrode achieved a wide linear range of 0.1–40 μM in sulfide detection with a high sensitivity of 1720 μA mM‑1 cm‑2 and a low detection limit of 0.027 μM. Additionally, the inhibition of sulfide on HRP is competitive inhibition with OPD as a substrate by Michaelis-Menten analysis. Notably, the recovery of HRP activity was quickly achieved by washing the HRP/NPG/GCE bioelectrode using differential pulse voltammetry (DPV) technique in deaerated PBS (50 mM, pH 7.0) for only 60 s. Furthermore, the real sample analysis of sulfide by the HRP/NPG/GCE bioelectrode was achieved. Based on above results, the HRP/NPG/GCE bioelectrode could be a better choice for the real determination of sulfide compared to inhibitive biosensors previously reported.

  17. Reactive Capture of Gold Nanoparticles by Strongly Physisorbed Monolayers on Graphite

    SciTech Connect

    Wei, Xiaoliang; Tong, Wenjun; Fidler, Vlastimil; Zimmt, Matthew B.

    2012-12-01

    Anthracene Diels Alder adducts (DAa) bearing two long side chains (H-(CH2)22O(CH2)6OCH2-) at the 1- and 5-positions form self-assembled monolayers (SAMs) at the phenyloctane - highly oriented pyrolytic graphite (HOPG) interface. The long DAa side chains promote strong physisorption of the monolayer to HOPG and maintain the monolayer morphology upon rinsing or incubation in ethanol and air-drying of the substrate. Incorporating a carboxylic acid group on the DAa core enables capture of 1 - 4 nm diameter gold nanoparticles (AuNP) provided (i) the monolayer containing DAa-carboxylic acids is treated with Cu2+ ions and (ii) the organic coating on the AuNP contains carboxylic acids (11-mercaptoundecanoic acid, MUA-AuNP). AuNP capture by the monolayer proceeds with formation of Cu2+ - carboxylate coordination complexes. The captured AuNP appear as mono- and multi-layered clusters at high coverage on HOPG. The surface density of the captured AuNPs can be adjusted from AuNP multi-layers to isolated AuNPs by varying incubation times, MUA-AuNP concentration, the number density of carboxylic acids in the monolayer, the number of MUA per AuNP, and the post-incubation treatments.

  18. Electrochemical and vibrational spectroscopic studies of coadsorption: Formation of mixed monolayers of methylene blue and long-chain dithioethers at sulfur-modified polycrystalline gold surfaces

    SciTech Connect

    Barner, B.J.; Corn, R.M. )

    1990-05-01

    Molecular conformation and order within mixed monolayers of methylene blue, sulfide, and the long-chain dithioether C{sub 14}H{sub 29}SC{sub 2}H{sub 4}SC{sub 14}H{sub 29} adsorbed onto polycrystalline evaporated gold films are studied by using electrochemical methods and ex situ vibrational spectroscopy. The methylene blue dye molecules directly chemisorb onto the sulfur-modified gold surface and do not significantly partition into the alkyl portions of the monolayer. However, upon reduction to leucomethylene blue, the dye molecules do partition into the alkyl subphase. Repeated electrochemical reduction and oxidation of the chemisorbed methylene blue result in an ordering of the adsorbed alkyl chains from a liquid-like structure to a close-packed configuration. The presence of a partial dithioether monolayer also leads to the formation of a stabilized leucomethylene blue film. The variations of the molecular structure observed in these mixed systems arise from the competing processes of chemisorption, aggregation, and hydrophobic solubilization occurring within the thin film.

  19. Near-Infrared Light Absorption and Scattering Based on a Mono-Layer of Gold Nanoparticles

    NASA Astrophysics Data System (ADS)

    Soltanmoradi, R.; Wang, Q.; Qiu, M.; Popov, S.; Yan, M.

    2015-06-01

    We report fabrication and characterization of large-area ultrathin near-infrared light absorbers and scatterers based on a mono-layer of gold nanoparticles laying on top of a dielectric spacer and an aluminum reflector. The nanoparticles are formed through thermal annealing of an evaporated continuous gold film. Through optimization of initial gold-film thickness, spacer thickness, as well as annealing temperature we obtained samples that exhibit very low (~2%) broadband specular reflectance at near-infrared (NIR) wavelength range. By considering also diffuse reflection, we identify that the low specular reflectance can be due to either relatively high light absorption (~70%) or high light scattering (over 60%), with the latter achieved for samples having relatively sparse gold nanoparticles. Both strong absorption and scattering of NIR light are not inherent properties of the bulk materials used for fabricating the samples. Such composite optical surfaces can potentially be integrated to solar-energy harvesting and LED devices.

  20. Preparing metal-complex surfaces based on self-assembled monolayers of thiols and disulfides on gold

    NASA Astrophysics Data System (ADS)

    Dolzhikova, V. D.; Bogdanova, Yu. G.; Majouga, A. G.; Beloglazkina, E. K.; Kudrinsky, A. A.

    2017-02-01

    The complexation of monolayers of sulfur-containing ligands self-assembled on surface of gold with Co(II) and Cu(II) ions is studied using quartz crystal microbalance (QCM) and wetting measurements. The optimum conditions for obtaining metal-complex surfaces and the compositions of the resulting monolayers are determined.

  1. Omega-Terminated Alkanethiolate Monolayers on Surfaces of Copper, Silver and Gold Have Similar Wettabilities

    DTIC Science & Technology

    1991-12-01

    metal cxides and form oriented, oleophobic monolayers,25 0-hydroxy- and W-amino-alkanoic acids adsorb and form poorly organized films that are not wet...gold. Experinental Materials . 1l-Bromo-undecyl t-butyldimethylsilyl ether and most alkanethiols were available from pcrevious studies;6, 2 1, 4 8 ctn...er materials were obtained from Aldrich and used as received unless Specified. Octadecanethiol was distilled under reduced pressure prior to use

  2. Significance of the amide functionality on DOPA-based monolayers on gold.

    PubMed

    Rībena, Dina; Alekseev, Alexander; van Asselen, Otto; Mannie, Gilbère J A; Hendrix, Marco M R M; van der Ven, Leendert G J; Sommerdijk, Nico A J M; de With, Gijsbertus

    2012-12-11

    The adhesive proteins secreted by marine mussels contain an unusual amino acid, 3,4-dihydroxyphenylalanine (DOPA), that is responsible for the cohesive and adhesive strength of this natural glue and gives mussels the ability to attach themselves to rocks, metals, and plastics. Here we report a detailed structural and spectroscopic investigation of the interface between N-stearoyldopamine and a single-crystalline Au(111) model surface and an amide-absent molecule, 4-stearylcatechol, also on Au(111), with the aim of understanding the role of the amide functionality in the packing, orientation, and fundamental interaction between the substrate and the monolayer formed from an aqueous environment by the Langmuir-Blodgett technique. The organization of monolayers on gold was observed directly and studied in detail by X-ray photoelectron spectroscopy (XPS), contact angle measurements (CA), surface-enhanced Raman spectroscopy (SERS), infrared reflection-absorption spectroscopy (IRRAS), and atomic force microscopy (AFM). Our study shows that within the monolayer the catecholic oxygen atoms are coordinated to the gold surface, having a more perpendicular orientation with respect to the aromatic ring and the apparently tilted alkyl chains, whereas the amide functionality stabilizes the monolayer that is formed.

  3. Coadsorption of ferrocene-terminated and unsubstituted alkanethiols on gold: Electroactive self-assembled monolayers

    SciTech Connect

    Chidsey, C.E.D.; Bertozzi, C.R.; Putvinski, T.M.; Mujsce, A.M. )

    1990-05-23

    Self-assembled monolayers provide an ideal system for disentangling the fundamental events in interfacial electron transfer. Coadsorption of ferrocene-terminated alkanethiols with unsubstituted n-alkanethiols on evaporated gold films yields stable, electroactive self-assembled monolayers. Monolayers containing low concentrations of alkanethiols linked to ferrocene by a polar ester group (FcCO{sub 2}(CH{sub 2}){sub n}SH, Fc = ({eta}{sup 5}-C{sub 5}H{sub 5})Fe({eta}{sup 5}-C{sub 5}H{sub 4})) show thermodynamically ideal surface electrochemistry in 1 M HClO{sub 4}, indicating the ferrocene groups to be homogeneous and noninteracting. Higher surface concentrations or use of alkanethiols linked directly to the nonpolar ferrocene group (Fc(CH{sub 2}){sub n}SH) lead to broadened electrochemical features, indicating interactions among ferrocene groups or inhomogeneous sites. Longer chain lengths and lower ferrocene surface concentrations result in slower electron-transfer kinetics with the ferrocene groups. A fraction of the thiols in a monolayer exchange with thiols in an ethanol solution, but much of the monolayer remains unequilibrated after 10 days.

  4. Removal of self-assembled monolayers of alkanethiolates on gold by plasma cleaning

    NASA Astrophysics Data System (ADS)

    Raiber, Kevin; Terfort, Andreas; Benndorf, Carsten; Krings, Norman; Strehblow, Hans-Henning

    2005-12-01

    Plasmas of hydrogen or oxygen were used to remove self-assembled monolayers (SAMs) of alkanethiolates from gold surfaces. X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), ellipsometry, and contact angle measurements were used to compare the efficiency of the different plasmas and to explore their respective influence on the surface topology. Both plasmas were able to remove the SAM from the gold surface within less than 60 s. While the hydrogen plasma produces a de facto sulfur-free surface, oxygen plasma cleaning leads to an Au 2O 3 surface contaminated with oxidized sulfur species (probably sulfonates and sulfate). Nevertheless, the plasmas alter the roughness of the gold surfaces only marginally, as demonstrated by STM.

  5. Inkjet printed electrode arrays for potential modulation of DNA self-assembled monolayers on gold.

    PubMed

    Li, Yunchao; Li, Paul C H; Parameswaran, M Ash; Yu, Hua-Zhong

    2008-11-15

    In this paper, we report a novel and cost-effective fabrication technique to produce electrode arrays that can be used for monitoring and electrical manipulation of the molecular orientation of DNA self-assembled monolayers (SAMs) on gold. The electrode arrays were prepared from gold coated glass sides or compact discs (CD-Rs) by using standard office inkjet printers without any hardware or software modifications. In this method, electrode arrays of varied shape and size (from submillimeter to centimeter) can be rapidly fabricated and are suitable for standard electrochemical measurements. We were able to use a dual-channel potentiostat to control the electrodes individually and a fluorescence (FL) scanner to image the electrode array simultaneously. With such an integrated modulation setup, the structural switching behavior (from "lying" to "standing" position) and the enhanced hybridization reactivity of thiolate DNA SAMs on gold under potential control have been successfully demonstrated.

  6. Fluorinated and Charged Hydrogenated Alkanethiolates Grafted on Gold: Expanding the Diversity of Mixed-Monolayer Nanoparticles for Biological Applications.

    PubMed

    Bidoggia, Silvia; Milocco, Francesca; Polizzi, Stefano; Canton, Patrizia; Saccani, Alessandra; Sanavio, Barbara; Krol, Silke; Stellacci, Francesco; Pengo, Paolo; Pasquato, Lucia

    2017-01-18

    Low intrinsic toxicity, high solubility, and stability are important and necessary features of gold nanoparticles to be used in the biomedical field. In this context, charged nanoparticles proved to be very versatile, and among them charged mixed-monolayer gold nanoparticles, displaying monolayers with well-defined morphologies, represent a paradigm. By using mixtures of hydrogenated and fluorinated thiols, the formation of monolayer domains may be brought to an extreme because of the immiscibility of fluorinated and hydrogenated chains. Following this rationale, mixed monolayer gold nanoparticles featuring ammonium, sulfonate, or carboxylic groups on their surface were prepared by using amphiphilic hydrogenated thiols and 1H,1H,2H,2H-perfluoro-alkanethiols. The toxicity of these systems was assessed in HeLa cells and was found to be, in general, low even for the cationic nanoparticles which usually show a high cytotoxicity and is comparable to that of homoligand gold nanoparticles displaying amphiphilic-charge neutral-hydrogenated or fluorinated thiolates in their monolayer. These properties make the mixed ligand monolayer gold nanoparticles an interesting new candidate for medical application.

  7. Self-assembly and structure of directly imaged inorganic-anion monolayers on a gold nanoparticle.

    PubMed

    Wang, Yifeng; Neyman, Alevtina; Arkhangelsky, Elizabeth; Gitis, Vitaly; Meshi, Louisa; Weinstock, Ira A

    2009-12-02

    Cryogenic "trapping" was used to obtain the first TEM images of self-assembled monolayers of inorganic anions on a gold nanoparticle. This unique structural information makes it possible to study the formation of a protecting-ligand shell at an unprecedented level of detail. The protecting ligands are polyoxometalates (POMs; alpha-X(n+)W(12)O(40)((8-n)-), X(n+) = Al(3+) and "2H(+)", and alpha-X(n+)W(11)O(39)((12-n)-), X(n+) = P(5+), Si(4+), and Al(3+)) with large negative charges for association with the gold surface and W atoms (Z = 74) for TEM imaging. The POM-anion shells were obtained by ligand exchange from citrate-protected 13.8 nm gold nanoparticles. Replacement of the organic (citrate) by inorganic (tungsten-oxide) ligand shells results in substantial changes in the surface plasmon resonance (SPR). By correlating cryo-TEM images with changes in the SPR, degrees of surface coverage were reliably quantified by UV-visible spectroscopy. Then, the kinetics and thermodynamics of ligand-shell formation were investigated by systematically varying POM structure and charge. Rates of POM association with the gold surface ("nucleation") are inhibited by the electric-potential barrier of the citrate-stabilized particles, while binding affinities increase linearly with the charges (from 5- to 9-) of structurally different POM anions, suggesting that no single orientation ("lattice matching") is required for monolayer self-assembly. Time-dependent cryo-TEM images reveal that monolayer growth occurs via "islands", a mechanism that points to cation-mediated attraction between bound POMs. Complete ligand shells comprised of 330 molecules of alpha-AlW(11)O(39)(9-) (1) possess small net charges (29e from zeta-potential measurements) and short Debye lengths (kappa(-1) = 1.0 nm), which indicate that approximately 99% of the 2970 K(+) counter cations lie within ca. 1.5 nm (approximately 3 hydrated K(+) ion diameters) from the outer surface of the POM shell. Energetic analysis of

  8. Disassembly mediated fluorescence recovery of gold nanodots for selective sulfide sensing

    NASA Astrophysics Data System (ADS)

    Yuan, Zhiqin; Peng, Meihua; Shi, Lei; Du, Yi; Cai, Na; He, Yan; Chang, Huan-Tsung; Yeung, Edward S.

    2013-05-01

    We report a one-pot, two-step strategy to synthesize fluorescent gold nanodots (AuNDs) co-modified with 1-(10-mercaptodecyl)-5-methylpyrimidine-2,4-dione (TSH) and 11-mercaptoundecanoic acid (MUA) through a ligand exchange reaction and demonstrate their capability of selective sulfide sensing in aqueous media on the basis of fluorescence recovery.We report a one-pot, two-step strategy to synthesize fluorescent gold nanodots (AuNDs) co-modified with 1-(10-mercaptodecyl)-5-methylpyrimidine-2,4-dione (TSH) and 11-mercaptoundecanoic acid (MUA) through a ligand exchange reaction and demonstrate their capability of selective sulfide sensing in aqueous media on the basis of fluorescence recovery. Electronic supplementary information (ESI) available: Experimental details, more characterization and other supporting data. See DOI: 10.1039/c2nr33202g

  9. Kinetic investigation of sulfidizing annealing of scorodite in processing of refractory oxidized gold-containing ores

    NASA Astrophysics Data System (ADS)

    Boboev, I. R.; Strizhko, L. S.; Bobozoda, Sh.; Gorbunov, E. P.

    2016-03-01

    The results of kinetic studies on the removal of arsenic from scorodite using sulfidizing annealing are presented. The reaction order with respect to the reactant and the activation energy are established from the experimental data. The rate-determining step of the sulfidizing annealing process is determined. The main reactions that occur during the sulfidizing of arsenic in scorodite are proposed on the basis of the obtained results and confirmed by thermodynamic calculations and chemical analyses. The major results of testing this technology, as applied to the refractory oxidized ores in which arsenic is mainly concentrated in scorodite, are presented. Arsenic removal from this ore is confirmed by chemical and quantitative X-ray diffraction analyses and by qualitative phase analysis. Industrial use of this technology provides safe and efficient processing of refractory gold-containing ores, where arsenic is mainly concentrated in scorodite.

  10. Detection of saccharides with a fluorescent sensing device based on a gold film modified with 4-mercaptophenylboronic acid monolayer

    NASA Astrophysics Data System (ADS)

    Chen, Shu-Jen; Chang, Jui-Feng; Cheng, Nai-Jen; Yih, Jeng-Nan; Chiu, Kuo-Chi

    2013-09-01

    An extremely sensitive fluorescent sensor based on a phenylboronic acid monolayer was developed for detecting saccharide molecules. The fluorescent sensor was prepared by assembling a monolayer of 4-mercaptophenylboronic acid (4-MPBA) onto a gold-coated compact disk. The change in the fluorescence of the 4-MPBA monolayer was extremely obvious in basic methanolic buffer containing monosaccharides down to the picomolar level. The fluorescence spectra demonstrated that the 4-MPBA monolayer was sensitive to monosaccharides and disaccharides, and the affinity of the monolayer toward saccharides was in the order of glucose < fructose < mannose < galactose < maltose > lactose > sucrose. Additionally, the fluorescence intensity of 4-MPBA monolayer was restorable after cleaning with weak acid, indicating that the reported fluorescent sensor with the detection limit of glucose down to the picomolar level is reusable for sensing saccharides.

  11. Superlattice of resonators on monolayer graphene created by intercalated gold nanoclusters

    NASA Astrophysics Data System (ADS)

    Cranney, M.; Vonau, F.; Pillai, P. B.; Denys, E.; Aubel, D.; De Souza, M. M.; Bena, C.; Simon, L.

    2010-09-01

    Here we report on a "new" type of ordering which allows to modify the electronic structure of a graphene monolayer (ML). We have intercalated small gold clusters between the top monolayer graphene and the buffer layer of epitaxial graphene. We show that these clusters perturb the quasiparticles on the ML graphene, acting as quantum dots creating a superlattice of resonators on the graphene ML, as revealed by a strong pattern of standing waves. A detailed analysis of the standing-wave pattern using Fourier Transform Scanning Tunneling Spectroscopy strongly indicates that this phenomenon can arise from a strong modification of the band structure of graphene and (or) from Charge Density Waves (CDW) where a large extension of Van Hove singularities is involved.

  12. Molecular simulations of mixed self-assembled monolayer coated gold nanoparticles in water.

    PubMed

    J, Meena Devi

    2015-06-01

    Molecular dynamics simulations have been employed to study the hydration of a series of nanoparticles, each of which was coated with a mixed self-assembled monolayer (SAM) comprising methyl- and hydroxy-terminated alkane thiol chains. The mixing ratio of those chains are different for each nanoparticle. The simulations focused on the wetting behavior of the SAM-coated gold nanoparticles and the distribution and structure of their interfacial water molecules. The interactions of the mixed SAM-coated gold nanoparticles with water were analyzed by evaluating the radial distribution function, hydrogen bonds, the dipole orientations of the water molecules, and the water residence time in the interfacial region. The wettability of the mixed SAM-coated gold nanoparticles improved as the concentration of terminal hydroxy moieties was increased. The distribution and dynamics of the interfacial water molecules were found to be influenced by the mixing ratio of the terminal moieties of the SAM chains. The results of our simulations suggest that the surface interactions of the mixed SAM-coated gold nanoparticles with the aqueous medium can be modulated by systematically altering the mixing ratio of the terminal methyl and hydroxy moieties. This work may lead to new biological and technological applications and inspire the development of novel biomimetic materials. Graphical Abstract Mixed SAM-coated gold nanoparticles.

  13. Direct patterning of self-assembled monolayers on gold using a laser beam.

    PubMed

    Shadnam, Mohammad R; Kirkwood, Sean E; Fedosejevs, Robert; Amirfazli, A

    2004-03-30

    The development of a methodology to manipulate surface properties of a self-assembled monolayer (SAM) of alkanethiol on a gold film using direct laser patterning is the objective of this paper. The present study demonstrates proof of the concept for the feasibility of laser patterning monolayers and outlines theoretical modeling of the process to predict the resulting feature size. This approach is unique in that it eliminates the need for photolithography, is noncontact, and can be extended to other systems such as SAMs on silicon wafers or potentially polymeric substrates. A homogeneous SAM made of 1-hexadecanethiol is formed on a 300-A sputtered film of gold (supported by a soda lime glass substrate). Localized regions are then desorbed by scanning the focal spot of a 488-nm continuous-wave argon ion laser beam under a nitrogen atmosphere. The desorption occurs as a result of a high substrate temperature produced by the moving laser beam with a Gaussian spatial profile at a constant speed of 200 microm/s. After completing the scans, the sample is dipped into a dilute solution of 16-mercaptohexadecanoic acid and a hydrophilic monolayer self-assembles along the previously irradiated regions. The resultant lines are viewed, and line widths are measured using both wetting with tridecane under a light microscope and scanning electron microscopy. Using the direct laser patterning method, we have produced straight line patterns with widths of 28-170 microm. A thermal model was constructed to predict the line width of the desorbed monolayer. The effect of the laser power, beam waist, and temperature dependence of the substrate conductivity on the theoretical predictions is considered. It is shown that the theoretical predictions are in good agreement with the experimental results, and, thus, the model can effectively be used to predict experimental results.

  14. Molecular Dynamics Study of Alkanethiolate Self-Assembled Monolayer Coated Gold Nanoparticle

    DTIC Science & Technology

    2007-06-01

    component of function results for the uncoated gold nanoparticle to the the Irving -Kirkwood (IK) pressure tensor. [321 The normal results for an...pp. 24-34, 1983. Studies." Langmuir , 4, pp. 546-558, 1988. 23. Shevade, A. V., J. Zhou, M. T. Zin, and S. Jiang. Phase 8. Rosenbaum, A.W, M.A. Freedman...Au(l 11): A Configurational-Bias Monte Carlo Assembled Monolayers of Varying Chain Length." Journal of Simulation Study. Langmuir 17, pp. 7566-7572

  15. A low voltage programmable unipolar inverter with a gold nanoparticle monolayer on plastic.

    PubMed

    Zhou, Ye; Han, Su-Ting; Huang, Long-Biao; Huang, Jing; Yan, Yan; Zhou, Li; Roy, V A L

    2013-05-24

    A programmable low voltage unipolar inverter with saturated-load configuration has been demonstrated on a plastic substrate. A self-assembled monolayer of gold (Au) nanoparticles was inserted into the dielectric layer acting as a charge trapping layer. The inverter operated well with supply voltages of < - 5 V and the switching voltage was tuned in a wide range under low program/erase bias. The retention and endurance test at ambient conditions confirmed the reliability of the inverter. Furthermore, the programmable behavior was maintained well at various bending states, demonstrating the adequate flexibility of our devices.

  16. Electrical resistivity of nanoporous gold modified with thiol self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Hakamada, Masataka; Kato, Naoki; Mabuchi, Mamoru

    2016-11-01

    The electrical resistivity of nanoporous gold (NPG) modified with thiol self-assembled monolayers (SAMs) has been measured at 298 K using a four-probe method. We found that the adsorption of thiol SAMs increases the electrical resistivity of NPG by up to 22.2%. Dependence of the electrical resistivity on the atmosphere (air or water) was also observed in SAMs-modified NPG, suggesting that the electronic states of the tail groups affect the electrons of the binding sulfur and adjacent surface gold atoms. The present results suggest that adsorption of thiol molecules can influence the behavior of the conducting electrons in NPG and that modification of NPG with SAMs may be useful for environmental sensing.

  17. Monolayer-precision synthesis of molybdenum sulfide nanoparticles and their nanoscale size effects in the hydrogen evolution reaction.

    PubMed

    Seo, Bora; Jung, Gwan Yeong; Sa, Young Jin; Jeong, Hu Young; Cheon, Jae Yeong; Lee, Jeong Hyeon; Kim, Ho Young; Kim, Jin Chul; Shin, Hyeon Suk; Kwak, Sang Kyu; Joo, Sang Hoon

    2015-04-28

    Metal sulfide-based nanostructured materials have emerged as promising catalysts for hydrogen evolution reaction (HER), and significant progress has been achieved in enhancing their activity and durability for the HER. The understanding of nanoscale size-dependent catalytic activities can suggest critical information regarding catalytic reactivity, providing the scientific basis for the design of advanced catalysts. However, nanoscale size effects in metal sulfide-based HER catalysts have not yet been established fully, due to the synthetic difficulty in precisely size-controlled metal sulfide nanoparticles. Here we report the preparation of molybdenum sulfide (MoS2) nanoparticles with monolayer precision from one to four layers with the nearly constant basal plane size of 5 nm, and their size-dependent catalytic activity in the HER. Using density functional theory (DFT) calculations, we identified the most favorable single-, double-, and triple-layer MoS2 model structures for the HER, and calculated elementary step energetics of the HER over these three model structures. Combining HER activity measurements and the DFT calculation results, we establish that the turnover frequency of MoS2 nanoparticles in the HER increases in a quasi-linear manner with decreased layer numbers. Cobalt-promoted MoS2 nanoparticles also exhibited similar HER activity trend. We attribute the higher HER activity of smaller metal sulfide nanoparticles to the higher degree of oxidation, higher Mo-S coordination number, formation of the 1T phase, and lower activation energy required to overcome transition state. This insight into the nanoscale size-dependent HER activity trend will facilitate the design of advanced HER catalysts as well as other hydrotreating catalysts.

  18. Colorimetric detection of biological hydrogen sulfide using fluorosurfactant functionalized gold nanorods.

    PubMed

    Zhang, Xuan; Zhou, Wenjuan; Yuan, Zhiqin; Lu, Chao

    2015-11-07

    As a well-known environmental pollutant but also an important gaseous transmitter, the specific detection of hydrogen sulfide (H2S) is significant in biological systems. In this study, fluorosurfactant functionalized gold nanorods (FSN-AuNRs) have been proposed to act as selective colorimetric nanoprobes for H2S. With the combination of strong gold-S interactions and small FSN bilayer interstices, FSN-AuNRs demonstrate favorable selectivity and sensitivity toward H2S over other anions and small biological molecules. The practical application of the present method in biological H2S detection was validated with human and mouse serum samples. Moreover, the proposed nanoprobe can also be used for evaluating the activity of H2S synthetase.

  19. Ultra stable self-assembled monolayers of N-heterocyclic carbenes on gold

    NASA Astrophysics Data System (ADS)

    Crudden, Cathleen M.; Horton, J. Hugh; Ebralidze, Iraklii I.; Zenkina, Olena V.; McLean, Alastair B.; Drevniok, Benedict; She, Zhe; Kraatz, Heinz-Bernhard; Mosey, Nicholas J.; Seki, Tomohiro; Keske, Eric C.; Leake, Joanna D.; Rousina-Webb, Alexander; Wu, Gang

    2014-05-01

    Since the first report of thiol-based self-assembled monolayers (SAMs) 30 years ago, these structures have been examined in a huge variety of applications. The oxidative and thermal instabilities of these systems are widely known, however, and are an impediment to their widespread commercial use. Here, we describe the generation of N-heterocyclic carbene (NHC)-based SAMs on gold that demonstrate considerably greater resistance to heat and chemical reagents than the thiol-based counterparts. This increased stability is related to the increased strength of the gold-carbon bond relative to that of a gold-sulfur bond, and to a different mode of bonding in the case of the carbene ligand. Once bound to gold, NHCs are not displaced by thiols or thioethers, and are stable to high temperatures, boiling water, organic solvents, pH extremes, electrochemical cycling above 0 V and 1% hydrogen peroxide. In particular, benzimidazole-derived carbenes provide films with the highest stabilities and evidence of short-range molecular ordering. Chemical derivatization can be employed to adjust the surface properties of NHC-based SAMs.

  20. Surface Coverage and Structure of Mixed DNA/Alkylthiol Monolayers on Gold: Characterization by XPS, NEXAFS, and Fluorescence Intensity Measurements

    PubMed Central

    Lee, Chi-Ying; Gong, Ping; Harbers, Gregory M.; Grainger, David W.; Castner, David G.; Gamble, Lara J.

    2006-01-01

    Self-assembly of thiol-terminated single-stranded DNA (HS-ssDNA) on gold has served as an important model system for DNA immobilization at surfaces. Here, we report a detailed study of the surface composition and structure of mixed self-assembled DNA monolayers containing a short alkylthiol surface diluent [11-mercapto-1-undecanol (MCU)] on gold supports. These mixed DNA monolayers were studied with X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS), and fluorescence intensity measurements. XPS results on sequentially adsorbed DNA/MCU monolayers on gold indicated that adsorbed MCU molecules first incorporate into the HS-ssDNA monolayer and, upon longer MCU exposures, displace adsorbed HS-ssDNA molecules from the surface. Thus, HS-ssDNA surface coverage steadily decreased with MCU exposure time. Polarization-dependent NEXAFS and fluorescence results both show changes in signals consistent with changes in DNA orientation after only 30 min of MCU exposure. NEXAFS polarization dependence (followed by monitoring the N 1s → π* transition) of the mixed DNA monolayers indicated that the DNA nucleotide base ring structures are oriented more parallel to the gold surface compared to DNA bases in pure HS-ssDNA monolayers. This indicates that HS-ssDNA oligomers reorient toward a more-upright position upon MCU incorporation. Fluorescence intensity results using end-labeled DNA probes on gold show little observable fluorescence on pure HS-ssDNA monolayers, likely due to substrate quenching effects between the fluorophore and the gold. MCU diluent incorporation into HS-ssDNA monolayers initially increases DNA fluorescence signal by densifying the chemisorbed monolayer, prompting an upright orientation of the DNA, and moving the terminal fluorophore away from the substrate. Immobilized DNA probe density and DNA target hybridization in these mixed DNA monolayers, as well as effects of MCU diluent on DNA hybridization in complex

  1. Surface Coverage and Structure of Mixed DNA/Alkylthiol Monolayers on Gold: Characterization by XPS, NEXAFS, and Fluorescence Intensity Measurements

    SciTech Connect

    Lee,C.; Gong, P.; Harbers, G.; Grainger, D.; Castner, D.; Gamble, L.

    2006-01-01

    Self-assembly of thiol-terminated single-stranded DNA (HS-ssDNA) on gold has served as an important model system for DNA immobilization at surfaces. Here, we report a detailed study of the surface composition and structure of mixed self-assembled DNA monolayers containing a short alkylthiol surface diluent [11-mercapto-1-undecanol (MCU)] on gold supports. These mixed DNA monolayers were studied with X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS), and fluorescence intensity measurements. XPS results on sequentially adsorbed DNA/MCU monolayers on gold indicated that adsorbed MCU molecules first incorporate into the HS-ssDNA monolayer and, upon longer MCU exposures, displace adsorbed HS-ssDNA molecules from the surface. Thus, HS-ssDNA surface coverage steadily decreased with MCU exposure time. Polarization-dependent NEXAFS and fluorescence results both show changes in signals consistent with changes in DNA orientation after only 30 min of MCU exposure. NEXAFS polarization dependence (followed by monitoring the N 1s{yields}{pi}* transition) of the mixed DNA monolayers indicated that the DNA nucleotide base ring structures are oriented more parallel to the gold surface compared to DNA bases in pure HS-ssDNA monolayers. This indicates that HS-ssDNA oligomers reorient toward a more-upright position upon MCU incorporation. Fluorescence intensity results using end-labeled DNA probes on gold show little observable fluorescence on pure HS-ssDNA monolayers, likely due to substrate quenching effects between the fluorophore and the gold. MCU diluent incorporation into HS-ssDNA monolayers initially increases DNA fluorescence signal by densifying the chemisorbed monolayer, prompting an upright orientation of the DNA, and moving the terminal fluorophore away from the substrate. Immobilized DNA probe density and DNA target hybridization in these mixed DNA monolayers, as well as effects of MCU diluent on DNA hybridization in

  2. Near-Edge X-ray Absorption Fine Structure Spectroscopy of Diamondoid Thiol Monolayers on Gold

    SciTech Connect

    Willey, T M; Fabbri, J; Lee, J I; Schreiner, P; Fokin, A A; Tkachenko, B A; Fokina, N A; Dahl, J; Carlson, B; Vance, A L; Yang, W; Terminello, L J; van Buuren, T; Melosh, N

    2007-11-27

    Diamondoids, hydrocarbon molecules with cubic-diamond-cage structures, have unique properties with potential value for nanotechnology. The availability and ability to selectively functionalize this special class of nanodiamond materials opens new possibilities for surface-modification, for high-efficiency field emitters in molecular electronics, as seed crystals for diamond growth, or as robust mechanical coatings. The properties of self-assembled monolayers (SAMs) of diamondoids are thus of fundamental interest for a variety of emerging applications. This paper presents the effects of thiol substitution position and polymantane order on diamondoid SAMs on gold using near-edge X-ray absorption fine structure spectroscopy (NEXAFS) and X-ray photoelectron spectroscopy (XPS). A framework to determine both molecular tilt and twist through NEXAFS is presented and reveals highly ordered diamondoid SAMs, with the molecular orientation controlled by the thiol location. C 1s and S 2p binding energies are lower in adamantane thiol than alkane thiols on gold by 0.67 {+-} 0.05 eV and 0.16 {+-} 0.04 eV respectively. These binding energies vary with diamondoid monolayer structure and thiol substitution position, consistent with different amounts of steric strain and electronic interaction with the substrate. This work demonstrates control over the assembly, in particular the orientational and electronic structure, providing a flexible design of surface properties with this exciting new class of diamond clusters.

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

    SciTech Connect

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

    2011-03-15

    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: {yields} Dithiols molecules create chemically bounded layers on a Au (111) surface. {yields} Gold nanoparticles can be chemically bounded to a self-assembled monolayer. {yields} Nanoparticles are stable during AFM probe interactions.

  4. Gold Nanoparticle Monolayers from Sequential Interfacial Ligand Exchange and Migration in a Three-Phase System

    PubMed Central

    Yang, Guang; Hallinan, Daniel T.

    2016-01-01

    Using a three-phase system, centimeter-scale monolayer gold nanoparticle (Au NP) films have been prepared that have long-range order and hydrophobic ligands. The system contains an interface between an aqueous phase containing Au NPs and an oil phase containing one of various types of amine ligands, and a water/air interface. As the Au NPs diffuse to the water/oil interface, ligand exchange takes place which temporarily traps them at the water/oil interface. The ligand-exchanged particles then spontaneously migrate to the air/water interface, where they self-assemble, forming a monolayer under certain conditions. The spontaneous formation of the NP film at the air/water interface was due to the minimization of the system Helmholtz free energy. However, the extent of surface functionalization was dictated by kinetics. This decouples interfacial ligand exchange from interfacial self-assembly, while maintaining the simplicity of a single system. The interparticle center-to-center distance was dictated by the amine ligand length. The Au NP monolayers exhibit tunable surface plasma resonance and excellent spatial homogeneity, which is useful for surface-enhanced Raman scattering. The “air/water/oil” self-assembly method developed here not only benefits the fundamental understanding of NP ligand conformations, but is also applicable to the manufacture of plasmonic nanoparticle devices with precisely designed optical properties. PMID:27762394

  5. Gold Nanoparticle Monolayers from Sequential Interfacial Ligand Exchange and Migration in a Three-Phase System

    NASA Astrophysics Data System (ADS)

    Yang, Guang; Hallinan, Daniel T.

    2016-10-01

    Using a three-phase system, centimeter-scale monolayer gold nanoparticle (Au NP) films have been prepared that have long-range order and hydrophobic ligands. The system contains an interface between an aqueous phase containing Au NPs and an oil phase containing one of various types of amine ligands, and a water/air interface. As the Au NPs diffuse to the water/oil interface, ligand exchange takes place which temporarily traps them at the water/oil interface. The ligand-exchanged particles then spontaneously migrate to the air/water interface, where they self-assemble, forming a monolayer under certain conditions. The spontaneous formation of the NP film at the air/water interface was due to the minimization of the system Helmholtz free energy. However, the extent of surface functionalization was dictated by kinetics. This decouples interfacial ligand exchange from interfacial self-assembly, while maintaining the simplicity of a single system. The interparticle center-to-center distance was dictated by the amine ligand length. The Au NP monolayers exhibit tunable surface plasma resonance and excellent spatial homogeneity, which is useful for surface-enhanced Raman scattering. The “air/water/oil” self-assembly method developed here not only benefits the fundamental understanding of NP ligand conformations, but is also applicable to the manufacture of plasmonic nanoparticle devices with precisely designed optical properties.

  6. Tribology of monolayer films: comparison between n-alkanethiols on gold and n-alkyl trichlorosilanes on silicon.

    PubMed

    Booth, Brandon D; Vilt, Steven G; McCabe, Clare; Jennings, G Kane

    2009-09-01

    This Article presents a quantitative comparison of the frictional performance for monolayers derived from n-alkanethiolates on gold and n-alkyl trichlorosilanes on silicon. Monolayers were characterized by pin-on-disk tribometry, contact angle analysis, ellipsometry, and electrochemical impedance spectroscopy (EIS). Pin-on-disk microtribometry provided frictional analysis at applied normal loads from 10 to 1000 mN at a speed of 0.1 mm/s. At low loads (10 mN), methyl-terminated n-alkanethiolate self-assembled monolayers (SAMs) exhibited a 3-fold improvement in coefficient of friction over SAMs with hydroxyl- or carboxylic-acid-terminated surfaces. For monolayers prepared from both n-alkanethiols on gold and n-alkyl trichlorosilanes on silicon, a critical chain length of at least eight carbons is required for beneficial tribological performance at an applied load of 9.8 mN. Evidence for disruption of chemisorbed alkanethiolate SAMs with chain lengths n monolayers shows that monolayers prepared from n-octadecyl dimethylchlorosilane and n-octadecyl trichlorosilane withstood normal loads at least 30 times larger than those that damaged octadecanethiolate SAMs. Collectively, our results show that the tribological properties of monolayer films are dependent on their internal stabilities, which are influenced by cohesive chain interactions (van der Waals) and the adsorbate-substrate bond.

  7. The development of volcanic hosted massive sulfide and barite gold orebodies on Wetar Island, Indonesia

    NASA Astrophysics Data System (ADS)

    Scotney, Philip M.; Roberts, Stephen; Herrington, Richard J.; Boyce, Adrian J.; Burgess, Ray

    2005-07-01

    Wetar Island is composed of Neogene volcanic rocks and minor oceanic sediments and forms part of the Inner Banda Arc. The island preserves precious metal-rich volcanogenic massive sulfide and barite deposits, which produced approximately 17 metric tonnes of gold. The polymetallic massive sulfides are dominantly pyrite (locally arsenian), with minor chalcopyrite which are cut by late fractures infilled with covellite, chalcocite, tennantite tetrahedrite, enargite, bornite and Fe-poor sphalerite. Barite orebodies are developed on the flanks and locally overly the massive sulfides. These orebodies comprise friable barite and minor sulfides, cemented by a series of complex arsenates, oxides, hydroxides and sulfate, with gold present as <10 μm free grains. Linear and pipe-like structures comprising barite and iron-oxides beneath the barite deposits are interpreted as feeder structures to the barite mineralization. Hydrothermal alteration around the orebodies is zoned and dominated by illite kaolinite smectite assemblages; however, local alunite and pyrophyllite are indicative of late acidic, oxidizing hydrothermal fluids proximal to mineralization. Altered footwall volcanic rocks give an illite K Ar age of 4.7±0.16 Ma and a 40Ar/39Ar age of 4.93±0.21 Ma. Fluid inclusion data suggest that hydrothermal fluid temperatures were around 250 270°C, showed no evidence of boiling, with a mean salinity of 3.2 wt% equivalent NaCl. The δ34S composition of sulfides ranges between +3.3‰ and +11.7‰ and suggests a significant contribution of sulfur from the underlying volcanic edifice. The δ34S barite data vary between +22.4‰ and +31.0‰, close to Miocene seawater sulfate. Whole rock 87Sr/86Sr analyses of unaltered volcanic rocks (0.70748 0.71106) reflect contributions from subducted continental material in their source region. The 87Sr/86Sr barite data (0.7076 0.7088) indicate a dominant Miocene seawater component to the hydrothermal system. The mineral deposits formed on

  8. m-Terphenyl thiols: rigid and bulky molecules for the formation of bioactive self-assembled monolayers on gold.

    PubMed

    Dickie, Diane A; Chan, Andy Y C; Jalali, Hanifa; Jenkins, Hilary A; Yu, Hua-Zhong; Clyburne, Jason A C

    2004-11-07

    The m-terphenyl 4-mercaptomethyl-2,6-diphenylbenzoic acid (3), was prepared and shown to form omega-carboxyl terminated self-assembled monolayers (SAMs) on gold with high surface pKa(10.1 +/- 0.2) and low density favourable for the binding of biological macromolecules.

  9. Gold Electrodes Modified with Self-Assembled Monolayers for Measuring L-Ascorbic Acid: An Undergraduate Analytical Chemistry Laboratory Experiment

    ERIC Educational Resources Information Center

    Ito, Takashi; Perera, D. M. Neluni T.; Nagasaka, Shinobu

    2008-01-01

    This article describes an undergraduate electrochemistry laboratory experiment in which the students measure the L-ascorbic acid content of a real sample. Gold electrodes modified with self-assembled monolayers (SAMs) of thioctic acid and cysteamine are prepared to study the effects of surface modification on the electrode reaction of L-ascorbic…

  10. Infrared spectroelectrochemical characterization of ferrocene-terminated alkanethiolate monolayers at gold

    SciTech Connect

    Popenoe, D.D.; Deinhammer, R.S.; Porter, M.D. Iowa State Univ., Ames, IA )

    1992-10-01

    Cyclic voltammetry and in situ infrared reflection-absorption spectroscopy with electrochemical modulation were applied to the study of monolayers self-assembled from 11-mercaptoundecyl ferrocene-carboxylate (FcCOOC[sub 11]SH) at gold. Voltammetry was used to assess both the reactivity and stability of the surface film in various aqueous electrolytes. The results of these studies indicated that the ferrocenyl monolayers are relatively unstable at pH > 2, except when perchlorate is the dominant anion present. A large change in double-layer capacitance observed upon oxidation of the ferrocenyl end group was attributed to the creation of cationic sites in the diffuse layer. Compositional and structural correlations between the monolayer and the redox chemistry of the ferrocenyl end group were probed using the in situ spectroscopic technique. The features observed in the differential spectra of the oxidized form of the film were ascribed to changes in the bond strengths of the adsorbate as a result of generation of a ferricinium ion. No detectable changes in orientation of the polymethylene chains as a function of applied voltage were observed. The spectral data also suggest that the redox chemistry leads to a reorientation of the water molecules in the region near the ferrocenyl end group. Vibrational mode assignments for FcCOOC[sub 11]SH, based on studies of several analogs with different alkoxy groups, are presented along with infrared spectra and band assignments for several isotopically labeled ferrocenyl esters (i.e., ethyl ferrocenecarboxylate, ethyl-d[sub 5] ferrocenecarboxylate, and 2-(dimethylamino)ethyl ferrocenecarboxylate). 55 refs., 7 figs., 2 tabs.

  11. Mechanism of lipid bilayer penetration by mixed monolayer-protected gold nanoparticles

    NASA Astrophysics Data System (ADS)

    van Lehn, Reid; Atukorale, Prabhani; Carney, Randy; Stellacci, Francesco; Irvine, Darrell; Alexander-Katz, Alfredo

    2013-03-01

    Recently, gold nanoparticles (AuNPs) protected by a binary mixture of hydrophobic and hydrophilic alkanethiol ligands were observed to spontaneously penetrate cellular membranes via a non-specific mechanism. Penetration was observed even at low temperatures and in the presence of endocytotic inhibitors, implying that AuNPs crossed the membrane by a non-endocytotic process. Furthermore, penetration was shown to depend on the amphiphilicity and nanoscale morphology of the protecting monolayer. In this work, we use a variety of simulation techniques to elucidate the mechanism of lipid bilayer penetration and compare our results to experiments with lipid vesicles. We show that these AuNPs can stably embed within lipid bilayers by ``snorkeling'' charges out of the bilayer core; the stability of such a state is a function of particle size, the composition of the protecting monolayer, and other environmental conditions. We use detailed simulations to analyze structural changes in the surrounding lipids and show that the energy barrier for embedding is considerably reduced in the presence of bilayer defects. We expect that these results will enable the design of novel drug delivery carriers and biosensors.

  12. Understanding the Phase Diagram of Self-Assembled Monolayers of Alkanethiolates on Gold

    PubMed Central

    2016-01-01

    Alkanethiolate monolayers on gold are important both for applications in nanoscience as well as fundamental studies of adsorption and self-assembly at metal surfaces. While considerable experimental effort has been put into understanding the phase diagram of these systems, theoretical work based on density functional theory (DFT) has long been hampered by the inability of conventional exchange-correlation functionals to describe dispersive interactions. In this work, we combine dispersion-corrected DFT calculations using the new vdW-DF-CX functional with the ab initio thermodynamics method to study the stability of dense standing-up and low-coverage lying-down phases on Au(111). We demonstrate that the lying-down phase has a thermodynamic region of stability starting from thiolates with alkyl chains consisting of n ≈ 3 methylene units. This phase emerges as a consequence of a competition between dispersive chain–chain and chain–substrate interactions, where the strength of the latter varies more strongly with n. A phase diagram is derived under ultrahigh-vacuum conditions, detailing the phase transition temperatures of the system as a function of the chain length. The present work illustrates that accurate ab initio modeling of dispersive interactions is both feasible and essential for describing self-assembled monolayers. PMID:27313813

  13. Highly sensitive hydrogen sulfide (H2 S) gas sensors from viral-templated nanocrystalline gold nanowires

    NASA Astrophysics Data System (ADS)

    Moon, Chung Hee; Zhang, Miluo; Myung, Nosang V.; Haberer, Elaine D.

    2014-04-01

    A facile, site-specific viral-templated assembly method was used to fabricate sensitive hydrogen sulfide (H2S) gas sensors at room temperature. A gold-binding M13 bacteriophage served to organize gold nanoparticles into linear arrays which were used as seeds for subsequent nanowire formation through electroless deposition. Nanowire widths and densities within the sensors were modified by electroless deposition time and phage concentration, respectively, to tune device resistance. Chemiresistive H2S gas sensors with superior room temperature sensing performance were produced with sensitivity of 654%/ppmv, theoretical lowest detection limit of 2 ppbv, and 70% recovery within 9 min for 0.025 ppmv. The role of the viral template and associated gold-binding peptide was elucidated by removing organics using a short O2 plasma treatment followed by an ethanol dip. The template and gold-binding peptide were crucial to electrical and sensor performance. Without surface organics, the resistance fell by several orders of magnitude, the sensitivity dropped by more than a factor of 100 to 6%/ppmv, the lower limit of detection increased, and no recovery was detected with dry air flow. Viral templates provide a novel, alternative fabrication route for highly sensitive, nanostructured H2S gas sensors.

  14. In situ growth of monolayer porous gold nanoparticles film as high-performance SERS substrates

    NASA Astrophysics Data System (ADS)

    Song, Chunyuan; Wei, Yuhan; Da, Bingtao; Zhang, Haiting; Cong, Xing; Yang, Boyue; Yang, Yanjun; Wang, Lianhui

    2016-07-01

    Surface-enhanced Raman scattering (SERS) has recently received considerable attention as an ultrasensitive analytic technique. However, its wide application is limited by lack of excellent SERS-active substrates. In this work a SERS substrate with arrayed monolayer films of porous gold nanoparticles is prepared on a solid substrate by a facile, in situ and one-step growth approach. Specifically, the solid substrate was coated with a layer of dense positive charges first by layer-by-layer assembly, followed by patterned a PDMS film with arrayed wells on the substrate. Then the growth solution including chlorauric acid, cetyltrimethylammonium chloride, and ascorbic acid in a certain proportion was transferred into the wells for in situ and one-step growth of porous gold nanoparticles on the substrate. The growth time, feed ratio of the reagents, and repeat times of the in situ growth were studied systematically to obtain optimal parameters for preparing an optimal SERS substrate. The as-prepared optimal SERS substrate not only has good SERS performance with the enhancement factor up to ∼1.10 × 106, but also shows good uniformity and stability. The SERS substrate was further utilized to be ultrasensitive SERS-based chemical sensors for ppb-level detection of highly toxic dyfonate. The preliminary result indicates that the as-prepared SERS substrate has good SERS performance and shows a number of great potential applications in SERS-based sensors.

  15. Comparative study of decyl thiocyanate and decanethiol self-assembled monolayers on gold substrates

    NASA Astrophysics Data System (ADS)

    Dreesen, L.; Volcke, C.; Sartenaer, Y.; Peremans, A.; Thiry, P. A.; Humbert, C.; Grugier, J.; Marchand-Brynaert, J.

    2006-09-01

    In a recent paper Ciszek et al. [J.W. Ciszek, M.P. Stewart, J.M. Tour, J. Am. Chem. Soc. 126 (2004) 13172] showed that organic thiocyanates may be an interesting alternative to the use of thiols for thiolate assemblies. We use scanning tunnelling microscopy (STM), infrared reflection absorption and sum-frequency generation spectroscopies (IRRAS and SFG) in order to study the adsorption properties of decyl thiocyanates (DTCN) and compare them to the decanethiol (DT) ones. Firstly, IRRAS measurements show that DTCN molecules form self-assembled monolayers (SAMs) on gold via a thiolate link with the metallic substrate. Secondly, the DTCN SAM on gold is less ordered than the DT one as highlighted by SFG spectroscopy. Indeed, the intensities of the methyl vibration modes vanish while the methylene ones increase when DTCN molecules are adsorbed on the substrate instead of DT. We explain the differences in SAMs quality on the basis of STM measurements which reveal differences in molecular order and packing.

  16. Formation of self-assembled monolayer of curcuminoid molecules on gold surfaces

    NASA Astrophysics Data System (ADS)

    Berlanga, Isadora; Etcheverry-Berríos, Álvaro; Mella, Andy; Jullian, Domingo; Gómez, Victoria Alejandra; Aliaga-Alcalde, Núria; Fuenzalida, Victor; Flores, Marcos; Soler, Monica

    2017-01-01

    We investigated the formation of self-assembled monolayers of two thiophene curcuminoid molecules, 2-thphCCM (1) and 3-thphCCM (2), on polycrystalline gold substrates prepared by immersion of the surfaces in a solution of the molecules during 24 h. The functionalized surfaces were studied by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). Despite the fact that both molecules have the same composition and almost the same structure, these molecules exhibit different behavior on the gold surface, which can be explained by the different positions of the sulfur atoms in the terminal aromatic rings. In the case of molecule 1, the complete formation of a SAM can be observed after 24 h of immersion. In the case of molecule 2, the transition from flat-lying to upright configuration on the surface is still in process after 24 h of immersion. This is attributed to the fact that molecule 2 have the sulfur atoms more exposed than molecule 1.

  17. Self-Assembled Monolayers of Perfluoroanthracenylaminoalkane Thiolates on Gold as Potential Electron Injection Layers.

    PubMed

    Zhang, Zibin; Wächter, Tobias; Kind, Martin; Schuster, Swen; Bats, Jan W; Nefedov, Alexei; Zharnikov, Michael; Terfort, Andreas

    2016-03-23

    As a material with relatively small band gap and low lying valence orbitals, perfluoroanthracene (PFA) is of interest for the modification of electrode surfaces, for example, as charge injection layers for n-type organic semiconductors. To covalently attach PFA in the form of self-assembled monolayers (SAMs), we developed a synthesis of derivatives with a sulfur termination, linked to the 2-position of the PFA moieties by an -NH- group and a short alkane chain with two and three methylene groups, respectively. Spectroscopic characterization of the SAMs reveals that the molecules adopt an almost upright orientation on the gold surface, with the packing density mostly determined by the steric demands of the PFA units. The number of the methylene groups in the -NH-alkyl linker has only a minor impact on the SAM structure because of the nonsymmetric attachment of the PFA units, which permits the compensation of the orientational constraints imposed by the bending potential. The investigated SAMs alter the work function of gold by +(0.59-0.64) eV, suggesting comparably strong depolarization effects, affecting the extent of the work function modification.

  18. Positioning of CNTs over the gold substrate via self-assembled monolayer functionalization using dip-pen nanowriting

    NASA Astrophysics Data System (ADS)

    Agarwal, Pankaj B.; Sahu, Smriti; Kapse, Pooja; Gupta, Sanjeev K.

    2012-10-01

    The most important aspect of fabrication of Carbon Nanotubes (CNTs) based devices/sensors is the selective and controlled positioning of CNTs, which is a challenging issue for the researchers now a days. Here, we have presented a simple and efficient methodology for positioning of CNTs using 16-MHA self-assembled monolayers (SAMs), written over the gold substrate using Dip-pen Nanowriting (DPN). The analysis of the obtained AFM images clearly shows significant height increment of nanopatterns, which corresponds to the attachment of carbonaceous material over the written nanopatterns. Carbon Nanotubes (CNTs), Dip-pen Nanowriting (DPN), 16-MHA, 1-ODT and Self-assembled Monolayer (SAM).

  19. Electrochemical sensor for immunoassay of carcinoembryonic antigen based on thionine monolayer modified gold electrode.

    PubMed

    Dai, Zong; Chen, Jin; Yan, Feng; Ju, Huangxian

    2005-01-01

    A sensor based on thionine monolayer modified gold electrode for determination of carcinoembryonic antigen (CEA) in human serum is proposed. The sensor is prepared by covalently binding thionine to a cysteamine self-assembled monolayer with p-phthaloyl chloride as a linkage, which gives a surface coverage of 8.97+/-3.28 x 10(-12)mol/cm(2) for thionine. The electrochemistry of the immobilized thionine displays a surface-controlled electrode process with an average electron transfer rate constant of 1.47+/-0.84 s(-1). Based on an electrochemical enzyme-linked immunoassay by using the immobilized thionine as an electron transfer mediator between the electrode and the horseradish peroxidase (HRP) labeled anti-CEA antibody, a calibration curve with two linear ranges from 0.6 to 17 and 17 to 200 ng/mL and a detection limit of 0.2 ng/mL for CEA determination is obtained in pH 4.2 PBS containing 2.0 mmol/L H(2)O(2) and 0.5 mol/L NaCl. The sensor shows a good accuracy. The precision and reproducibility are acceptable with the intra-assay CV of 4.9% and 5.9% at 10 and 100 ng/mL CEA concentrations, respectively, and the inter-assays CV of 7.8% at 100 ng/mL CEA. The response of thionine modified electrode shows only 1.6% decrease after 100 replicate measurements and the storage stability is acceptable in a pH 7.0 PBS at 4 degrees C for 1 week. The method avoids the addition of electron transfer mediator to the solution, thus is much simpler. The proposed method would be valuable for the diagnosis and monitoring of carcinoma and its metastasis.

  20. Excitons in a mirror: Formation of “optical bilayers” using MoS{sub 2} monolayers on gold substrates

    SciTech Connect

    Mertens, Jan; Baumberg, Jeremy J.; Shi, Yumeng; Yang, Hui Ying; Molina-Sánchez, Alejandro; Wirtz, Ludger

    2014-05-12

    We report coupling of excitons in monolayers of molybdenum disulphide to their mirror image in an underlying gold substrate. Excitons at the direct band gap are little affected by the substrate whereas strongly bound C-excitons associated with a van-Hove singularity change drastically. On quartz substrates only one C-exciton is visible (in the blue) but on gold substrates a strong red-shifted extra resonance in the green is seen. Exciton coupling to its image leads to formation of a “mirror biexciton” with enhanced binding energy. Estimates of this energy shift in an emitter-gold system match experiments well. The absorption spectrum of MoS{sub 2} on gold thus resembles a bilayer of MoS{sub 2} which has been created by optical coupling. Additional top-mirrors produce an “optical bulk.”.

  1. Simultaneous optimization of monolayer formation factors, including temperature, to significantly improve nucleic acid hybridization efficiency on gold substrates.

    PubMed

    Pris, Andrew D; Ostrowski, Sara G; Garaas, Sarah D

    2010-04-20

    Past literature investigations have optimized various single factors used in the formation of thiolated, single stranded DNA (ss-DNA) monolayers on gold. In this study a more comprehensive approach is taken, where a design of experiment (DOE) is employed to simultaneously optimize all of the factors involved in construction of the capture monolayer used in a fluorescence-based hybridization assay. Statistical analysis of the fluorescent intensities resulting from the DOE provides empirical evidence for the importance and the optimal levels of traditional and novel factors included in this investigation. We report on the statistical importance of a novel factor, temperature of the system during monolayer formation of the capture molecule and lateral spacer molecule, and how proper usage of this temperature factor increased the hybridization signal 50%. An initial theory of how the physical factor of heat is mechanistically supplementing the function of the lateral spacer molecule is provided.

  2. Gold enrichment and the Bi-Au association in pyrrhotite-rich massive sulfide deposits, Escanaba trough, Southern Gorda Ridge

    USGS Publications Warehouse

    Tormanen, T.O.; Koski, R.A.

    2005-01-01

    High gold contents (to 10.1 ppm, avg 1.4 ppm, n = 34) occur in pyrrhotite-rich massive sulfide samples from the sediment-covered floor of the Escanaba trough, the slow-spreading, southernmost segment of Gorda Ridge. These concentrations reflect the presence of primary gold, formed during high-temperature hydrothermal activity in mounds and chimneys, and secondary gold deposited during sea-floor weathering of massive sulfide. Primary gold occurs as fine-grained (2 ??m) secondary gold grains have a porous, flaky morphology and occur in samples in which pyrrhotite is oxidized and replaced by Fe oxyhydroxides, Fe sulfate, and sulfur. Mounds and chimneys dominated by pyrrhotite and containing lesser amounts of isocubanite, chalcopyrite, and Fe-rich sphalerite were formed by high-temperature (estimated range 325??-275??C), reduced, low-sulfur vent fluids. The mineral and fluid compositions during this main stage of hydrothermal venting reflect subsurface interaction between circulating hydrothermal fluids and turbiditic sediment containing as much as 1.1 percent organic carbon. As the deposition of pyrrhotite, Cu-Fe sulfides, and sphalerite waned, a volumetrically minor suite of sulfarsenide, arsenide, Bi, and Au minerals was deposited from highly reduced, late main-stage fluids diffusing through mounds and chimneys. The low solubility of Au as a bisulfide complex and the absence of fluid mixing during this stage of hydrothermal activity apparently inhibited the precipitation of gold directly from solution. Instead, gold precipitation is thought to be linked to elevated concentrations of Bi in the late main-stage fluids. The textural relationships of Au and Bi minerals in pyrrhotite-rich samples, low melting point of native bismuth (271.4??C), and recent experimental results on Au and Bi in hydrothermal fluids contribute to the hypothesis that gold was effectively scavenged from the Escanaba trough vent fluids by coexisting droplets of liquid bismuth. Additional phase

  3. EQCM Measurements: Redox-Induced Changes in Solvent and Ion Content in Anchored Redox Monolayers of Organosulfur Compounds and Their Electrocatalysis on Gold Electrodes

    DTIC Science & Technology

    1990-08-01

    EQCM Mwasurements: Redox-Induced Changes in Solvent and M0 Content in Anchored Redox Monolayers of Organosulfur CD Compounds and their Electrocatalysis ...REDOX-INDUCED CHANGES IN SOLVENT AND ION CONTENT IN ANCHORED REDOX MONOLAYERS OF ORGANOSULFUR COMPOUNDS AND THEIR ELECTROCATALYSIS ON GOLD...Measurements: Redox-Induced Changes in Solvent and Ion Content in Anchored Redox Monolayers of Organosulfur Compounds and their Electrocatalysis on

  4. Electrocatalysts having platium monolayers on palladium, palladium alloy, and gold alloy core-shell nanoparticles, and uses thereof

    DOEpatents

    Adzic, Radoslav; Mo, Yibo; Vukmirovic, Miomir; Zhang, Junliang

    2010-12-21

    The invention relates to platinum-coated particles useful as fuel cell electrocatalysts. The particles are composed of a noble metal or metal alloy core at least partially encapsulated by an atomically thin surface layer of platinum atoms. The invention particularly relates to such particles having a palladium, palladium alloy, gold alloy, or rhenium alloy core encapsulated by an atomic monolayer of platinum. In other embodiments, the invention relates to fuel cells containing these electrocatalysts and methods for generating electrical energy therefrom.

  5. One-pot reaction for the preparation of biofunctionalized self-assembled monolayers on gold surfaces

    NASA Astrophysics Data System (ADS)

    Raigoza, Annette F.; Fies, Whitney; Lim, Amber; Onyirioha, Kristeen; Webb, Lauren J.

    2017-02-01

    The Huisgen cycloaddition reaction ("click" chemistry) has been used extensively to functionalize surfaces with macromolecules in a straightforward manner. We have previously developed a procedure using the copper(I)-catalyzed click reaction to tether synthetic α-helical peptides carrying two alkyne groups to a well-ordered azide-terminated alkanethiol self-assembled monolayer (SAM) on a Au(111) surface. While convenient, click-based strategies potentially pose significant problems from reagents, solvents, and reaction temperatures that may irreversibly damage some molecules or substrates. Tuning click chemistry conditions would allow individual optimization of reaction conditions for a wide variety of biomolecules and substrate materials. Here, we explore the utility of simultaneous SAM formation and peptide-attachment chemistry in a one-pot reaction. We demonstrate that a formerly multistep reaction can be successfully carried out concurrently by mixing azide-terminated alkanethiols, CuCl, and a propargylglycine-containing peptide over a bare gold surface in ethanol and reacting at 70 °C. X-ray photoelectron spectroscopy (XPS), surface infrared spectroscopy, surface circular dichroic (CD) spectroscopy, and scanning tunneling microscopy (STM) were used to determine that this one-pot reaction strategy resulted in a high density of surface-bound α-helices without aggregation. This work demonstrates the simplicity and versatility of a SAM-plus-click chemistry strategy for functionalizing Au surfaces with structured biomolecules.

  6. Optical properties of Yeast Cytochrome c monolayer on gold: an in situ spectroscopic ellipsometry investigation.

    PubMed

    Toccafondi, Chiara; Prato, Mirko; Maidecchi, Giulia; Penco, Amanda; Bisio, Francesco; Cavalleri, Ornella; Canepa, Maurizio

    2011-12-01

    The adsorption of Yeast Cytochrome c (YCC) on well defined, flat gold substrates has been studied by Spectroscopic Ellipsometry (SE) in the 245-1000 nm wavelength range. The investigation has been performed in aqueous ambient at room temperature, focusing on monolayer-thick films. In situ δΨ and δΔ difference spectra have shown reproducibly well-defined features related to molecular optical absorptions typical of the so-called heme group. The data have been reproduced quantitatively by a simple isotropic optical model, accounting for the molecular absorption spectrum and film-substrate interface effects. The simulations allowed a reliable estimate of the film thickness and the determination of the position and the shape of the so-called Soret absorption peak that, within the experimental uncertainty, is the same found for molecules in liquid. These findings suggest that YCC preserves its native structure upon adsorption. The same optical model was able to reproduce also ex situ results on rinsed and dried samples, dominated by the spectral features associated to the polypeptide chain that tend to overwhelm the heme absorption features.

  7. Orientated binding of photosynthetic reaction centers on gold using Ni-NTA self-assembled monolayers.

    PubMed

    Trammell, Scott A; Wang, Leyu; Zullo, Joseph M; Shashidhar, Ranganathan; Lebedev, Nikolai

    2004-07-15

    Coupling of photosynthetic reaction centers (RCs) with inorganic surfaces is attractive for the identification of the mechanisms of interprotein electron transfer (ET) and for possible applications in construction of photo- and chemosensors. Here we show that RCs from Rhodobacter sphaeroides can be immobilized on gold surfaces with the RC primary donor looking towards the substrate by using a genetically engineered poly-histidine tag (His(7)) at the C-terminal end of the M-subunit and a Ni-NTA terminated self-assembled monolayer (SAM). In the presence of an electron acceptor, ubiquinone-10, illumination of this RC electrode generates a cathodic photocurrent. The action spectrum of the photocurrent coincides with the absorption spectrum of RC and the photocurrent decreases in response to the herbicide, atrazine, confirming that the RC is the primary source of the photoresponse. Disruption of the Ni-NTA-RC bond by imidazole leads to about 80% reduction of the photocurrent indicating that most of the photoactive protein is specifically bound to the electrode through the linker.

  8. A detrital model for the origin of gold and sulfides in the Witwatersrand basin based on Re-Os isotopes

    NASA Astrophysics Data System (ADS)

    Kirk, Jason; Ruiz, Joaquin; Chesley, John; Titley, Spencer; Walshe, John

    2001-07-01

    The Re-Os systematics of gold and sulfides from the Witwatersrand basin were utilized to determine whether the gold is detrital or was introduced by hydrothermal solutions from outside the basin. Gold from a gravity concentrate from the Western Areas Gold Plant and gold from the Vaal Reef have very high Os concentrations of approximately 73 to 10000 ppb and 3 to 32 ppb Re, resulting in 187Re/ 188Os ratios of 0.010 to 0.185. The gold has subchondritic 187Os/ 188Os ratios between 0.1056 to 0.1099 and an average value of 0.1067. Rhenium depletion ages (T RD) range from 3.5 Ga to 2.9 Ga, with a median age of 3.3 Ga. Pyrite from the Vaal Reef have Os concentrations ranging from 0.26 to 0.68 ppb, Re concentrations of 1.7 to 2.8 ppb and 187Re/ 188Os ratios of approximately 14 to 87. The pyrite samples have measured 187Os/ 188Os ratios of 0.84 to 4.7 and define an isochron with an age of 2.99 ± 0.11 Ga (MSWD = 0.77). The Os isotopic data from the direct measurement of gold preclude introduction of gold to the Witwatersrand basin from crustally derived metamorphic or hydrothermal fluids between 2.7 to 2.0 Ga. The unradiogenic 187Os/ 188Os ratios, old T RD ages of the Western Areas and Vaal Reef gold samples, as well as the contemporaneously old age of the Vaal Reef pyrite are consistent with detrital deposition of gold during the formation of the Witswatersrand basin. The Os data will allow for minor hydrothermal remobilization and/or overprinting of hydrothermal gold on preexisting detrital gold grains but does not support the introduction of gold solely by hydrothermal fluids.

  9. OPTIMIZATION OF VOLTAMMETRIC METHODS FOR AN IN SITU DETERMINATION OF TOTAL SULFIDE IN ANOXIC POREWATER USING A MERCURY PLATED GOLD ELECTRODE

    EPA Science Inventory

    Voltammetric methods for determination of total sulfide concentrations in anoxic sediments utilizing a previously described [1] gold-based mercury amalgam microelectrode were optimized. Systematic studies in NaCl (supporting electrolyte) and porewater indicate variations in ionic...

  10. Kinetics of electron transfer through ferrocene-terminated alkanethiol monolayers on gold

    SciTech Connect

    Smalley, J.F.; Feldberg, S.W.; Newton, M.D.; Liu, Y.P.; Chidsey, C.E.D.; Linford, M.R.

    1995-08-31

    The kinetics of electron transfer between a substrate gold electrode and a self-assembled monolayer formed from CH{sub 3}(CH{sub 2}){sub n-1}SH and ({eta}{sup 5} C{sub 5}H{sub 5})Fe ({eta}{sup 5}-C{sub 5}H{sub 4})CO{sub 2}(CH{sub 2}){sub n}SH were studied as a function of n, the number of methylenes in the alkyl chain tethering the ferrocene moiety to the electrode, using the indirect laser-induced temperature jump method (ILIT). For 5 {<=} n {<=} 9 the standard electron-transfer rate constants vary according to {kappa}{sub {tau}a,n=0} exp[-{beta}{sub n}n] where {kappa}{sub {tau}a,n=0} is the (extrapolated) rate constant for the electron transfer at n = 0. At {Tau} = 25{degree}C, {kappa}{sub {tau}a,n} 0 {approx_equal} 6 x 10{sup 8} s{sup -1} and {beta}{sub n} = 1.21 x 0.05. The ILIT method allows rates to be measured that are too fast to be measured by conventional chronoamperometry at a macroelectrode, which is limited to rate constants of {<=} 10{sup 4} s{sup -1}. Using a Marcus formalism, the reorganization energy, {lambda}, for the electron-transfer process at a given n was determined from the slope of an Arrhenius plot over the temperature range 15-55{degree}C. Values of {lambda} determined from Arrhenius slopes for n = 8 and 9 using ILIT are in reasonable agreement with the value of {lambda} previously deduced from the potential dependence of the rate constant for n = 16. 39 refs., 13 figs., 3 tabs.

  11. Absolute timing of sulfide and gold mineralization: A comparison of Re-Os molybdenite and Ar-Ar mica methods from the Tintina Gold Belt, Alaska

    USGS Publications Warehouse

    Selby, D.; Creaser, R.A.; Hart, C.J.R.; Rombach, C.S.; Thompson, J.F.H.; Smith, M.T.; Bakke, A.A.; Goldfarb, R.J.

    2002-01-01

    New Re-Os molybdenite dates from two lode gold deposits of the Tintina Gold Belt, Alaska, provide direct timing constraints for sulfide and gold mineralization. At Fort Knox, the Re-Os molybdenite date is identical to the U-Pb zircon age for the host intrusion, supporting an intrusive-related origin for the deposit. However, 40Ar/39Ar dates from hydrothermal and igneous mica are considerably younger. At the Pogo deposit, Re-Os molybdenite dates are also much older than 40Ar/39Ar dates from hydrothermal mica, but dissimilar to the age of local granites. These age relationships indicate that the Re-Os molybdenite method records the timing of sulfide and gold mineralization, whereas much younger 40Ar/39Ar dates are affected by post-ore thermal events, slow cooling, and/or systemic analytical effects. The results of this study complement a growing body of evidence to indicate that the Re-Os chronometer in molybdenite can be an accurate and robust tool for establishing timing relations in ore systems.

  12. Magmatic-vapor expansion and the formation of high-sulfidation gold deposits: Chemical controls on alteration and mineralization

    USGS Publications Warehouse

    Henley, R.W.; Berger, B.R.

    2011-01-01

    Large bulk-tonnage high-sulfidation gold deposits, such as Yanacocha, Peru, are the surface expression of structurally-controlled lode gold deposits, such as El Indio, Chile. Both formed in active andesite-dacite volcanic terranes. Fluid inclusion, stable isotope and geologic data show that lode deposits formed within 1500. m of the paleo-surface as a consequence of the expansion of low-salinity, low-density magmatic vapor with very limited, if any, groundwater mixing. They are characterized by an initial 'Sulfate' Stage of advanced argillic wallrock alteration ?? alunite commonly with intense silicification followed by a 'Sulfide' Stage - a succession of discrete sulfide-sulfosalt veins that may be ore grade in gold and silver. Fluid inclusions in quartz formed during wallrock alteration have homogenization temperatures between 100 and over 500 ??C and preserve a record of a vapor-rich environment. Recent data for El Indio and similar deposits show that at the commencement of the Sulfide Stage, 'condensation' of Cu-As-S sulfosalt melts with trace concentrations of Sb, Te, Bi, Ag and Au occurred at > 600 ??C following pyrite deposition. Euhedral quartz crystals were simultaneously deposited from the vapor phase during crystallization of the vapor-saturated melt occurs to Fe-tennantite with progressive non-equilibrium fractionation of heavy metals between melt-vapor and solid. Vugs containing a range of sulfides, sulfosalts and gold record the changing composition of the vapor. Published fluid inclusion and mineralogical data are reviewed in the context of geological relationships to establish boundary conditions through which to trace the expansion of magmatic vapor from source to surface and consequent alteration and mineralization. Initially heat loss from the vapor is high resulting in the formation of acid condensate permeating through the wallrock. This Sulfate Stage alteration effectively isolates the expansion of magmatic vapor in subsurface fracture arrays

  13. Comprehensive recovery of gold and base-metal sulfide minerals from a low-grade refractory ore

    NASA Astrophysics Data System (ADS)

    Li, Wen-juan; Liu, Shuang; Song, Yong-sheng; Wen, Jian-kang; Zhou, Gui-ying; Chen, Yong

    2016-12-01

    The comprehensive recovery of small amounts of valuable minerals such as gold and base-metal sulfide minerals from a low-grade refractory ore was investigated. The following treatment strategy was applied to a sample of this ore: gold flotation-gold concentrate leaching-lead and zinc flotation from the gold concentrate leaching residue. Closed-circuit trials of gold flotation yielded a gold concentrate that assayed at 40.23 g·t-1 Au with a recovery of 86.25%. The gold concentrate leaching rate was 98.76%. Two variants of lead-zinc flotation from the residue—preferential flotation of lead and zinc and bulk flotation of lead and zinc—were tested using the middling processing method. Foam from the reflotation was returned to the lead rougher flotation or lead-zinc bulk flotation, whereas middlings from reflotation were discarded. Sulfur concentrate was a byproduct. The combined strategy of flotation, leaching, and flotation is recommended for the treatment of this kind of ore.

  14. The Chahnaly low sulfidation epithermal gold deposit, western Makran volcanic arc, southeastern Iran

    USGS Publications Warehouse

    Sholeh, Ali; Rastad, Ebrahim; Huston, David L.; Gemmell, J. Bruce; Taylor, Ryan D.

    2016-01-01

    The Chahnaly Au deposit formed during the early stages of magmatism. LA-ICP-MS zircon U-Pb geochronology of host andesite and 40Ar/39Ar dating of two samples of gold-associated adularia show that the ore-stage adularia (19.83 ± 0.10 and 19.2 ± 0.5 Ma) is younger, by as much as 1.5 million years, than the volcanic host rock (20.32 ± 0.4 Ma). Therefore, either hydrothermal activity continued well after volcanism or a second magmatic event rejuvenated hydrothermal activity. This second magmatic event may be related to eruption of porphyritic andesite at ~20.32 ± 0.40 Ma, which is within error of ~19.83 ± 0.10 Ma adularia. The new LA-ICP-MS zircon U-Pb host rock and vein adularia 40Ar/39Ar ages suggest that early Miocene magmatism and mineralization in the Bazman area is of a similar age to that of the Saindak porphyry and Tanjeel porphyry center of the giant Reko Diq deposit. This confirms the existence of early Miocene arc magmatism and mineralization along the Iranian part of the Makran volcanic arc. Ore, alteration mineralogy, and alteration patterns indicate that the Chahnaly deposit is a typical low-sulfidation epithermal Au deposit, located in a poorly explored part of the Makran volcanic arc in Iran.                   

  15. Potential driven deposition of poly(diallyldimethylammonium chloride) onto the surface of 3-mercaptopropionic acid monolayers assembled on gold.

    PubMed

    Sanders, Wesley; Anderson, Mark R

    2008-11-18

    Electrochemical impedance spectroscopy (EIS) and quartz crystal microbalance (QCM) measurements are used to examine the ability of applied potential to drive the ionic self-assembly of poly(diallyldimethylammonium) chloride (PDDA) onto a substrate modified with a monolayer of 3-mercaptopropionic acid (3-MPA). The potential of zero charge (PZC) of the gold electrode modified with a monolayer of 3-MPA was found by differential capacitance measurements to be -0.12 (+/-0.01) V versus Ag-AgCl. Changing the substrate potential to values positive (-0.01 V vs Ag-AgCl) of the PZC induces interfacial conditions that are favorable for the electrostatic deposition of cationic polymers onto the surface of 3-MPA monolayers. This result is also consistent with experimental observations obtained when the 3-MPA-modified substrate is exposed to 0.10 mol L (-1) NaOH solutions. When potentials equal or negative to the PZC are applied to the substrate, no significant accumulation of the PDDA is found by either QCM or EIS measurement. This result is consistent with results obtained when the 3-MPA modified substrate is exposed to 0.10 mol L (-1) HCl solutions where no PDDA adsorption is expected because the monolayer is neutral under these conditions. Changes in the impedance and quartz crystal frequency obtained after potential is applied to the substrate are interpreted in terms of the applied potential creating interfacial conditions that are favorable for the deprotonation of the terminal carboxylic acid groups and the subsequent electrostatic assembly of the polycation onto the negatively charged monolayer.

  16. Patterning Self-Assembled Monolayers on Gold: Green Materials Chemistry in the Teaching Laboratory

    ERIC Educational Resources Information Center

    McFarland, Adam D.; Huffman, Lauren M.; Parent, Kathryn, E.; Hutchison, James E.; Thompson, John E.

    2004-01-01

    An experiment demonstrating self-assembled monolayer (SAM) chemistry, organic thin-film patterning and the use of molecular functionality to control macroscopic properties is described. Several important green chemistry principles are introduced.

  17. Formation of Monolayer Films by the Spontaneous Assembly of Organic Thiols from Solution onto Gold

    DTIC Science & Technology

    1988-09-01

    structure of the terminal group, X, widely and thus permit the introduction of a great range of functional groups into a surface. Studies of wettability of...permit the introduction of a great range of functional groups into a surface. Studies of wettability of these monolayers, and of their composition using...relationships between the microscopic structure of organic surfaces and their macroscopic properties (especially wettability ). Studies of organic monolayer films

  18. Plasmonic Gold Nanorods Coverage Influence on Enhancement of the Photoluminescence of Two-Dimensional MoS2 Monolayer

    PubMed Central

    Lee, Kevin C. J.; Chen, Yi-Huan; Lin, Hsiang-Yu; Cheng, Chia-Chin; Chen, Pei-Ying; Wu, Ting-Yi; Shih, Min-Hsiung; Wei, Kung-Hwa; Li, Lain-Jong; Chang, Chien-Wen

    2015-01-01

    The 2-D transition metal dichalcogenide (TMD) semiconductors, has received great attention due to its excellent optical and electronic properties and potential applications in field-effect transistors, light emitting and sensing devices. Recently surface plasmon enhanced photoluminescence (PL) of the weak 2-D TMD atomic layers was developed to realize the potential optoelectronic devices. However, we noticed that the enhancement would not increase monotonically with increasing of metal plasmonic objects and the emission drop after the certain coverage. This study presents the optimized PL enhancement of a monolayer MoS2 in the presence of gold (Au) nanorods. A localized surface plasmon wave of Au nanorods that generated around the monolayer MoS2 can provide resonance wavelength overlapping with that of the MoS2 gain spectrum. These spatial and spectral overlapping between the localized surface plasmon polariton waves and that from MoS2 emission drastically enhanced the light emission from the MoS2 monolayer. We gave a simple model and physical interpretations to explain the phenomena. The plasmonic Au nanostructures approach provides a valuable avenue to enhancing the emitting efficiency of the 2-D nano-materials and their devices for the future optoelectronic devices and systems. PMID:26576041

  19. Size dependent gold nanoparticle interaction at nano-micro interface using both monolayer and multilayer (tissue-like) cell models

    NASA Astrophysics Data System (ADS)

    Yohan, Darren; Yang, Celina; Lu, Xiaofeng; Chithrani, Devika B.

    2016-03-01

    Gold nanoparticles (GNPs) can be used as a model NP system to improve the interface between nanotechnology and medicine since their size and surface properties can be tailored easily. GNPs are being used as radiation dose enhancers and as drug carriers in cancer research. Hence, it is important to know the optimum NP size for uptake not only at monolayer level but also at tissue level. Once GNPs leave tumor vasculature, they enter the tumor tissue. Success of any therapeutic technique using NPs depends on how well NPs penetrate the tumor tissue and reach individual tumor cells. In this work, multicellular layers (MCLs) were grown to model the post-vascular tumor environment. GNPs of 20 nm and 50 nm diameters were used to elucidate the effects of size on the GNP penetration and distribution dynamics. Larger NPs (50 nm) were better at monolayer level, but smaller NPs (20 nm) were at tissue level. The MCLs exhibited a much more extensive extracellular matrix (ECM) than monolayer cell cultures. This increased ECM created a barrier for NP transport and ECM was also dependent on the tumor cell lines. Smaller NPs penetrated better compared to larger NPs. Transport of NPs was better in MDA-MB231 vs MCF-7. This MCL model tissue structures are better tools to optimize NP transport through tissue before using them in animal models. Based on our study, we believe that smaller NPs are better for improved outcome in future cancer therapeutics.

  20. Scanning probe microscopies for the creation and characterization of interfacial architectures: Studies of alkyl thiolate monolayers at gold

    SciTech Connect

    Green, John -Bruce

    1997-01-10

    Scanning probe microscopy (SPM) offers access to the structural and material properties of interfaces, and when combined with macroscopic characterization techniques results in a powerful interfacial development tool. However, the relative infancy of SPM techniques has dictated that initial investigations concentrate on model interfacial systems as benchmarks for testing the control and characterization capabilities of SPM. One such family of model interfacial systems results from the spontaneous adsorption of alkyl thiols to gold. This dissertation examines the application of SPM to the investigation of the interfacial properties of these alkyl thiolate monolayers. Structural investigations result in a proposed explanation for counterintuitive correlations between substrate roughness and heterogeneous electron transfer barrier properties. Frictional measurements are used for characterization of the surface free energy of a series of end-group functionalized monolayers, as well as for the material properties of monolayers composed of varying chain length alkyl thiols. Additional investigations used these characterization techniques to monitor the real-time evolution of chemical and electrochemical surface reactions. The results of these investigations demonstrates the value of SPM technology to the compositional mapping of surfaces, elucidation of interfacial defects, creation of molecularly sized chemically heterogeneous architectures, as well as to the monitoring of surface reactions. However, it is the future which will demonstrate the usefulness of SPM technology to the advancement of science and technology.

  1. Chemical transformation of chiral monolayer-protected gold clusters: observation of ligand size effects on optical and chiroptical responses

    NASA Astrophysics Data System (ADS)

    Yao, Hiroshi; Kitaoka, Noriyuki; Sasaki, Akito

    2012-01-01

    Versatile functionalization of metal clusters is a key step in understanding the reactivity of protective monolayers. We here demonstrate that reaction of the outermost amino groups on (S)-/(R)-penicillamine-protected gold clusters with ethyl isocyanate readily modifies the chiral surface structure through carbamoylation. Interestingly, the clusters are electrophoretically separated by the size of the surface ligand, not by the size of the gold core, which is revealed by UV-vis, IR, and energy dispersive X-ray (EDX) spectroscopy as well as SAXS measurements. The ligand size (or length) is extended through additional reactions of the carbamoylated amino groups with isocyanate, while the chemical similarity in ligand structures is realized by their IR spectral similarity. Optical and chiroptical responses of the separated cluster compounds are thus overall similar to each other, but a close inspection reveals that the ligand size has a small but distinct influence on the chiroptical response of the gold clusters.Versatile functionalization of metal clusters is a key step in understanding the reactivity of protective monolayers. We here demonstrate that reaction of the outermost amino groups on (S)-/(R)-penicillamine-protected gold clusters with ethyl isocyanate readily modifies the chiral surface structure through carbamoylation. Interestingly, the clusters are electrophoretically separated by the size of the surface ligand, not by the size of the gold core, which is revealed by UV-vis, IR, and energy dispersive X-ray (EDX) spectroscopy as well as SAXS measurements. The ligand size (or length) is extended through additional reactions of the carbamoylated amino groups with isocyanate, while the chemical similarity in ligand structures is realized by their IR spectral similarity. Optical and chiroptical responses of the separated cluster compounds are thus overall similar to each other, but a close inspection reveals that the ligand size has a small but distinct

  2. Electrocatalysts having gold monolayers on platinum nanoparticle cores, and uses thereof

    DOEpatents

    Adzic, Radoslav; Zhang, Junliang

    2010-04-27

    The invention relates to gold-coated particles useful as fuel cell electrocatalysts. The particles are composed of an electrocatalytically active core at least partially encapsulated by an outer shell of gold or gold alloy. The invention more particularly relates to such particles having a noble metal-containing core, and more particularly, a platinum or platinum alloy core. In other embodiments, the invention relates to fuel cells containing these electrocatalysts and methods for generating electrical energy therefrom.

  3. Characterization and reactivity of organic monolayers on gold and platinum surfaces

    SciTech Connect

    Wu, Chien-Ching

    1995-12-06

    Purpose is to understand how the mobilization, dielectric, orientation, composition, coverage, and structure of self-assembled organic monolayers on metal surfaces affects the surface reactivities and properties of these films in order to facilitate the construction of desired films. Two model systems were used: tiols at Au and aromatic acids at Pt. Surface analysis methods, including contact angle, electrochemistry, ellipsometry, infrared reflection absorption spectroscopy (IRRAS), and x-ray photospectroscopy, were used to study the self-assembled organic monolayers on Au and Pt. IRRAS, contact angle, and electrochemistry were used to determine the surface pKa of phenylcarboxylic acids and pyridylcarboxylic acids monolayers on Pt. These techniques were also used to determine the orientation of polymethylene chain axis and the carboxylic follow the structural evolution of the chains and end group of the thiolate monolayers during formation. IRRAS was also used to assess the carboxylic acid group in terms of its possible existence as the non-hydrogen-bonded species, the hydrogen-bonded dimeric group, and the hydrogen-bonded polymeric group. These different forms of the end group were also followed vs coverage, as well as the reactivity vs solution pH. IRRAS and contact angle were used to calculate the rate constant of the esterification of carboxylic acid-terminated monolayers on Au.

  4. Ion transport and electron transfer at self-assembled alkylthiol/gold monolayers

    NASA Astrophysics Data System (ADS)

    Boubour, Emmanuelle

    The electrical and electrochemical properties of self-assembled n-alkylthiol monolayers (SAMs) on gold are important if SAMs are to be used as molecular building blocks in biomimetic membranes and in micro- or nano-electronics. Ion transport and electron transfer at SAM/electrolyte interfaces are two important processes which have been characterized by cyclic voltammetry and a.c. impedance spectroscopy. Ion transport from an aqueous phase to the hydrophobic SAM region has been addressed by investigating the insulating properties of a wide variety of X(CH2)nS/Au SAMs (X = CH3, OH, CO2H and CF 3, and n = 7, 9, 11, 15). It was established that when the phase angle at a frequency characteristic of ion diffusion processes ( i.e. 1 Hz) is ≥88°, the SAM is defect-free and obeys the Helmholtz ideal capacitor model. However, when ϕ1HZ < 88°, the SAM is no longer an ionic insulator and ion/water penetration from the electrolyte into the SAM hydrophobic region is observed. The behavior of the phase angle with frequency was used to characterize the permeability of SAMs to electrolyte ions (K+, H2PO4 -, and HPO42-) as a function of the applied d.c. potential. A critical potential, Vc, was identified for each type of SAM corresponding to a transition from an insulating state to a more permeable state. When X = CH3, V c becomes more cathodic with increasing chainlength, i.e. Vc = -0.15 V (vs. Ag/AgCl) for n = 7, -0.25 V for n = 9, 11, and -0.35 V for n = 15. The SAM ionic permeability can also be modulated by maintaining n constant (15) and by varying the terminal group X. Vc is considerably more anodic for hydrophilic SAM/electrolyte interfaces (+0.25 V vs . Ag/AgCl for X = OH and + 0.15 V for X = CO2H) than for hydrophobic interfaces (-0.35 V for X = CH3). The kinetics of electron transfer at CH3(CH2)15CH3 SAMs have been investigated by a.c. impedance spectroscopy at various d.c. overpotentials with three redox couples, Ru(NH3)63+/2+, Fe(CN)63-/4-, and Co(bpy)3 3+/2+. Fits

  5. Microwave-Accelerated Surface Modification of Plasmonic Gold Thin Films with Self-Assembled Monolayers of Alkanethiols

    PubMed Central

    Grell, Tsehai A.J.; Alabanza, Anginelle M.; Gaskell, Karen; Aslan, Kadir

    2013-01-01

    A rapid surface modification technique for the formation of self-assembled monolayers (SAMs) of alkanethiols on gold thin films using microwave heating in less than 10 min is reported. In this regard, SAMs of two model alkanethiols, 11-mercaptoundecanoic acid (11-MUDA, to generate a hydrophilic surface) and undecanethiol (UDET, a hydrophobic surface), were successfully formed on gold thin films using selective microwave heating in 1) a semi-continuous and 2) a continuous fashion and at room temperature (24 hours, control experiment, no microwave heating). The formation of SAMs of 11-MUDA and UDET were confirmed by contact angle measurements, Fourier–transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The contact angles for water on SAMs formed by the selective microwave heating and conventional room temperature incubation technique (24 hours) were measured to be similar for 11-MUDA and UDET. FT-IR spectroscopy results confirmed that the internal structure of SAMs prepared using both microwave heating and at room temperature were similar. XPS results revealed that the organic and sulfate contaminants found on bare gold thin films were replaced by SAMs after the surface modification process was carried out using both microwave heating and at room temperature. PMID:24083414

  6. Microwave-accelerated surface modification of plasmonic gold thin films with self-assembled monolayers of alkanethiols.

    PubMed

    Grell, Tsehai A J; Alabanza, Anginelle M; Gaskell, Karen; Aslan, Kadir

    2013-10-29

    A rapid surface modification technique for the formation of self-assembled monolayers (SAMs) of alkanethiols on gold thin films using microwave heating in <10 min is reported. In this regard, SAMs of two model alkanethiols, 11-mercaptoundecanoic acid (11-MUDA, to generate a hydrophilic surface) and undecanethiol (UDET, a hydrophobic surface), were successfully formed on gold thin films using selective microwave heating in (1) a semicontinuous fashion and (2) a continuous fashion at room temperature (24 h, control experiment, no microwave heating). The formation of SAMs of 11-MUDA and UDET was confirmed by contact angle measurements, Fourier transform infrared (FT-IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). The contact angles for water on SAMs formed by the selective microwave heating and conventional room temperature incubation technique (24 h) were measured to be similar for 11-MUDA and UDET. FT-IR spectroscopy results confirmed that the internal structures of SAMs prepared using both microwave heating and room temperature were similar. XPS results revealed that the organic and sulfate contaminants found on bare gold thin films were replaced by SAMs after the surface modification process had been conducted using both microwave heating and room temperature.

  7. Building a Low-Cost, Six-Electrode Instrument to Measure Electrical Properties of Self-Assembled Monolayers of Gold Nanoparticles

    ERIC Educational Resources Information Center

    Gerber, Ralph W.; Oliver-Hoyo, Maria

    2007-01-01

    The development of a new low-cost, six-electrode instrument for measuring the electrical properties of the self-assembled monolayers of gold particles is being described. The system can also be used to measure conductive liquids, except for those that contain aqua region.

  8. IMPACT OF POLYCYCLIC AROMATIC HYDROCARBONS OF THE ELECTROCHEMICAL RESPONSES OF A FERRICYNIDE PROBE AT TEMPLATE-MODIFIED SELF ASSEMBLED MONOLAYERS ON GOLD ELECTRODES

    EPA Science Inventory

    The impact of pyrene on the electrochemical response of the ferricyanide probe using Self Assembled Monolayer (SAM)-modified gold electrodes was investigated using Cyclic Voltammetry (CV) and Square Wave Voltammetry (SWV). These results suggest the feasibility of using SAMs, par...

  9. Mixed monolayer protected gold atom-oxide cluster synthesis and characterization.

    PubMed

    Nambiar, Sindhu R; Aneesh, Padamadathil K; Sukumar, Chinthu; Rao, Talasila P

    2012-07-21

    Small atomic gold clusters in solution, Au(n), stabilized by cetyl trimethylammonium bromide (CTAB) and cysteine, have been synthesized potentiodynamically in quiescent aqueous solutions. The electrodissolution of gold to gold ions during an anodic scan and subsequent cluster formation during a cathodic scan in underpotential (UPDD) and overpotential dissolution-deposition (OPDD) regions were studied. The experimental potentiodynamic I-E profiles and chronoamperometric i-t transients are fit into reported theoretical models of adsorption and electrocrystallization. The plausible application of clusters/cluster film to cysteine sensing based on fluorescence quenching and square wave stripping voltammetry is demonstrated.

  10. Self-assembled monolayer films of C[sub 60]/on cysteamine-modified gold

    SciTech Connect

    Caldwell, W.B.; Chen, K.; Mirkin, C.A.; Babinec, S.J. Dow Chemical Company, Midland, MI )

    1993-08-01

    Self-assembled monolayer films (SAMs) of C[sub 60] on cysteamine-modified and cysteamine/ethanethiol-modified Au are reported. The monolayers were characterized via contact angle measurements, X-ray photoelectron spectroscopy, electrochemistry, and quartz crystal microbalance (QCM) measurements. C[sub 60] surface coverage (2.0 [times] 10[sup [minus]10] mol/cm[sup 2]) for a film formed on pure cysteamine was determined by QCM measurements and compares remarkably well with monolayer coverage (1.9 [times] 10[sup [minus]10] mol/cm[sup 2]) predicted by a model based on crystallographic data for C[sub 60]. These experiments demonstrate the utility of the QCM in characterizing and monitoring the growth of fullerene SAMs. C[sub 60] SAMs formed on pure cysteamine yield strikingly different electrochemical responses than those formed on prelayers consisting of varying ratios of ethanethiol and cysteamine and previously reported monolayers of C[sub 60] on (aminopropyl)silanized oxide surfaces. Although the C[sub 60] SAMs are stable under ambient conditions, the fullerenes may be desorbed from the surface through electrochemical reduction of the films for extended periods of time (> 10 min). 11 refs., 2 figs.

  11. Unraveling the dynamics and structure of functionalized self-assembled monolayers on gold using 2D IR spectroscopy and MD simulations

    PubMed Central

    Yan, Chang; Yuan, Rongfeng; Pfalzgraff, William C.; Nishida, Jun; Wang, Lu; Markland, Thomas E.; Fayer, Michael D.

    2016-01-01

    Functionalized self-assembled monolayers (SAMs) are the focus of ongoing investigations because they can be chemically tuned to control their structure and dynamics for a wide variety of applications, including electrochemistry, catalysis, and as models of biological interfaces. Here we combine reflection 2D infrared vibrational echo spectroscopy (R-2D IR) and molecular dynamics simulations to determine the relationship between the structures of functionalized alkanethiol SAMs on gold surfaces and their underlying molecular motions on timescales of tens to hundreds of picoseconds. We find that at higher head group density, the monolayers have more disorder in the alkyl chain packing and faster dynamics. The dynamics of alkanethiol SAMs on gold are much slower than the dynamics of alkylsiloxane SAMs on silica. Using the simulations, we assess how the different molecular motions of the alkyl chain monolayers give rise to the dynamics observed in the experiments. PMID:27044113

  12. Determination of low levels of cadmium ions by the under potential deposition on a self-assembled monolayer on gold electrode.

    PubMed

    Noyhouzer, Tomer; Mandler, Daniel

    2011-01-17

    The electrochemical determination of low levels of Cd using a self-assembled monolayer (SAM) modified Au electrode is reported. Determination was based on the stripping of Cd, which was deposited by under potential deposition (UPD). A series of short alkanethiol SAMs bearing different end groups, i.e., sulfonate, carboxylate and ammonium, were examined. Lowest level of detection (ca. 50 ngL(-1)) was achieved with a 3-mercaptopropionic acid (MPA) monolayer using subtractive anodic square wave voltammetry (SASV). Additional surface methods, namely, reductive desorption and X-ray photoelectron spectroscopy, were applied to determine the interfacial structure of the electrodeposited Cd on the modified electrodes. We conclude that the deposited Cd forms a monoatomic layer, which bridges between the gold surface and the alkanethiol monolayer associating with both the gold and the sulfur atoms.

  13. Optimized modification of gold nanoparticles with a self-assembled monolayer for suppression of nonspecific binding in DNA assays

    NASA Astrophysics Data System (ADS)

    Esashika, Keiko; Saiki, Toshiharu

    2016-10-01

    Homogeneous DNA assays using gold nanoparticles (AuNPs) require the reduction of nonspecific binding between AuNPs to improve sensitivity in detecting the target molecule. In this study, we employed alkanethiol self-assembled monolayers (SAMs) for modifying the AuNP surface to attain both good dispersability and high hybridization efficiency. The alkanethiol SAMs enhance the repulsive interaction between AuNPs, reducing nonspecific binding and promoting the extension of surface-immobilized ssDNA into the solvent, thus enhancing the hybridization process. Introduction of oligoethylene glycol into the alkanethiol prevented nonspecific binding caused by the entanglement of alkane chains. Finally, the conditions were optimized by controlling the surface charge density through the introduction of a COOH group at the alkanethiol terminus, resulting in the complete blocking of nonspecific binding and the maintenance of high hybridization efficiency.

  14. Dithienylcyclopentene-functionalised subphthalocyaninatoboron complexes: photochromism, fluorescence modulation and formation of self-assembled monolayers on gold

    PubMed Central

    Weidner, Tobias; Baio, Joe E.; Seibel, Johannes

    2012-01-01

    Subphthalocyaninatoboron (SubPc) complexes bearing six peripheral n-dodecylthio substituents and an apical photochromic dithienylperfluorocyclopentene unit were prepared. The photoinduced isomerisation of the apical substitutent from the open to the ring-closed form significantly influences the photoluminescence of the covalently attached SubPc unit, which is more efficiently quenched by the ring-closed form. Films on gold were fabricated from these multifunctional conjugates and characterised by near-edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS). The results are in accord with the formation of self-assembled monolayers based on dome-shaped SubPc-based anchor groups. Their chemisorption is primarily due to the peripheral n-dodecylthio substituents, giving rise to covalently attached thiolate as well as coordinatively bound thioether units, whose alkyl chains are in an almost parallel orientation to the surface. PMID:22138955

  15. Mixed monolayer protected gold atom-oxide cluster synthesis and characterization

    NASA Astrophysics Data System (ADS)

    Nambiar, Sindhu R.; Aneesh, Padamadathil K.; Sukumar, Chinthu; Rao, Talasila P.

    2012-06-01

    Small atomic gold clusters in solution, Aun, stabilized by cetyl trimethylammonium bromide (CTAB) and cysteine, have been synthesized potentiodynamically in quiescent aqueous solutions. The electrodissolution of gold to gold ions during an anodic scan and subsequent cluster formation during a cathodic scan in underpotential (UPDD) and overpotential dissolution-deposition (OPDD) regions were studied. The experimental potentiodynamic I-E profiles and chronoamperometric i-t transients are fit into reported theoretical models of adsorption and electrocrystallization. The plausible application of clusters/cluster film to cysteine sensing based on fluorescence quenching and square wave stripping voltammetry is demonstrated.Small atomic gold clusters in solution, Aun, stabilized by cetyl trimethylammonium bromide (CTAB) and cysteine, have been synthesized potentiodynamically in quiescent aqueous solutions. The electrodissolution of gold to gold ions during an anodic scan and subsequent cluster formation during a cathodic scan in underpotential (UPDD) and overpotential dissolution-deposition (OPDD) regions were studied. The experimental potentiodynamic I-E profiles and chronoamperometric i-t transients are fit into reported theoretical models of adsorption and electrocrystallization. The plausible application of clusters/cluster film to cysteine sensing based on fluorescence quenching and square wave stripping voltammetry is demonstrated. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr30446e

  16. The stability of self-organized 1-nonanethiol-capped gold nanoparticle monolayer

    NASA Astrophysics Data System (ADS)

    Jiang, Peng; Xie, Si-shen; Yao, Jian-nian; Pang, Shi-jin; Gao, Hong-jun

    2001-08-01

    1-Nonanethiol-protected gold nanoparticles with the size of about 2 nm have been prepared by a wet chemical method through choosing a suitable ratio of Au:S (2.5:1). Size selective precipitation of nanoparticles has been used to narrow their size distribution, which facilitates the formation of an ordered nanoparticle close-packed structure. A Fourier transform infrared investigation provides the evidence of the encapsulation of Au nanoparticles by 1-nonanethiol while an ultraviolet-visible spectrum shows a broad absorption around 520 nm, corresponding to surface plasmon band of Au nanoparticles. X-ray photoelectron spectroscopy of the samples demonstrates the metallic state of the gold (Au0) and the existence of sulfur (S). The data from x-ray powder diffraction measurements confirm that the gold nanoparticles have the same face-centred cubic crystalline structure as the bulk gold phase. Finally, transmission electron microscopy (TEM) characterization indicates that the size of the monodisperse colloidal gold nanoparticles is about 2 nm and they can self-organize to form a two-dimensional hexagonal close-packed structure after evaporating a concentrated drop of nanoparticles-toluene solution on a carbon-coated TEM copper grid.

  17. Sample Preconcentration Utilizing Nanofractures Generated by Junction Gap Breakdown Assisted by Self-Assembled Monolayer of Gold Nanoparticles

    PubMed Central

    Jen, Chun-Ping; Amstislavskaya, Tamara G.; Chen, Kuan-Fu; Chen, Yu-Hung

    2015-01-01

    The preconcentration of proteins with low concentrations can be used to increase the sensitivity and accuracy of detection. A nonlinear electrokinetic flow is induced in a nanofluidic channel due to the overlap of electrical double layers, resulting in the fast accumulation of proteins, referred to as the exclusion-enrichment effect. The proposed chip for protein preconcentration was fabricated using simple standard soft lithography with a polydimethylsiloxane replica. This study extends our previous paper, in which gold nanoparticles were manually deposited onto the surface of a protein preconcentrator. In the present work, nanofractures were formed by utilizing the self-assembly of gold-nanoparticle-assisted electric breakdown. This reliable method for nanofracture formation, involving self-assembled monolayers of nanoparticles at the junction gap between microchannels, also decreases the required electric breakdown voltage. The experimental results reveal that a high concentration factor of 1.5×104 for a protein sample with an extremely low concentration of 1 nM was achieved in 30 min by using the proposed chip, which is faster than our previously proposed chip at the same conditions. Moreover, an immunoassay of bovine serum albumin (BSA) and anti-BSA was carried out to demonstrate the applicability of the proposed chip. PMID:25970592

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

    DTIC Science & Technology

    2013-03-20

    n]uril-based rotaxane or pseudorotaxane devices connected to gold electrode surfaces and spherical gold nanoparticles have previously been developed...PAL (blue), PAL@CB[7] (black), and RGNRs (red) recorded from a thin film coated onto glassy carbon electrodes in an electrolyte solution of Bu4NPF6...0.10 m) in acetonitrile with an Ag/AgCl (0.10 m) reference electrode . Scan rate: 0.05 V/s. Conclusions GNRs protected by a hydrophilic CB[7]-based-pseudo

  19. Facile Attachment of TAT Peptide on Gold Monolayer Protected Clusters: Synthesis and Characterization

    PubMed Central

    Sosibo, Ndabenhle M.; Keter, Frankline K.; Skepu, Amanda; Tshikhudo, Robert T.; Revaprasadu, Neerish

    2015-01-01

    High affinity thiolate-based polymeric capping ligands are known to impart stability onto nanosized gold nanoparticles. Due to the stable gold-sulfur bond, the ligand forms a protective layer around the gold core and subsequently controls the physicochemical properties of the resultant nanogold mononuclear protected clusters (AuMPCs). The choice of ligands to use as surfactants for AuMPCs largely depends on the desired degree of hydrophilicity and biocompatibility of the MPCs, normally dictated by the intended application. Subsequent surface modification of AuMPCs allows further conjugation of additional biomolecules yielding bilayer or multilayered clusters suitable for bioanalytical applications ranging from targeted drug delivery to diagnostics. In this study, we discuss our recent laboratory findings on a simple route for the introduction of Trans-Activator of Transcription (TAT) peptide onto the surface of biotin-derivatised gold MPCs via the biotin-strepavidin interaction. By changing the surface loading of biotin, controlled amounts of TAT could be attached. This bioconjugate system is very attractive as a carrier in intercellular delivery of various delivery cargoes such as antibodies, proteins and oligonucleotides.

  20. Molecular Simulations of Gold Nanoparticles Coated With Self-Assembled Alkanethiolate Monolayers

    DTIC Science & Technology

    2006-11-01

    computed us- ing the Irving -Kirkwood pressure tensor [26]. The Irving - Kirkwood pressure tensor, equation 8, has contributions from two terms, namely the...surface tension. 6 S1 ri rj rA rB rij A B O Figure 8. Illustration of forces and posi- tion vectors used to calculate configurational term in Irving ...1000 K Surface Pressure Figure 9. Radial distribution of the normal component of the Irving -Kirkwood pressure tensor for bare 5nm gold nanoparticles at

  1. Determination of monolayer-protected gold nanoparticle ligand–shell morphology using NMR

    PubMed Central

    Liu, Xiang; Yu, Miao; Kim, Hyewon; Mameli, Marta; Stellacci, Francesco

    2012-01-01

    It is accepted that the ligand shell morphology of nanoparticles coated with a monolayer of molecules can be partly responsible for important properties such as cell membrane penetration and wetting. When binary mixtures of molecules coat a nanoparticle, they can arrange randomly or separate into domains, for example, forming Janus, patchy or striped particles. To date, there is no straightforward method for the determination of such structures. Here we show that a combination of one-dimensional and two-dimensional NMR can be used to determine the ligand shell structure of a series of particles covered with aliphatic and aromatic ligands of varying composition. This approach is a powerful way to determine the ligand shell structure of patchy particles; it has the limitation of needing a whole series of compositions and ligands' combinations with NMR peaks well separated and whose shifts due to the surrounding environment can be large enough. PMID:23149727

  2. Atom and Amine Adsorption on Flat and Stepped Gold Surfaces & Structure, Stability and Spin Ordering in Manganese Sulfide Clusters

    NASA Astrophysics Data System (ADS)

    Lewoczko, April D.

    In part I, we investigate gold catalysis in the chemistry of organonitrogen compounds. We examine the adsorption of oxygen, nitrogen and sulfur atoms on the gold (111), (100) and (211) surfaces using density functional theory (DFT). Sulfur atoms bind most strongly, followed by oxygen and nitrogen atoms with stronger adsorption for greater coordination to the surface. We see a trend of stronger adsorption to undercoordinated gold, but find it is non-universal with the adsorption strength trend: (111) > (211) > (100). We consider the diffusion of oxygen, nitrogen and sulfur adatoms and find facile long-range diffusion of oxygen atoms on the (100) surface. Lastly, we compare the adsorption of methylamine on gold to that of a selection of alkylamines, methanol and methanethiol. In each case, the ontop site is preferred with stronger adsorption at low coordinated gold. At oxygen atom coverages of 0.125 -- 0.25 ML on Au (111), we find cooperative adsorption of methylamine and oxygen atoms. Energetic costs for adsorbate tilt from the surface normal and rotation about the gold-nitrogen bond are calculated. While methylamine rotation is barrierless on the (111) and (211) surfaces, it has a low energetic barrier for the 0.125 ML and 0.25 ML O atom pre-covered Au (111) surfaces. In part II, we interpret the experimental mass spectrum of small gas phase manganese sulfide clusters using DFT and elucidate the role of ionicity and spin ordering in sizes with special stability, i.e. magic clusters. We first consider nine low lying minima (MnS)6 structures and reveal antiferromagnetic (AFM) spin ordering with a ˜0.1 eV/pair AFM energy benefit and a ˜0.1 A shrinkage of average Mn-Mn distances over clusters with ferromagnetic (FM) spin ordering. We calculate energetic barriers for interconversion between the two lowest lying (MnS)6 isomers and predict an elevated cluster melting temperature due to increased configurational entropy in a pre-melted state. Second, we demonstrate the

  3. Simulation and Modeling of Self-Assembled Monolayers of Carboxylic Acid Thiols on Flat and Nanoparticle Gold Surfaces

    SciTech Connect

    Techane, Sirnegeda D.; Baer, Donald R.; Castner, David G.

    2011-09-01

    Quantitative analysis of the 16-mercaptohexadecanoic acid self-assembled monolayer (C16 COOH-SAM) layer thickness on gold nanoparticles (AuNPs) was performed using simulation of electron spectra for surface analysis (SESSA) and x-ray photoelectron spectroscopy (XPS). XPS measurements of C16 COOH SAMs on flat gold surfaces were made at 9 different photoelectron take-off angles (5o to 85o in 5o increments), corrected using geometric weighting factors and then summed together to approximate spherical AuNPs. The SAM thickness and relative surface roughness (RSA) in SESSA were optimized to determine the best agreement between simulated and experimental surface composition. Based on the glancing angle results, it was found that inclusion of a hydrocarbon contamination layer on top the C16 COOH-SAM was necessary to improve the agreement between the SESSA and XPS results. For the 16 COOH-SAMs on flat Au surfaces, using a SAM thickness of 1.1Å/CH2 group, an RSA of 1.05 and a 1.5Å CH2-contamination overlayer (total film thickness = 21.5Å) for the SESSA calculations provided the best agreement with the experimental XPS data. After applying the appropriate geometric corrections and summing the SESSA flat surface compositions, the best fit results for the 16 COOH-SAM thickness and surface roughness on the AuNPs were determined to be 0.9Å/CH2 group and 1.06 RSA with a 1.5Å CH2-contamination overlayer (total film thickness = 18.5Å). The three angstrom difference in SAM thickness between the flat Au and AuNP surfaces suggests the alkyl chains of the SAM are slightly more tilted or disordered on the AuNP surfaces.

  4. Simulation and modeling of self-assembled monolayers of carboxylic acid thiols on flat and nanoparticle gold surfaces.

    PubMed

    Techane, Sirnegeda; Baer, Donald R; Castner, David G

    2011-09-01

    Quantitative analysis of the 16-mercaptohexadecanoic acid self-assembled monolayer (C16 COOH-SAM) layer thickness on gold nanoparticles (AuNPs) was performed using simulation of electron spectra for surface analysis (SESSA) software and X-ray photoelectron spectroscopy (XPS) experimental measurements. XPS measurements of C16 COOH-SAMs on flat gold surfaces were made at nine different photoelectron emission angles (5-85° in 10° increments), corrected using geometric weighting factors and then summed together to approximate spherical AuNPs. The SAM thickness and relative surface roughness (RSA) in SESSA were optimized to determine the best agreement between simulated and experimental surface composition. On the basis of the glancing-angle results, it was found that inclusion of a hydrocarbon-contamination layer on top the C16 COOH-SAM was necessary to improve the agreement between the SESSA and XPS results. For the 16 COOH-SAMs on flat Au surfaces, using a SAM thickness of 1.1 Å/CH(2) group, an RSA of 1.05, and a 1.5 Å CH(2)-contamination overlayer (total film thickness = 21.5 Å) for the SESSA calculations provided the best agreement with the experimental XPS data. After applying the appropriate geometric corrections and summing the SESSA flat-surface compositions, the best fit results for the 16 COOH-SAM thickness and surface roughness on the AuNPs indicated a slightly thinner overlayer with parameters of 0.9 Å/CH(2) group in the SAM, an RSA of 1.06 RSA, and a 1.5 Å CH(2)-contamination overlayer (total film thickness = 18.5 Å). The 3 Å difference in SAM thickness between the flat Au and AuNP surfaces suggests that the alkyl chains of the SAM are slightly more tilted or disordered on the AuNP surfaces.

  5. The electric dipole moments in the ground states of gold oxide, AuO, and gold sulfide, AuS

    NASA Astrophysics Data System (ADS)

    Zhang, Ruohan; Yu, Yuanqin; Steimle, Timothy C.; Cheng, Lan

    2017-02-01

    The B2Σ- - X2Π3/2(0,0) bands of a cold molecular beam sample of gold monoxide, AuO, and gold monosulfide, AuS, have been recorded at high resolution both field free and in the presence of a static electric field. The observed electric field induced splittings and shifts were analyzed to produce permanent electric dipole moments, μ→ e l, of 2.94±0.06 D and 2.22±0.05 D for the X2Π3/2(v = 0) states of AuO and AuS, respectively. A molecular orbital correlation diagram is used to rationalize the trend in ground state μ→ e l values for AuX (X = F, Cl, O, and S) molecules. The experimentally determined μ→ e l are compared to those computed at the coupled-cluster singles and doubles (CCSD) level augmented with a perturbative inclusion of triple excitations (CCSD(T)) level of theory.

  6. Ordered Monolayer Gold Nano-urchin Structures and Their Size Induced Control for High Gas Sensing Performance

    PubMed Central

    Sabri, Ylias M.; Kandjani, Ahmad Esmaielzadeh; Ippolito, Samuel J.; Bhargava, Suresh K.

    2016-01-01

    The synthesis of ordered monolayers of gold nano-urchin (Au-NU) nanostructures with controlled size, directly on thin films using a simple electrochemical method is reported in this study. In order to demonstrate one of the vast potential applications, the developed Au-NUs were formed on the electrodes of transducers (QCM) to selectively detect low concentrations of elemental mercury (Hg0) vapor. It was found that the sensitivity and selectivity of the sensor device is enhanced by increasing the size of the nanospikes on the Au-NUs. The Au-NU-12 min QCM (Au-NUs with nanospikes grown on it for a period of 12 min) had the best performance in terms of transducer based Hg0 vapor detection. The sensor had 98% accuracy, 92% recovery, 96% precision (repeatability) and significantly, showed the highest sensitivity reported to date, resulting in a limit of detection (LoD) of only 32 μg/m3 at 75 °C. When compared to the control counterpart, the accuracy and sensitivity of the Au-NU-12 min was enhanced by ~2 and ~5 times, respectively. The results demonstrate the excellent activity of the developed materials which can be applied to a range of applications due to their long range order, tunable size and ability to form directly on thin-films. PMID:27090570

  7. Square Wave Voltammetry of TNT at Gold Electrodes Modified with Self-Assembled Monolayers Containing Aromatic Structures

    PubMed Central

    Trammell, Scott A.; Zabetakis, Dan; Moore, Martin; Verbarg, Jasenka; Stenger, David A.

    2014-01-01

    Square wave voltammetry for the reduction of 2,4,6-trinitrotoluene (TNT) was measured in 100 mM potassium phosphate buffer (pH 8) at gold electrodes modified with self-assembled monolayers (SAMs) containing either an alkane thiol or aromatic ring thiol structures. At 15 Hz, the electrochemical sensitivity (µA/ppm) was similar for all SAMs tested. However, at 60 Hz, the SAMs containing aromatic structures had a greater sensitivity than the alkane thiol SAM. In fact, the alkane thiol SAM had a decrease in sensitivity at the higher frequency. When comparing the electrochemical response between simulations and experimental data, a general trend was observed in which most of the SAMs had similar heterogeneous rate constants within experimental error for the reduction of TNT. This most likely describes a rate limiting step for the reduction of TNT. However, in the case of the alkane SAM at higher frequency, the decrease in sensitivity suggests that the rate limiting step in this case may be electron tunneling through the SAM. Our results show that SAMs containing aromatic rings increased the sensitivity for the reduction of TNT when higher frequencies were employed and at the same time suppressed the electrochemical reduction of dissolved oxygen. PMID:25549081

  8. Ordered Monolayer Gold Nano-urchin Structures and Their Size Induced Control for High Gas Sensing Performance

    NASA Astrophysics Data System (ADS)

    Sabri, Ylias M.; Kandjani, Ahmad Esmaielzadeh; Ippolito, Samuel J.; Bhargava, Suresh K.

    2016-04-01

    The synthesis of ordered monolayers of gold nano-urchin (Au-NU) nanostructures with controlled size, directly on thin films using a simple electrochemical method is reported in this study. In order to demonstrate one of the vast potential applications, the developed Au-NUs were formed on the electrodes of transducers (QCM) to selectively detect low concentrations of elemental mercury (Hg0) vapor. It was found that the sensitivity and selectivity of the sensor device is enhanced by increasing the size of the nanospikes on the Au-NUs. The Au-NU-12 min QCM (Au-NUs with nanospikes grown on it for a period of 12 min) had the best performance in terms of transducer based Hg0 vapor detection. The sensor had 98% accuracy, 92% recovery, 96% precision (repeatability) and significantly, showed the highest sensitivity reported to date, resulting in a limit of detection (LoD) of only 32 μg/m3 at 75 °C. When compared to the control counterpart, the accuracy and sensitivity of the Au-NU-12 min was enhanced by ~2 and ~5 times, respectively. The results demonstrate the excellent activity of the developed materials which can be applied to a range of applications due to their long range order, tunable size and ability to form directly on thin-films.

  9. Thermo-kinetics study of laser-induced desorption of self-assembled monolayers from gold: case of laser micropatterning.

    PubMed

    Shadnam, Mohammad R; Kirkwood, Sean E; Fedosejevs, Robert; Amirfazli, A

    2005-06-23

    Laser-induced desorption of self-assembled monolayers (SAMs) from gold surfaces within context of the direct laser patterning methodology was investigated through combining results of a heat diffusion thermal model with desorption kinetics of alkanethiol SAMs. It was found that contrast plots of experimental scanning electron microscopy (SEM) images, which are correlated to surface coverage of SAMs desorbed after laser irradiation, agreed with the theoretically predicted surface composition of SAMs. The surface composition of SAM was then interpreted in terms of the wetting property of the resulting surface. The effect of incident laser beam power and size on the final spatial coverage of SAMs on the surface and feature sizes was investigated both experimentally and by modeling. Theoretical modeling and experimental evidence showed that the resulting feature sizes are wider when the surface is heated by a laser of higher power. Increasing the laser beam size results in broadening of feature sizes. Considering the correlation of the theoretical and experimental results, we concluded that the feature sizes are controllable in a predictable way (using the presented thermal-kinetics model) through varying laser beam power and beam size.

  10. Sub-monolayer silver loss from large gold nanospheres detected by surface plasmon resonance in the sigmoidal region.

    PubMed

    Lien, Jennifer; Peck, Kristin A; Su, Mengqi; Guo, Ting

    2016-10-01

    Nanosilver becomes labile upon entering the human body or the environment. This lability creates silver species with antimicrobial properties that make nanosilver attractive as active components in many consumer products, wound dressings, and agricultural applications. Because lability depends strongly on morphology, it is imperative to use a material with constant lability throughout kinetic studies so that accurate lability data can be acquired with efficient detection. Here 2.5nm thick silver was coated onto 90-nm diameter gold nanosphere cores and this surface silver layer was gradually removed by either chemical or X-ray radiation etching. The most sensitive region of a sigmoidal surface plasmon resonance (SPR) response as a function of silver thickness was found for the first time between 0.9- and 1.6-nm thick silver, revealing a new nanosilver standard for lability studies. The SPR peak position detection sensitivity is 8nm (SPR peak shift)/nm (silver thickness change) within this steepest region of the plasmon response curve whereas outside, sensitivity drops to 1nm/nm. Since the centroid of SPR profiles can be discerned with 0.25nm precision, the 8-nm/nm sensitivity means it is possible to detect a 0.3-angstrom or sub-monolayer change in silver thickness. The SPR response simulated by discrete dipole approximation (DDA) was an identical sigmoidal function between 0 and 2nm of silver coating. These findings were supported by several other analytical measurements, which confirmed no silver recoating during these etching processes.

  11. Sensitive detection of clozapine using a gold electrode modified with 16-mercaptohexadecanoic acid self-assembled monolayer.

    PubMed

    Huang, Fei; Qu, Song; Zhang, Song; Liu, Baohong; Kong, Jilie

    2007-04-30

    Clozapine, an effective antipsychotic drug, was found generating a pair of redox peaks at about 0.33-0.4V (versus SCE) at 16-mercaptohexadecanoic acid (i.e. MHA) self-assembled monolayer (SAM) modified gold electrode (i.e. MHA/Au) in 0.05molL(-1) Tris-HCl (pH 8.1) buffer solution. Sensitive and quantitative measurement of clozapine based on anodic peak was established under optimum conditions. The anodic peak current was linear to clozapine concentration in the range from 1x10(-6) to 5x10(-5)molL(-1) with the detection limit of 7x10(-9)molL(-1). This method was successfully applied to the detection of clozapine in drug tablets and proved to be reliable compared with ultraviolet spectrophotometry (UV). The MHA SAM was characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), contact angle goniometry, electrochemical impedance spectroscopy (EIS) and electrochemical probe.

  12. Inflammatory responses and cell adhesion to self-assembled monolayers of alkanethiolates on gold.

    PubMed

    Barbosa, Judite N; Barbosa, Mário A; Aguas, Artur P

    2004-06-01

    The acute inflammatory response and the adhesion of cells to self-assembled monolayers (SAMs) of well-defined surface chemistry was studied in vivo using a rodent air-pouch model of inflammation. SAMs with three different terminal functional groups (OH, COOH and CH3) were implanted in subcutaneous air pouches induced in BALB/c mice. After 24 h, inflammatory cells were recovered from the air pouches and the implants were removed and prepared for observation by scanning electron microscopy (SEM). The implants coated with OH and CH3, were found to cause the highest recruitment of inflammatory cells into the subcutaneous pouches. Polymorphonuclear neutrophils (PMNs) leukocytes predominated over mononuclear cells in inflammatory exudates of SAMs-coated implants, the opposite being found in uncoated implants (controls). CH3-coated implants induced the highest number of inflammatory cells and also the largest percentage of PMNs seen in the subcutaneous pouches. Control and OH-covered implants presented the higher densities of attached inflammatory cells detected by SEM. In contrast, the CH3-coated implants showed a very low density of cells adherent to the implant surface. We conclude that the chemical nature and the degree of hydrophobicity of the surface of implants modulate both the local acute inflammatory reaction and the adhesion of leukocytes.

  13. Surface-enhanced Raman scattering-active gold nanoparticles modified with a monolayer of silver film.

    PubMed

    Chang, Chun-Chao; Yang, Kuang-Hsuan; Liu, Yu-Chuan; Yu, Chung-Chin; Wu, Yi-Hao

    2012-11-07

    As shown in the literature, electrochemical underpotential deposition (UPD) offers the ability to deposit up to a monolayer of one metal onto a more noble metal with a flat surface. In this work, we develop an electrochemical pathway to prepare more surface-enhanced Raman scattering (SERS)-active substrates with Ag UPD-modified Au nanoparticles (NPs) by using sonoelectrochemical deposition-dissolution cycles (SEDDCs). Encouragingly, the SERS of Rhodamine 6G (R6G) adsorbed on these Ag UPD-modified Au NPs exhibits a higher intensity by ca. 12-fold magnitude, as compared with that of R6G adsorbed on unmodified Au NPs. The prepared SERS-active substrate demonstrates a large Raman scattering enhancement for R6G with a detection limit of 2 × 10(-14) M and an enhancement factor of 5.0 × 10(8). Also, the strategy proposed in this work to improve the SERS effects by using UPD Ag based on SEDDCs has an effect on the smaller probe molecules of 2,2'-bipyridine (BPy).

  14. Electron Transfer Mechanism in Gold Surface Modified with Self-Assembly Monolayers from First Principles

    NASA Astrophysics Data System (ADS)

    Lima, Filipe C. D. A.; Iost, Rodrigo M.; Crespilho, Frank N.; Caldas, Marília J.; Calzolari, Arrigo; Petrilli, Helena M.

    2013-03-01

    We report the investigation of electron tunneling mechanism of peptide ferrocenyl-glycylcystamine self-assembled monolayers (SAMs) onto Au (111) electrode surfaces. Recent experimental investigations showed that electron transfer in peptides can occur across long distances by separating the donor from the acceptor. This mechanism can be further fostered by the presence of electron donor terminations of Fc terminal units on SAMs but the charge transfer mechanism is still not clear. We study the interaction of the peptide ferrocenyl-glycylcystamine on the Au (111) from first principles calculations to evaluate the electron transfer mechanism. For this purpose, we used the Kohn Sham (KS) scheme for the Density Functional Theory (DFT) as implemented in the Quantum-ESPRESSO suit of codes, using Vandebilt ultrasoft pseudopotentials and GGA-PBE exchange correlation functional to evaluate the ground-state atomic and electronic structure of the system. The analysis of KS orbital at the Fermi Energy showed high electronic density localized in Fc molecules and the observation of a minor contribution from the solvent and counter ion. Based on the results, we infer evidences of electron tunneling mechanism from the molecule to the Au(111). We acknowledge FAPESP for grant support. Also, LCCA/USP, RICE and CENAPAD for computational resources.

  15. Self-assembled monolayers of ferrocene-substituted biphenyl ethynyl thiols on gold.

    PubMed

    Shaporenko, Andrey; Rössler, Katrin; Lang, Heinrich; Zharnikov, Michael

    2006-12-07

    Homogeneous and mixed [with biphenylthiol (BPT)] self-assembled monolayers (SAMs) of ferrocene-substituted biphenyl ethynyl thiols (Fc) were prepared on Au(111) substrates and characterized by several complementary spectroscopic techniques. The mixed films were fabricated either by subsequent immersion of the substrates into the BPT and Fc solutions or by immersion of the substrate into a mixed solution of BPT and Fc. The first procedure resulted in the preparation of high-quality mixed SAMs, in which the Fc molecules were stochastically distributed in the BPT matrix and well-separated from each other. The portion of these molecules in such films could be precisely varied from ca. 7 to 42% by selection of the immersion time in the BPT solution. The films prepared from the mixed solution exhibited a phase separation between the Fc and BPT constituents. These films contained mostly the Fc molecules ( approximately 80-90%), showing, thus, a significant deviation from the relative content of the target molecules in the primary solution (a 1:1 ratio). This finding shows that the Fc molecules, when competing with BPT, preferably adsorb onto Au(111) substrate, suggesting a significant impact of the ferrocene groups onto the structure-building interactions responsible for molecular self-assembly.

  16. Optical Properties of Self-Ensemble Monolayers of Gold Metallic Nanostructures

    NASA Astrophysics Data System (ADS)

    Macuil, R. Delgado; Gayou, V. López; López, M. Rojas; Contreras, R. Molina; Servin, J. L. Garcí; Ramírez, J. F. Sánchez

    2008-04-01

    This work analyzes the optical properties of nanostructures metallic surfaces of gold, at different sizes, in glass silanized substrates. Silanized substrates were immersed in the colloid solution for one and half hour at room temperature and dried at room temperature for four hours. The optical properties were analyzed by three spectroscopy techniques and by TEM microscopy. UV/VIS was used to observe changes in absorption due to the aminopropiltrimethoxysilane added to the glass substrate and due to the colloid added to silanized substrate. Infrared vibrational spectroscopy in ATR mode was used to observe the new generation peaks due to substrate silanization and SEIRA effect due to the colloid added to silanized substrate. And finally Z-Scan technique was used to observe the nonlinear properties of these funtionalization metallic nanostructures in function of nanostructures size. TEM images confirm the sizes observed in the UV/VIS spectra.

  17. Stabilization of gold nanoparticles by 6-mercaptopurine monolayers. Effects of the solvent properties.

    PubMed

    Viudez, Alfonso J; Madueño, Rafael; Pineda, Teresa; Blázquez, Manuel

    2006-09-14

    6-Mercaptopurine-coated gold nanoparticles (6MP-AuNPs) have been prepared by modification of the nanoparticle surface with 6MP upon displacement of the protective layer of citrate anions. The modification has been studied by UV-vis and FTIR spectroscopies. A study of the stability of these 6MP-AuNPs in aqueous solutions as a function of ionic strength and pH has shown the importance of the charges on the stabilization. The protonation of N9 of the 6MP molecules brings about a sudden flocculation phenomenon. However, the flocculation is reversible upon changing the pH to values where the molecules become newly charged. Evidence of the competence between the interaction of capping solvent molecules and the attractive forces between particles is also shown in this paper.

  18. Thermodynamic profiles at the solvated inorganic-organic interface: the case of gold-thiolate monolayers.

    PubMed

    Ravi, Venkataramanan; Binz, Jason M; Rioux, Robert M

    2013-09-11

    The thermodynamic adsorption profile at a solvated organic-inorganic interface is probed by following the binding and organization of carboxylic acid-terminated alkanethiols of varying chain lengths (C2, C3, and C6) to the surface of gold nanoparticles (NPs) (5.4 ± 0.7, 9.5 ± 0.6, and 19.4 ± 1.1 nm diameter) using isothermal titration calorimetry (ITC). We discuss the effect of alkyl chain length, temperature, and Au NP size on the energetics at an organic-inorganic interface. ITC allows for the quantification of the adsorption constant, enthalpy of adsorption, entropy of adsorption, and the binding stoichiometry in a single experiment. The thermodynamic parameters support a mechanism of stepwise adsorption of thiols to the surface of Au NPs and secondary ordering of the thiols at the organic-inorganic interface. The adsorption enthalpies are chain-length dependent; enthalpy becomes more exothermic as longer chains are confined, compensating for greater decreases in entropy with increasing chain length. We observe an apparent compensation effect: the negative ΔH is compensated by a negative ΔS as the thiols self-assemble on the Au NP surface. A comparison of the thermodynamic parameters indicates thiol-Au NP association is enthalpy-driven because of the large, exothermic enthalpies accompanied by an unfavorable entropic contribution associated with confinement of alkyl chains, reduced trans-gauche interconversion, and the apparent ordering of solvent molecules around the hydrophobic organic thiols (hydrophobic effect). Understanding the thermodynamics of adsorption at NP surfaces will provide critical insight into the role of ligands in directing size and shape during NP synthesis since thiols are a common ligand choice (i.e., Brust method). The ITC technique is applicable to a larger number of structure-directing ligands and solvent combinations and therefore should become an important tool for understanding reaction mechanisms in nanostructure synthesis.

  19. Magmatic-vapor expansion and the formation of high-sulfidation gold deposits: Structural controls on hydrothermal alteration and ore mineralization

    USGS Publications Warehouse

    Berger, B.R.; Henley, R.W.

    2011-01-01

    High-sulfidation copper-gold lode deposits such as Chinkuashih, Taiwan, Lepanto, Philippines, and Goldfield, Nevada, formed within 1500. m of the paleosurface in volcanic terranes. All underwent an early stage of extensive advanced argillic silica-alunite alteration followed by an abrupt change to spatially much more restricted stages of fracture-controlled sulfide-sulfosalt mineral assemblages and gold-silver mineralization. The alteration as well as ore mineralization stages of these deposits were controlled by the dynamics and history of syn-hydrothermal faulting. At the Sulfate Stage, aggressive advanced argillic alteration and silicification were consequent on the in situ formation of acidic condensate from magmatic vapor as it expanded through secondary fracture networks alongside active faults. The reduction of permeability at this stage due to alteration decreased fluid flow to the surface, and progressively developed a barrier between magmatic-vapor expansion constrained by the active faults and peripheral hydrothermal activity dominated by hot-water flow. In conjunction with the increased rock strength resulting from alteration, subsequent fault-slip inversion in response to an increase in compressional stress generated new, highly permeable fractures localized by the embrittled, altered rock. The new fractures focused magmatic-vapor expansion with much lower heat loss so that condensation occurred. Sulfide Stage sulfosalt, sulfide, and gold-silver deposition then resulted from destabilization of vapor phase metal species due to vapor decompression through the new fracture array. The switch from sulfate to sulfide assemblages is, therefore, a logical consequence of changes in structural permeability due to the coupling of alteration and fracture dynamics rather than to changes in the chemistry of the fluid phase at its magmatic source. ?? 2010.

  20. Thiol-ene immobilisation of carbohydrates onto glass slides as a simple alternative to gold-thiol monolayers, amines or lipid binding.

    PubMed

    Biggs, Caroline I; Edmondson, Steve; Gibson, Matthew I

    2015-01-01

    Carbohydrate arrays are a vital tool in studying infection, probing the mechanisms of bacterial, viral and toxin adhesion and the development of new treatments, by mimicking the structure of the glycocalyx. Current methods rely on the formation of monolayers of carbohydrates that have been chemically modified with a linker to enable interaction with a functionalised surface. This includes amines, biotin, lipids or thiols. Thiol-addition to gold to form self-assembled monolayers is perhaps the simplest method for immobilisation as thiolated glycans are readily accessible from reducing carbohydrates in a single step, but are limited to gold surfaces. Here we have developed a quick and versatile methodology which enables the use of thiolated carbohydrates to be immobilised as monolayers directly onto acrylate-functional glass slides via a 'thiol-ene'/Michael-type reaction. By combining the ease of thiol chemistry with glass slides, which are compatible with microarray scanners this offers a cost effective, but also useful method to assemble arrays.

  1. Immobilization of Monolayers Incorporating Cu Funnel Complexes onto Gold Electrodes. Application to the Selective Electrochemical Recognition of Primary Alkylamines in Water.

    PubMed

    De Leener, Gaël; Evoung-Evoung, Ferdinand; Lascaux, Angélique; Mertens, Jeremy; Porras-Gutierrez, Ana Gabriela; Le Poul, Nicolas; Lagrost, Corinne; Over, Diana; Leroux, Yann R; Reniers, François; Hapiot, Philippe; Le Mest, Yves; Jabin, Ivan; Reinaud, Olivia

    2016-10-05

    The immobilization of a copper calix[6]azacryptand funnel complex on gold-modified electrodes is reported. Two different methodologies are described. One is based on alkyne-terminated thiol self-assembled monolayers. The other relies on the electrografting of a calix[4]arene platform bearing diazonium functionalities at its large rim and carboxylic functions at its small rim, which is post-functionalized with alkyne moieties. In both cases, the CuAAC electroclick methodology proved to be the method of choice for grafting the calix[6]azacryptand onto the monolayers. The surface-immobilized complex was fully characterized by surface spectroscopies and electrochemistry in organic and aqueous solvents. The Cu complex displays a well-defined quasi-reversible system in cyclic voltammetry associated with the Cu(II)/Cu(I) redox process. Remarkably, this redox process triggers a powerful selective detection of primary alkylamines in water at a micromolar level, based on a cavitary recognition process.

  2. Selective surface activation of a functional monolayer for the fabrication of nanometer scale thiol patterns and directed self-assembly of gold nanoparticles.

    PubMed

    Fresco, Zachary M; Fréchet, Jean M J

    2005-06-15

    Application of a voltage bias between the tip of an atomic force microscope (AFM) and a silicon substrate causes the localized modification of a specially designed self-assembled monolayer (SAM), transforming a surface-bound thiocarbonate into a surface-bound thiol. The resulting surface-bound thiols are used to direct the patternwise self-assembly of gold nanoparticles (AuNPs). This methodology is applied to deposit individual AuNPs onto a surface with nanometer precision and to produce 10 nm lines of closely spaced AuNPs that are a single nanoparticle in width.

  3. A comparative study of hollow copper sulfide nanoparticles and hollow gold nanospheres on degradability and toxicity.

    PubMed

    Guo, Liangran; Panderi, Irene; Yan, Daisy D; Szulak, Kevin; Li, Yajuan; Chen, Yi-Tzai; Ma, Hang; Niesen, Daniel B; Seeram, Navindra; Ahmed, Aftab; Yan, Bingfang; Pantazatos, Dionysios; Lu, Wei

    2013-10-22

    Gold and copper nanoparticles have been widely investigated for photothermal therapy of cancer. However, degradability and toxicity of these nanoparticles remain concerns. Here, we compare hollow CuS nanoparticles (HCuSNPs) with hollow gold nanospheres (HAuNS) in similar particle sizes and morphology following intravenous administration to mice. The injected pegylated HCuSNPs (PEG-HCuSNPs) are eliminated through both hepatobiliary (67 percentage of injected dose, %ID) and renal (23 %ID) excretion within one month postinjection. By contrast, 3.98 %ID of Au is excreted from liver and kidney within one month after iv injection of pegylated HAuNS (PEG-HAuNS). Comparatively, PEG-HAuNS are almost nonmetabolizable, while PEG-HCuSNPs are considered biodegradable nanoparticles. PEG-HCuSNPs do not show significant toxicity by histological or blood chemistry analysis. Principal component analysis and 2-D peak distribution plots of data from matrix-assisted laser desorption ionization-time-of-flight imaging mass spectrometry (MALDI-TOF IMS) of liver tissues demonstrated a reversible change in the proteomic profile in mice receiving PEG-HCuSNPs. This is attributed to slow dissociation of Cu ion from CuS nanoparticles along with effective Cu elimination for maintaining homeostasis. Nonetheless, an irreversible change in the proteomic profile is observed in the liver from mice receiving PEG-HAuNS by analysis of MALDI-TOF IMS data, probably due to the nonmetabolizability of Au. This finding correlates with the elevated serum lactate dehydrogenase at 3 months after PEG-HAuNS injection, indicating potential long-term toxicity. The comparative results between the two types of nanoparticles will advance the development of HCuSNPs as a new class of biodegradable inorganic nanomaterials for photothermal therapy.

  4. Platinum-group element, Gold, Silver and Base Metal distribution in compositionally zoned sulfide droplets from the Medvezky Creek Mine, Noril'sk, Russia

    USGS Publications Warehouse

    Barnes, S.-J.; Cox, R.A.; Zientek, M.L.

    2006-01-01

    Concentrations of Ag, Au, Cd, Co, Re, Zn and Platinum-group elements (PGE) have been determined in sulfide minerals from zoned sulfide droplets of the Noril'sk 1 Medvezky Creek Mine. The aims of the study were; to establish whether these elements are located in the major sulfide minerals (pentlandite, pyrrhotite, chalcopyrite and cubanite), to establish whether the elements show a preference for a particular sulfide mineral and to investigate the model, which suggests that the zonation in the droplets is caused by the crystal fractionation of monosulfide solid solution (mss). Nickel, Cu, Ag, Re, Os, Ir, Ru, Rh and Pd, were found to be largely located in the major sulfide minerals. In contrast, less than 25% of the Au, Cd, Pt and Zn in the rock was found to be present in these sulfides. Osmium, Ir, Ru, Rh and Re were found to be concentrated in pyrrhotite and pentlandite. Palladium and Co was found to be concentrated in pentlandite. Silver, Cd and Zn concentrations are highest in chalcopyrite and cubanite. Gold and platinum showed no preference for any of the major sulfide minerals. The enrichment of Os, Ir, Ru, Rh and Re in pyrrhotite and pentlandite (exsolution products of mss) and the low levels of these elements in the cubanite and chalcopyrite (exsolution products of intermediate solid solution, iss) support the mss crystal fractionation model, because Os, Ir, Ru, Rh and Re are compatible with mss. The enrichment of Ag, Cd and Zn in chalcopyrite and cubanite also supports the mss fractionation model these minerals are derived from the fractionated liquid and these elements are incompatible with mss and thus should be enriched in the fractionated liquid. Gold and Pt do not partition into either iss or mss and become sufficiently enriched in the final fractionated liquid to crystallize among the iss and mss grains as tellurides, bismithides and alloys. During pentlandite exsolution Pd appears to have diffused from the Cu-rich portion of the droplet into

  5. Geologic setting and genesis of the Mule Canyon low-sulfidation epithermal gold-silver deposit, north-central Nevada

    USGS Publications Warehouse

    John, D.A.; Hofstra, A.H.; Fleck, R.J.; Brummer, J.E.; Saderholm, E.C.

    2003-01-01

    /or marcasite veins. Ore minerals consist mostly of electrum and Ag sulfide and selenide minerals, with minor to major amounts of pyrite, marcasite, and arsenopyrite, and local stibnite. Both types of ores have similar geochemical signatures, characterized by high Au, Ag, As, Sb, and Se contents, locally high Hg, Mo, Tl, and W contents, and low Cu, Pb, and Zn contents. Stable isotope data indicate that ore fluids consisted dominantly of meteoric water that evolved by deep circulation through Paleozoic sedimentary rocks at low water/rock ratios (about 1) and high temperatures (>200??C). Calculated isotopic compositions of ore fluids are ??18OH2O = -3 to -7 per mil, ??DH2O = -107 to -124 per mil, ??13CCO2 = 0 to -6 per mil, and ??34SH2S = -3 to +8 per mil. The ore fluids obtained much of their H2S and CO2 and probably scavenged ore metals and trace elements from the Paleozoic sedimentary rocks. Some H2S and CO2 may have been derived from degassing Miocene magmas. Mule Canyon formed at shallow depths, probably about 100 m below the paleosurface. Ore fluids were dilute, nearly neutral in pH, reduced, H2S-rich, and CO2-bearing. Peak temperatures in ore zones reached 230?? to 265??C at nearly lithostatic pressures when some crystalline quartz ?? adularia precipitated, but most ore formed at temperatures <200??C at near hydrostatic pressures and was accompanied by precipitation of opaline and chalcedonic silica ?? adularia ?? calcite and dolomite. Deposition of gold in As-rich overgrowths on pyrite and/or marcasite in disseminated ores occurred owing to decreasing H2S in the ore fluids resulting from sulfidation reactions. Later electrum and Ag selenide precipitation in open spaces occurred owing to boiling, loss of H2S to the vapor phase, and cooling. Mule Canyon is similar to most other low-sulfidation Au-Ag deposits associated with Miocene tholeiitic bimodal basalt-rhyolite magmatism in the Great Basin, such as Sleeper, Midas, and Buckhorn. Major differences at Mule Canyon are

  6. Gold in the Brunswick No. 12 volcanogenic massive sulfide deposit, Bathurst Mining Camp, Canada: Evidence from bulk ore analysis and laser ablation ICP-MS data on sulfide phases

    NASA Astrophysics Data System (ADS)

    McClenaghan, Sean H.; Lentz, David R.; Martin, Jillian; Diegor, Wilfredo G.

    2009-07-01

    pyrite ( n = 97) from the north end of the Main Zone average 2.6 ppm Au and range from the detection limit (0.015 ppm) to 21 ppm. Overall, these analyses reveal a distinct Au-Sb-As-Ag-Hg-Mn association within pyrite grains. Gold is strongly enriched in large pseudo-primary masses of pyrite that exhibit relict banding and fine-grained cores; smaller euhedral pyrite porphyroblasts, and euhedral rims of metamorphic origin surrounding the pyrite masses, contain much less Au, Sb, Ag, As, and Sn. Arsenopyrite, occurring chiefly as late porphyroblasts, contains less Au, averaging 1.0 ppm and ranging from the detection limit (0.027 ppm) to 6.9 ppm. Depth profiles for single-spot laser ablation ICP-MS analyses of pyrite and arsenopyrite display uniform values of Au and an absence of discrete microscopic inclusions of Au-bearing minerals, which is consistent with chemically bonded Au in the sulfide structure. The pervasive correlation of Au with Sn in the Zn-Pb-rich banded sulfide facies suggests similar hydrothermal behavior during the waxing stages of deposition on the seafloor. Under high temperature (>350ºC) and moderate- to low-pH conditions, Au and Sn in hydrothermal fluids would be transported as chlorocomplexes. An abrupt decrease in temperature and aH2S, accompanied by an increase in fO2 and pH during mixing with seawater, would lead to the simultaneous destabilization of both Au and Sn chlorocomplexes. The enrichment of Au in fine-grained laminated sulfides on the periphery of the deposit, accompanied by sporadic occurrences of barite and Fe-poor sphalerite, supports lower hydrothermal fluid temperatures analogous to white smoker activity on the flanks of a large volcanogenic massive sulfide system. In lower temperature (<350ºC) and mildly acidic hydrothermal fluids, Au would be transported by thiocomplexes, which exhibit multifunctional (retrograde-prograde) solubility and a capacity to mobilize Au to the outer parts of the sulfide mound. The sluggish nature of this

  7. Gold

    USGS Publications Warehouse

    Kirkemo, Harold; Newman, William L.; Ashley, Roger P.

    1998-01-01

    Through the ages, men and women have cherished gold, and many have had a compelling desire to amass great quantities of it -- so compelling a desire, in fact, that the frantic need to seek and hoard gold has been aptly named "gold fever." Gold was among the first metals to be mined because it commonly occurs in its native form -- that is, not combined with other elements -- because it is beautiful and imperishable, and because exquisite objects can be made from it.

  8. Formation of Monolayers by the Coadsorption of Thiols on Gold: Variation in the Length of the Alkyl Chain

    DTIC Science & Technology

    1989-05-01

    Methyl- terminated thiols generate surfaces that are composed of densely packed methyl groups and are both hydrophobic (Oa(H20) = 1120) and oleophobic ...Details of the purification and synthesis of the materials used in these studies and general description of procedures have been provided in the preceding...together with monolayers of the two pure thiols. Both pure monolayers were autophobic and oleophobic : Oa(HD) = 470 for HS(CH2)2 1CH 3, 0a(HD) = 460 for

  9. Laboratory partitioning of platinum-group elements (PGE) and gold with application to magmatic sulfide PGE deposits

    NASA Astrophysics Data System (ADS)

    Fleet, M. E.; Crocket, J. H.; Liu, Menghua; Stone, W. E.

    1999-06-01

    Apparent diversity in laboratory partitioning of platinum-group elements (PGE)-Au between (Fe,Ni)-sulfide liquid and S-saturated basaltic melt is resolved by recognizing the marked control exerted by variation in metal/S ratio of the sulfide liquid. Partition coefficients ( D) increase markedly for Os, Ir and Pd and somewhat for Pt with increase in S content. In addition, the partitioning is markedly dependent on concentration of PGE-Au in the sulfide fraction, for all precious metals in metal-rich sulfide, and for Ru, Pt and Pd in relatively S-rich sulfide. Reversal of partitioning of PGE-Au is presently demonstrated for experiments with metal-rich sulfide liquids. Erratic partitioning behaviour, with anomalously high D(PGE-Au) values, is minimised by degassing starting materials. Summary D(PGE-Au) values for metal-rich sulfide liquids and near-natural PGE-Au abundances are: Os(2.2), Ir(1.8), Ru(2.4), Pt(1.4), Pd(2.9), Au(0.9) (×10 3) for the CCO oxygen buffer and molar Ni/(Fe+Ni)=0.02, and Os(3.7), Ir(3.2), Ru(4.4), Pt(4.6), Pd(5.0), Au(3.0) (×10 3) for the IQF buffer and Ni/(Fe+Ni)=0.12. Thus, PGE-Au would not be extensively fractionated for equilibrium between sulfide and deep mantle melts. For more S-rich sulfide liquids (WM oxygen buffer) and 100-1000 ppm in the sulfide, D(PGE-Au) values are: Os(30), Ir(26), Ru(6.4), Pt(10), Pd(17) (×10 3) at Ni/(Fe+Ni)=0.36, and Os(10), Ir(51), Ru(3.5), Pt(13), Pd(25), Au (1.2) (×10 3) at Ni/(Fe+Ni)=0.66. The laboratory partitioning is notably differential within the PGE-Au group, with relatively high Ds for Ir and Pd and low Ds for Ru and Au. Although separation of an early-magmatic sulfide liquid would result in significant concentration of some PGE (e.g., Ir and Pd), sulfide liquid immiscibility alone would not account for the high abundance of PGE-Au in the reef deposits of the Bushveld and Stillwater Complexes.

  10. Electron and ion transfer through multilayers of gold nanoclusters covered by self-assembled monolayers of alkylthiols with various functional groups.

    PubMed

    Uosaki, Kohei; Kondo, Toshihiro; Okamura, Masayuki; Song, Wenbo

    2002-01-01

    The electrochemical characteristics of various kinds of multilayers of gold nanoclusters (GNCs) were investigated. Two types of gold nanoclusters, one covered by self-assembled monolayers (SAMs) of mercaptoundecanoic acid (MUA), hexanethiol (C6SH), and ferrocenylhexanethiol (FcC6SH), MHF-GNC, and the other with MUA and C6SH, MH-GNC, were used. The multilayers were constructed on a Au(111) surface based on a carboxylate/metal cation (Cu++)/carboxylate or carboxylate/cationic polymer (poly(allylamine hydrochloride):PAH)/carboxylate electrostatic interaction. While the multilayers constructed by the former method were stable only in nonaqueous solutions, those constructed by the latter method were stable even in aqueous solutions. Electrochemical measurements of the multilayers of MHF-GNCs showed a pair of waves corresponding to the redox of the ferrocene group around 350-480 mV and the charge of these peaks, i.e., the amount of adsorbed GNC, increased linearly with the construction cycle up to 6 cycles in the former and to 18 cycles in the latter. A rather reversible redox response of the ferrocene moiety was observed even at the gold electrodes with five GNC layers of two different sequences in which MHF-GNC exists as the layer closest to the gold electrode, ie., the first layer, or as the outermost layer with MH-GNC in the other layers. These results show the facile transfer of electrons and ions through the multilayers of the SAM-covered GNCs and electron transfer between the ferrocene moiety and the Au(111) electrode takes place through the GNC cores by hopping.

  11. Fast, simple, combinatorial routes to the fabrication of reusable, plasmonically active gold nanostructures by interferometric lithography of self-assembled monolayers.

    PubMed

    Tsargorodska, Anna; El Zubir, Osama; Darroch, Brice; Cartron, Michaël L; Basova, Tamara; Hunter, C Neil; Nabok, Alexei V; Leggett, Graham J

    2014-08-26

    We describe a fast, simple method for the fabrication of reusable, robust gold nanostructures over macroscopic (cm(2)) areas. A wide range of nanostructure morphologies is accessible in a combinatorial fashion. Self-assembled monolayers of alkylthiolates on chromium-primed polycrystalline gold films are patterned using a Lloyd's mirror interferometer and etched using mercaptoethylamine in ethanol in a rapid process that does not require access to clean-room facilities. The use of a Cr adhesion layer facilitates the cleaning of specimens by immersion in piranha solution, enabling their repeated reuse without significant change in their absorbance spectra over two years. A library of 200 different nanostructures was prepared and found to exhibit a range of optical behavior. Annealing yielded structures with a uniformly high degree of crystallinity that exhibited strong plasmon bands. Using a combinatorial approach, correlations were established between the preannealing morphologies (determined by the fabrication conditions) and the postannealing optical properties that enabled specimens to be prepared "to order" with a selected localized surface plasmon resonance. The refractive index sensitivity of gold nanostructures formed in this way was found to correlate closely with measurements reported for structures fabricated by other methods. Strong enhancements were observed in the Raman spectra of tetra-tert-butyl-substituted phthalocyanine. The shift in the position of the plasmon band after site-specific attachment of histidine-tagged green fluorescent protein (His-GFP) and bacteriochlorophyll a was measured for a range of nanostructured films, enabling the rapid identification of the one that yielded the largest shift. This approach offers a simple route to the production of durable, reusable, macroscopic arrays of gold nanostructures with precisely controllable morphologies.

  12. Mixed self-assembled monolayers of alkanethiolates on ultrasmooth gold do not exhibit contact-angle hysteresis.

    PubMed

    Gupta, Pooja; Ulman, Abraham; Fanfan, Stephanie; Korniakov, Alexander; Loos, Katja

    2005-01-12

    We present the first study of mixed alkanethiolate SAMs on ultrasmooth gold surfaces. By eliminating surface roughness, it became possible, for the first time, to investigate wetting properties as a function of surface chemical composition. In three different surface compositions, it was found that contact-angle hysteresis apparently vanished. This suggests that surface chemical heterogeneity does not contribute to contact-angle hysteresis in mixed SAMs on ultrasmooth gold surfaces.

  13. Study on the reversible changes of the surface properties of an L-cysteine self-assembled monolayer on gold as a function of pH.

    PubMed

    Filimon, Andrei-Daniel; Jacob, Peter; Hergenröder, Roland; Jürgensen, Astrid

    2012-06-12

    A stimuli-response biological surface of L-cysteine was prepared on a polycrystalline gold surface from aqueous solution. The effect of the pH value of the rinsing solution on the surface composition was studied with X-ray photoelectron spectroscopy (XPS). Qualitative and quantitative analysis of the amino, carboxyl, and thiol functional groups of these self-assembled monolayers indicate that L-cysteine molecules exist in the neutral and zwitterionic forms and that they are sensitive to the pH of the rinsing solution. In addition, the wetting properties of the functionalized surface were studied by contact angle (CA) analysis: they were also dependent on the pH of the rinsing solution. Furthermore, it was shown that this functionalization process was reversible.

  14. Redistribution of elements between wastes and organic-bearing material in the dispersion train of gold-bearing sulfide tailings: Part I. Geochemistry and mineralogy.

    PubMed

    Saryg-Ool, B Yu; Myagkaya, I N; Kirichenko, I S; Gustaytis, M A; Shuvaeva, O V; Zhmodik, S M; Lazareva, E V

    2017-03-01

    Migration and redistribution of elements during prolonged interaction of cyanide wastes with the underlying natural organic-bearing material have been studied in two ~40cm deep cores that sample primary ores and their weathering profile (wastes I and II, respectively) in the dispersion train of gold-bearing sulfide tailings in Siberia. Analytical results of SR-XRF, whole-rock XRF, AAS, CHNS, and SEM measurements of core samples show high K, Sr, Ti, and Fe enrichments and correlation of P2O5 and Mn with LOI and Corg. Organic material interlayered or mixed with the wastes accumulates Cu, Zn, Se, Cd, Ag, Au, and Hg. The peat that contacts wastes II bears up to 3wt.% Zn, 1000g/t Se, 100g/t Cd, and 8000g/t Hg. New phases of Zn and Hg sulfides and Hg selenides occur as abundant sheaths over bacterial cells suggesting microbial mediation in sorption of elements. Organic-bearing material in the cores contains 10-30g/t Au in 2-5cm thick intervals, both within and outside the intervals rich in sulfides and selenides. Most of gold is invisible but reaches 345g/t and forms 50nm to 1.5μm Au(0) particles in a thin 2-3cm interval of organic remnants mixed with wastes I. Vertical and lateral infiltration of AMD waters in peat and oxidative dissolution of wastes within the dispersion train of the Ursk tailings lead to redistribution of elements and their accumulation by combined physical (material's permeability, direction AMD), chemical (complexing, sorption by organic matter and Fe(III) hydroxides) and biochemical (metabolism of sulfate-reducing bacteria) processes. The accumulated elements form secondary sulfates, and Hg and Zn selenides. The results provide insights into accumulation of elements in the early history of coal and black shale deposits and have implications for remediation of polluted areas and for secondary enrichment technologies.

  15. Quantitative imaging of 2 nm monolayer-protected gold nanoparticle distributions in tissues using laser ablation inductively-coupled plasma mass spectrometry (LA-ICP-MS).

    PubMed

    Elci, S Gokhan; Yan, Bo; Kim, Sung Tae; Saha, Krishnendu; Jiang, Ying; Klemmer, Gunnar A; Moyano, Daniel F; Tonga, Gulen Yesilbag; Rotello, Vincent M; Vachet, Richard W

    2016-04-21

    Functionalized gold nanoparticles (AuNPs) have unique properties that make them important biomedical materials. Optimal use of these materials, though, requires an understanding of their fate in vivo. Here we describe the use of laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to image the biodistributions of AuNPs in tissues from mice intravenously injected with AuNPs. We demonstrate for the first time that the distributions of very small (∼2 nm core) monolayer-protected AuNPs can be imaged in animal tissues at concentrations in the low parts-per-billion range. Moreover, the LA-ICP-MS images reveal that the monolayer coatings on the injected AuNPs influence their distributions, suggesting that the AuNPs remain intact in vivo and their surface chemistry influences how they interact with different organs. We also demonstrate that quantitative images of the AuNPs can be generated when the appropriate tissue homogenates are chosen for matrix matching. Overall, these results demonstrate the utility of LA-ICP-MS for tracking the fate of biomedically-relevant AuNPs in vivo, facilitating the design of improved AuNP-based therapeutics.

  16. Highly Sensitive Aluminium(III) Ion Sensor Based on a Self-assembled Monolayer on a Gold Nanoparticles Modified Screen-printed Carbon Electrode.

    PubMed

    See, Wong Pooi; Heng, Lee Yook; Nathan, Sheila

    2015-01-01

    A new approach for the development of a highly sensitive aluminium(III) ion sensor via the preconcentration of aluminium(III) ion with a self-assembled monolayer on a gold nanoparticles modified screen-printed carbon electrode and current mediation by potassium ferricyanide redox behavior during aluminium(III) ion binding has been attempted. A monolayer of mercaptosuccinic acid served as an effective complexation ligand for the preconcentration of trace aluminium; this led to an enhancement of aluminium(III) ion capture and thus improved the sensitivity of the sensor with a detection limit of down to the ppb level. Under the optimum experimental conditions, the sensor exhibited a wide linear dynamic range from 0.041 to 12.4 μM. The lower detection limit of the developed sensor was 0.037 μM (8.90 ppb) using a 10 min preconcentration time. The sensor showed excellent selectivity towards aluminium(III) ion over other interference ions.

  17. EXAFS in total reflection (reflEXAFS) for the study of organometallic Pd(II) thiol complexes based self-assembled monolayers on gold

    NASA Astrophysics Data System (ADS)

    Battocchio, C.; Fratoddi, I.; Venditti, I.; Yarzhemsky, V. G.; Norov, Yu. V.; Russo, M. V.; Polzonetti, G.

    2011-01-01

    The molecular structure and organization of self-assembled monolayers (SAMs) and multilayer films grafted onto Au/Si(1 1 1) surfaces of mononuclear transition metal dialkynyl bridged Pd(II) complexes trans-[HS-Pd(PBu 3) 2-SH] ( 1), trans-[HS-Pd(PBu 3) 2(-C tbnd C-C 6H 5)] ( 2) and of the binuclear complex trans, trans-[HS-Pd(PBu 3) 2(-C tbnd C-C 6H 4-C 6H 4-C tbnd C-Pd(PBu 3) 2-SH] ( 3), have been investigated by extended X-ray absorption fine structure spectroscopy in total reflection conditions (reflEXAFS). ReflEXAFS analysis of the data lead to determine the local structure around Pd atoms, assessing the square-planar geometry around the transition metal in the multilayers case, preserved in the monolayer regime. The investigation on the SAMs also provided the assessment of the S-Au bond length and Pd-S-Au bond angle and on the molecular orientation on the gold substrate of the complexes, confirmed by quantum chemical calculations.

  18. Gold atomic clusters extracting the valence electrons to shield the carbon monoxide passivation on near-monolayer core-shell nanocatalysts in methanol oxidation reactions.

    PubMed

    Chen, Tsan-Yao; Li, Hong Dao; Lee, Guo-Wei; Huang, Po-Chun; Yang, Po-Wei; Liu, Yu-Ting; Liao, Yen-Fa; Jeng, Horng-Tay; Lin, Deng-Sung; Lin, Tsang-Lang

    2015-06-21

    Atomic-scale gold clusters were intercalated at the inter-facet corner sites of Pt-shell Ru-core nanocatalysts with near-monolayer shell thickness. We demonstrated that these unique clusters could serve as a drain of valence electrons in the kink region of the core-shell heterojunction. As jointly revealed by density functional theory calculations and valence band spectra, these Au clusters extract core-level electrons to the valence band. They prevent corrosion due to protonation and enhance the tolerance of CO by increasing the electronegativity at the outermost surface of the NCs during the methanol oxidation reaction (MOR). In these circumstances, the retained current density of Pt-shell Ru-core NCs is doubled in a long-term (2 hours) MOR at a fixed voltage (0.5 V vs. SCE) by intercalating these sub-nanometer gold clusters. Such novel structural confinement provides a possible strategy for developing direct-methanol fuel cell (DMFC) modules with high power and stability.

  19. Successive coordination of palladium(II)-ions and terpyridine-ligands to a pyridyl-terminated self-assembled monolayer on gold

    NASA Astrophysics Data System (ADS)

    Poppenberg, Johannes; Richter, Sebastian; Darlatt, Erik; Traulsen, Christoph H.-H.; Min, Hyegeun; Unger, Wolfgang E. S.; Schalley, Christoph A.

    2012-02-01

    The deposition of palladium on a novel, reversibly protonatable, pyridyl-terminated self-assembled monolayer on gold substrates has been studied by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS spectroscopy) and time of flight-secondary ion mass spectrometry (ToF-SIMS). For this purpose, 12-(pyridin-4-yl)dodecane-1-thiol, consisting of a surface-active head group, an unfunctionalized hydrocarbon backbone and a terminal pyridyl group, has been synthesized and deposited on gold surfaces. Coordination of Pd(II) ions to the pyridyl group was examined. Furthermore, a reversible protonation/deprotonation cycle has been applied, and the relation between protonation and the amount of complexed palladium was studied. Investigation of the SAM by angle-resolved NEXAFS spectroscopy revealed the aliphatic backbone to be preferentially upright oriented with the aromatic head group being not preferentially oriented. The palladium layer was further coordinated with a CF3-labeled terpyridine ligand in order to prove the accessibility of the Pd(II) ions to further complexation and the platform useful for deposition of further layers toward a multi-layered system.

  20. Poly(glycidyl ether)-Based Monolayers on Gold Surfaces: Control of Grafting Density and Chain Conformation by Grafting Procedure, Surface Anchor, and Molecular Weight.

    PubMed

    Heinen, Silke; Weinhart, Marie

    2017-03-07

    For a meaningful correlation of surface coatings with their respective biological response reproducible coating procedures, well-defined surface coatings, and thorough surface characterization with respect to layer thickness and grafting density are indispensable. The same applies to polymeric monolayer coatings which are intended to be used for, e.g., fundamental studies on the volume phase transition of surface end-tethered thermoresponsive polymer chains. Planar gold surfaces are frequently used as model substrates, since they allow a variety of straightforward surface characterization methods. Herein we present reproducible grafting-to procedures performed with thermoresponsive poly(glycidyl ether) copolymers composed of glycidyl methyl ether (GME) and ethyl glycidyl ether (EGE). The copolymers feature different molecular weights (2 kDa, 9 kDa, 24 kDa) and are equipped with varying sulfur-containing anchor groups in order to achieve adjustable grafting densities on gold surfaces and hence control the tethered polymers' chain conformation. We determined "wet" and "dry" thicknesses of these coatings by QCM-D and ellipsometry measurements and deduced anchor distances and degrees of chain overlap of the polymer chains assembled on gold. Grafting under cloud point conditions allowed for higher degrees of chain overlap compared to grafting from a good solvent like ethanol, independent of the used sulfur-containing anchor group for polymers with low (2 kDa) and medium (9 kDa) molecular weights. By contrast, the achieved grafting densities and thus chain overlaps of surface-tethered polymers with high (24 kDa) molecular weights were identical for both grafting methods. Monolayers prepared from an ethanolic solution of poly(glycidyl ether)s equipped with sterically demanding disulfide-containing anchors revealed the lowest degrees of chain overlap. The ratio of the radius of gyration to the anchor distance (2 Rg/l) of the latter coating was found to be lower than 1

  1. Controlled hierarchical assembly of gold nanoparticles in macroscopic films: from densely packed monolayers to networks of micropores and nanobundles.

    PubMed

    Gravelsins, Steven; Hasham, Minhal; Lin, Yi; Yu, Kevin; Tie, Monique; Goh, Cynthia; Dhirani, Al-Amin

    2017-03-29

    The present study demonstrates the ability of excess, weakly amphiphilic n-alkanethiols (n = 4, 12, 18) and solvent composition to tune through a wide range of large-scale, macroscopic architectures formed by alkanethiol-capped Au nanoparticles (NPs). Both the alkanethiols and NPs are significantly hydrophobic species and compete for surface area at an air-water interface. When solutions of the two species are spread on a large (50 cm(2)) water surface in a Teflon well, a thin film forms and exhibits co-existing macroscopic regions with various distinct NP self-assembled architectures, namely a close packed monolayer, a network phase characterized by micron-sized pores (micropores) surrounded by quasi-linear bundles of nanoparticles, and finally aggregates. We hypothesize that the co-existence of various NP architectures results from fast, non-uniform evaporation across the large water surface. When solutions are instead deposited on a smaller (5 cm(2)) water surface contained within a Teflon ring to control the water surface curvature and the evaporation rate is slowed, we show for the first time that NPs form macroscopically uniform self-assemblies whose architectures can be tuned from monolayersmonolayers with micropores → extended micropore/NP bundle networks by varying excess alkanethiol concentration and solvent composition. We propose that competition between NPs and excess alkanethiols for water surface area, and alkanethiol self-assembly as well as solvent dewetting play important roles in the formation of the network phase, and discuss a potential mechanism for its formation.

  2. Electrochemical biosensor based on self-assembled monolayers modified with gold nanoparticles for detection of HER-3.

    PubMed

    Canbaz, Mehmet Çetin; Simşek, Ciğdem Sayıklı; Sezgintürk, Mustafa Kemal

    2014-03-03

    We have developed a new immunological biosensor for ultrasensitive quantification of human epidermal growth factor receptor-3(HER-3). In order to construct the biosensor, the gold electrode surface was layered with, hexanedithiol, gold nanoparticles, and cysteamine, respectively. Anti-HER-3 antibody was covalently attached to cysteamine by glutaraldehyde and used as a bioreceptor in a biosensor system for the first time by this study. Surface characterization was obtained by means of electrochemical impedance spectroscopy and voltammetry. The proposed biosensor showed a good analytical performance for the detection of HER-3 ranging from 0.2 to 1.4 pg mL(-1). Kramers-Kronig transform was performed on the experimental impedance data. Moreover, in an immunosensor system, the single frequency impedance technique was firstly used for characterization of interaction between HER-3 and anti-HER-3. Finally the presented biosensor was applied to artificial serum samples spiked with HER-3.

  3. Grazing Incidence X-Ray Diffraction of Lead Monolayers at a Silver (111) and Gold (111) Electrode/Electrolyte Interface.

    DTIC Science & Technology

    1987-05-12

    and electronic properties of underpotentially deposited (UPD) layers on single crystal electrodes have been explored by a number of investigators...of the reversible Nernst potential at which bulk deposition occurs. This first stage of deposition has been termed underpotential deposition (UPD...potentials (150 mV for lead on silver and 400 mV for gold) between the potential at which the " underpotential deposition " occurs and the potential for

  4. Self-induced "electroclick" immobilization of a copper complex onto self-assembled monolayers on a gold electrode.

    PubMed

    Gomila, Antoine; Le Poul, Nicolas; Cosquer, Nathalie; Kerbaol, Jean-Michel; Noël, Jean-Marc; Reddy, Madhusudana T; Jabin, Ivan; Reinaud, Olivia; Conan, Francoise; Le Mest, Yves

    2010-12-28

    We report the self-induced "electroclick" immobilization of the [Cu(II)(6-ethynyl-TMPA)(H(2)O)](2+) complex, by its simple electro-reduction, onto a mixed azidoundodecane-/decane-thiol modified gold electrode. The redox response of the grafted [Cu(II/I)(TMPA)] at the modified electrode is fully reversible indicating no Cu coordination change and a fast electron transfer.

  5. Electrochemical Properties of a Thiol Monolayers Coated Gold Electrode Modified with Osmium Gel Membrane as Enzyme Sensor

    NASA Astrophysics Data System (ADS)

    Yabutani, Tomoki; Okada, Nobuyuki; Maruyama, Kenichi; Motonaka, Junko

    The electrochemical behavior of an enzyme sensor for glucose using a gold electrode modified with thiol self-assembled membrane and osmium complex gel as an electron transferring mediator has further been investigated by electrochemical analysis. The gold electrode was initially coated with aminomethanethiol self assembling mono layer membrane(thiol-SAM) and then immobilized with glucose oxidase using poly(vinylpyridine-co-allylamine) (PVP-co-AA), gel coordinated with osmium bipyridine complexes (GOD/Os-PVP-co-AA gel). The cleaning condition of the surface of the Au electrode prior to coating thiol SAM was optimized for reduction of interference caused by concomitant compounds. It was found that interfering influence was most efficiently reduced in the case of use of the Au electrode immersed into nitric acid. The current ratio with a thiol coated gold electrode modified with Os-PVP-co-AA gel in glucose solution in the presence to absence of ascorbic acid, acetaminophen, and uric acid (ID+I/II) was 1.006, 1.014, and 1.018, respectively. The peak current response of glucose in the electrode modified with thiol SAM was dropped to 60 98% as compared with that without thiol SAM.

  6. Paleoproterozoic high-sulfidation mineralization in the Tapajós gold province, Amazonian Craton, Brazil: geology, mineralogy, alunite argon age, and stable-isotope constraints

    USGS Publications Warehouse

    Juliani, Caetano; Rye, Robert O.; Nunes, Carmen M.D.; Snee, Lawrence W.; Correa, Rafael H.; Monteiro, Lena V.S.; Bettencourt, Jorge S.; Neumann, Rainer; Neto, Arnaldo A.

    2005-01-01

    The Brazilian Tapajós gold province contains the first evidence of high-sulfidation gold mineralization in the Amazonian Craton. The mineralization appears to be in large nested calderas. The Tapajós–Parima (or Ventuari–Tapajós) geological province consists of a metamorphic, igneous, and sedimentary sequence formed during a 2.10 to 1.87 Ga ocean−continent orogeny. The high-sulfidation mineralization with magmatic-hydrothermal alunite is related to hydrothermal breccias hosted in a rhyolitic volcanic ring complex that contains granitic stocks ranging in age from 1.89 to 1.87 Ga. Cone-shaped hydrothermal breccias, which flare upward, contain vuggy silica and have an overlying brecciated cap of massive silica; the deposits are located in the uppermost part of a ring-structure volcanic cone. Drill cores of one of the hydrothermal breccias contain alunite, natroalunite, pyrophyllite, andalusite, quartz, rutile, diaspore, woodhouseite–svanbergite, kaolinite, and pyrite along with inclusions of enargite–luzonite, chalcopyrite, bornite, and covellite. The siliceous core of this alteration center is surrounded by advanced argillic and argillic alteration zones that grade outward into large areas of propylitically altered rocks with sericitic alteration assemblages at depth. Several occurrences and generations of alunite are observed. Alunite is disseminated in the advanced argillic haloes that envelop massive and vuggy silica or that underlie the brecciated silica cap. Coarse-grained alunite also occurs in branching veins and locally is partly replaced by a later generation of fine-grained alunite. Silicified hydrothermal breccias associated with the alunite contain an estimated reserve of 30 tonnes of gold in rock that grades up to 4.5 g t−1 Au. Seven alunite samples gave 40Ar/39Ar ages of 1.869 to 1.846 Ga, with various degrees of apparent minor Ar loss. Stable isotopic data require a magmatic-hydrothermal origin for the alunite, typical for high-sulfidation

  7. Quartz crystal microbalance study of bovine serum albumin adsorption onto self-assembled monolayer-functionalized gold with subsequent ligand binding.

    PubMed

    Thourson, Scott B; Marsh, Caitlin A; Doyle, Brian J; Timpe, Shannon J

    2013-11-01

    Adsorption characteristics of the model protein bovine serum albumin (BSA) onto gold surfaces were examined using a 5 MHz quartz crystal microbalance. Protein immobilization was executed in the presence and absence of a homogenous self-assembled monolayer (SAM) of NHS-terminated alkanethiols. BSA concentrations in the range of 3.2 × 10(-6) to 1.0 × 10(-3)mol/L were found to saturate both SAM-functionalized and non-functionalized surfaces with similar densities of 450 ± 26 ng/cm(2). The lack of functionalization dependence is attributed to the large protein size relative to the density of available binding sites in either surface condition. The BSA ligand 8-anilino-1-naphthalenesulfonic acid (ANS) was subsequently introduced to the immobilized BSA to determine any effects of the protein immobilization conditions on ligand binding. The rate of ANS binding to BSA was found to increase with increasing BSA concentration used in the immobilization step. This suggests that protein concentration affects morphology and ligand binding affinity without significantly altering adsorption quantity.

  8. Revealing and Resolving the Restrained Enzymatic Cleavage of DNA Self-Assembled Monolayers on Gold: Electrochemical Quantitation and ESI-MS Confirmation.

    PubMed

    Gao, Xiaoyi; Geng, Mingxi; Li, Yunchao; Wang, Xinglin; Yu, Hua-Zhong

    2017-02-21

    Herein, we report a combined electrochemical and ESI-MS study of the enzymatic hydrolysis efficiency of DNA self-assembled monolayers (SAMs) on gold, platform systems for understanding nucleic acid surface chemistry, and for constructing DNA-based biosensors. Our electrochemical approach is based on the comparison of the amounts of surface-tethered DNA nucleotides before and after exonuclease I (Exo I) incubation using electrostatically bound [Ru(NH3)6](3+) as redox indicators. It is surprising to reveal that the hydrolysis efficiency of ssDNA SAMs does not depend on the packing density and base sequence, and that the cleavage ends with surface-bound shorter strands (9-13 mers). The ex-situ ESI-MS observations confirmed that the hydrolysis products for ssDNA SAMs (from 24 to 56 mers) are dominated with 10-15 mer fragments, in contrast to the complete digestion in solution. Such surface-restrained hydrolysis behavior is due to the steric hindrance of the underneath electrode to the Exo I/DNA binding, which is essential for the occurrence of Exo I-catalyzed processive cleavage. More importantly, we have shown that the hydrolysis efficiency of ssDNA SAMs can be remarkably improved by adopting long alkyl linkers (locating DNA strands further away from the substrates).

  9. An Electrochemical Immunosensor for Detection of Staphylococcus aureus Bacteria Based on Immobilization of Antibodies on Self-Assembled Monolayers-Functionalized Gold Electrode

    PubMed Central

    Braiek, Mohamed; Rokbani, Karima Bekir; Chrouda, Amani; Mrabet, Béchir; Bakhrouf, Amina; Maaref, Abderrazak; Jaffrezic-Renault, Nicole

    2012-01-01

    The detection of pathogenic bacteria remains a challenge for the struggle against biological weapons, nosocomial diseases, and for food safety. In this research, our aim was to develop an easy-to-use electrochemical immunosensor for the detection of pathogenic Staphylococcus aureus ATCC25923. The biosensor was elaborated by the immobilization of anti-S. aureus antibodies using a self-assembled monolayer (SAMs) of 3-Mercaptopropionic acid (MPA). These molecular assemblies were spontaneously formed by the immersion of the substrate in an organic solvent containing the SAMs that can covalently bond to the gold surface. The functionalization of the immunosensor was characterized using two electrochemical techniques: cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Here, the analysis was performed in phosphate buffer with ferro/ferricyanide as the redox probe. The EIS technique was used for affinity assays: antibody-cell binding. A linear relationship between the increment in the electron transfer resistance (RCT) and the logarithmic value of S. aureus concentration was observed between 10 and 106 CFU/mL. The limit of detection (LOD) was observed at 10 CFU/mL, and the reproducibility was calculated to 8%. Finally, a good selectivity versus E. coli and S. epidermidis was obtained for our developed immunosensor demonstrating its specificity towards only S. aureus. PMID:25586032

  10. Structural Order in Ultrathin Films of the Monolayer Protected Clusters Based Upon 4-nm Gold Nanocrystals: An Experimental and Theoretical Study

    PubMed Central

    Bhattarai, Nabraj; Khanal, Subarna; Bahena, Daniel; Olmos-Asar, Jimena A.; Ponce, Arturo; Whetten, Robert L.; Mariscal, Marcelo M.; Jose-Yacaman, Miguel

    2014-01-01

    The structural order in ultrathin films of monolayer protected clusters (MPCs) is important in a number of application areas but can be difficult to demonstrate by conventional methods, particularly when the metallic core dimension, d, is in the intermediate size-range, 1.5 < d < 5.0 nm. Here, improved techniques for the synthesis of monodisperse thiolate-protected gold nanoparticles have made possible the production of dodecane-thiolate saturated ~ 4 ± 0.5 nm Au clusters with single-crystal core structure and morphology. An ultrathin ordered film or superlattice of these nanocrystal-core MPCs is prepared and investigated using aberration corrected scanning/transmission electron microscopy (STEM) which allowed imaging of long-range hexagonally ordered superlattices of the nanocrystals, separated by the thiolate groups. The lattice constants determined by direct imaging are in good agreement with those determined by small-angle electron diffraction. The STEM image revealed the characteristic grain boundary (GB) with sigma (Σ) 13 in the interface between two crystals. The formation and structures found are interpreted on the basis of theoretical calculations employing molecular dynamics (MD) simulations and coarse-grained (CG) approach. PMID:24875295

  11. The role of the crystalline face in the ordering of 6-mercaptopurine self-assembled monolayers on gold.

    PubMed

    Lobo Maza, Flavia; Grumelli, Doris; Carro, Pilar; Vericat, Carolina; Kern, Klaus; Salvarezza, Roberto C

    2016-10-06

    Well-ordered molecular films play an important role in nanotechnology, from device fabrication to surface patterning. Self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) on the Au(100)-(1 × 1) and Au(111)-(1 × 1) have been used to understand the interplay of molecule-substrate interactions for heterocyclic thiols capable of binding to the surface by two anchors, which spontaneously form a highly disordered film on Au(111). Our results reveal that for the same surface coverage the simple change of the substrate from Au(111)-(1 × 1) to Au(100)-(1 × 1) eliminates molecular disorder and yields well-ordered SAMs. We discuss these findings in terms of differences in the surface mobility of 6MP species on these surfaces, the energetics of the adsorption sites, and the number of degrees of freedom of these substrates for a molecule with reduced surface mobility resulting from its two surface anchors. These results reveal the presence of subtle molecule-substrate interactions involving the heteroatom that drastically alter SAM properties and therefore strongly impact on our ability to control physical properties and to build devices at the nanoscale.

  12. Substrate effects in poly(ethylene glycol) self-assembled monolayers on granular and flame-annealed gold.

    PubMed

    Rundqvist, Jonas; Hoh, Jan H; Haviland, David B

    2006-09-01

    Poly(ethylene glycol) (PEG) self-assembled monolayers (SAMs) are surface coatings that efficiently prevent nonspecific adhesion of biomolecules to surfaces. Here, we report on SAM formation of the PEG thiol CH3O(CH2CH2O)17NHCO(CH2)2SH (PEG(17)) on three types of Au films: thermally evaporated granular Au and two types of Au films from hydrogen flame annealing of granular Au, Au(111), and Au silicide. The different Au surfaces clearly affects the morphology and mechanical properties of the PEG(17) SAM, which is shown by AFM topographs and force distance curves. The two types of SAMs found on flame-annealed Au were denoted "soft" and "hard" due to their difference in stiffness and resistance to scratching by the AFM probe. With the aim of nanometer scale patterning of the PEG(17), the SAMs were exposed by low energy (1 kV) electron beam lithography (EBL). Two distinctly different types of behaviour were observed on the different types of SAM; the soft PEG(17) SAM was destroyed in a self-developing process while material deposition was dominant for the hard PEG(17) SAM.

  13. Investigation of the mechanism of electroless deposition of copper on functionalized alkanethiolate self-assembled monolayers adsorbed on gold.

    PubMed

    Lu, Peng; Walker, Amy V

    2007-12-04

    We have investigated the reaction pathways involved in the unseeded electroless deposition of copper on self-assembled monolayers (SAMs) adsorbed on Au, using time-of-flight secondary ion mass spectrometry, optical microscopy, and scanning electron microscopy. At 22 degrees C copper deposits on both -CH3 and -COOH terminated SAMs. No copper deposition is observed on -OH terminated SAMs because the hydroxyl terminal groups react with formaldehyde in the plating solution, forming an acetal which prevents Cu deposition. At higher deposition temperatures (45 degrees C), no Cu is observed to deposit on -CH3 terminated SAMs because Cu2+ ions are not stabilized on the SAM surface. Copper complexes are still able to form with the -COOH terminal group at 45 degrees C, and so copper continues to be deposited on -COOH terminated SAMs. Copper also penetrates through -CH3 and -COOH terminated SAMs to the Au/S interface, suggesting that soft deposition techniques do not prevent the penetration of low-to-moderate reactivity metals through organic films.

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

    PubMed

    Liu, Jian; Jian, Nan; Ornelas, Isabel; Pattison, Alexander J; Lahtinen, Tanja; Salorinne, Kirsi; Häkkinen, Hannu; Palmer, Richard E

    2016-11-22

    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 Au144(SCH2CH2Ph)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 Au144(SR)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.

  15. Switching on/off the chemisorption of thioctic-based self-assembled monolayers on gold by applying a moderate cathodic/anodic potential.

    PubMed

    Sahli, Rihab; Fave, Claire; Raouafi, Noureddine; Boujlel, Khaled; Schöllhorn, Bernd; Limoges, Benoît

    2013-04-30

    An in situ and real-time electrochemical method has been devised for quantitatively monitoring the self-assembly of a ferrocene-labeled cyclic disulfide derivative (i.e., a thioctic acid derivative) on a polycrystalline gold electrode under electrode polarization. Taking advantage of the high sensitivity, specificity, accuracy, and temporal resolution of this method, we were able to demonstrate an unexpectedly facilitated formation of the redox-active SAM when the electrode was held at a moderate cathodic potential (-0.4 V vs SCE in CH3CN), affording a saturated monolayer from only micromolar solutions in less than 10 min, and a totally impeded SAM growth when the electrode was polarized at a slightly anodic potential (+0.5 V vs SCE in CH3CN). This method literally allows for switching on/off the formation of SAMs under "soft" conditions. Moreover the cyclic disulfide-based SAM was completely desorbed at this potential contrary to the facilitated deposition of a ferrocene-labeled alkanethiol. Such a strikingly contrasting behavior could be explained by an energetically favored release of the thioctic-based SAM through homolytic cleavage of the Au-S bond followed by intramolecular cyclization of the generated thiyl diradicals. Moreover, the absence of a discernible transient faradaic current response during the potential-assisted adsorption/desorption of the redox-labeled cyclic disulfide led us to conclude in a potential-dependent reversible surface reaction where no electron is released or consumed. These results provide new insights into the formation of disulfide-based SAMs on gold but also raise some fundamental questions about the intimate mechanism involved in the facilitated adsorption/desorption of SAMs under electrode polarization. Finally, the possibility to easily and selectively address the formation/removal of thioctic-based SAMs on gold by applying a moderate cathodic/anodic potential offers another degree of freedom in tailoring their properties and

  16. Simple direct formation of self-assembled N-heterocyclic carbene monolayers on gold and their application in biosensing

    PubMed Central

    Crudden, Cathleen M.; Horton, J. Hugh; Narouz, Mina R.; Li, Zhijun; Smith, Christene A.; Munro, Kim; Baddeley, Christopher J.; Larrea, Christian R.; Drevniok, Benedict; Thanabalasingam, Bheeshmon; McLean, Alastair B.; Zenkina, Olena V.; Ebralidze, Iraklii I.; She, Zhe; Kraatz, Heinz-Bernhard; Mosey, Nicholas J.; Saunders, Lisa N.; Yagi, Akiko

    2016-01-01

    The formation of organic films on gold employing N-heterocyclic carbenes (NHCs) has been previously shown to be a useful strategy for generating stable organic films. However, NHCs or NHC precursors typically require inert atmosphere and harsh conditions for their generation and use. Herein we describe the use of benzimidazolium hydrogen carbonates as bench stable solid precursors for the preparation of NHC films in solution or by vapour-phase deposition from the solid state. The ability to prepare these films by vapour-phase deposition permitted the analysis of the films by a variety of surface science techniques, resulting in the first measurement of NHC desorption energy (158±10 kJ mol−1) and confirmation that the NHC sits upright on the surface. The use of these films in surface plasmon resonance-type biosensing is described, where they provide specific advantages versus traditional thiol-based films. PMID:27585494

  17. Method of making gold thiolate and photochemically functionalized microcantilevers

    DOEpatents

    Boiadjiev, Vassil I [Knoxville, TN; Brown, Gilbert M [Knoxville, TN; Pinnaduwage, Lal A [Knoxville, TN; Thundat, Thomas G [Knoxville, TN; Bonnesen, Peter V [Knoxville, TN; Goretzki, Gudrun [Nottingham, GB

    2009-08-25

    Highly sensitive sensor platforms for the detection of specific reagents, such as chromate, gasoline and biological species, using microcantilevers and other microelectromechanical systems (MEMS) whose surfaces have been modified with photochemically attached organic monolayers, such as self-assembled monolayers (SAM), or gold-thiol surface linkage are taught. The microcantilever sensors use photochemical hydrosilylation to modify silicon surfaces and gold-thiol chemistry to modify metallic surfaces thereby enabling individual microcantilevers in multicantilever array chips to be modified separately. Terminal vinyl substituted hydrocarbons with a variety of molecular recognition sites can be attached to the surface of silicon via the photochemical hydrosilylation process. By focusing the activating UV light sequentially on selected silicon or silicon nitride hydrogen terminated surfaces and soaking or spotting selected metallic surfaces with organic thiols, sulfides, or disulfides, the microcantilevers are functionalized. The device and photochemical method are intended to be integrated into systems for detecting specific agents including chromate groundwater contamination, gasoline, and biological species.

  18. Lead-Sulfide-Selenide Quantum Dots and Gold-Copper Alloy Nanoparticles Augment the Light-Harvesting Ability of Solar Cells.

    PubMed

    Das, Aparajita; Deepa, Melepurath; Ghosal, Partha

    2017-01-10

    Lead-sulfide-selenide (PbSSe) quantum dots (QDs) and gold-copper (AuCu) alloy nanoparticles (NPs) were incorporated into a cadmium sulfide (CdS)/titanium oxide (TiO2 ) photoanode for the first time to achieve enhanced conversion of solar energy into electricity. PbSSe QDs with a band gap of 1.02 eV extend the light-harvesting range of the photoanode from the visible region to the near-infrared region. The conduction band (CB) edge of the PbSSe QDs is wedged between the CBs of TiO2 and CdS; this additional level coupled with the good electrical conductivity of the dots facilitate charge transport and collection, and a high power conversion efficiency (PCE) of 4.44 % is achieved for the champion cell with the TiO2 /PbSSe/CdS electrode. Upon including AuCu alloy NPs in the QD-sensitized electrodes, light absorption is enhance by plasmonic and light-scattering effects and also by the injection of hot electrons to the CBs of the QDs. Comparison of the incident photon-to-current conversion efficiency enhancement factors in addition to fluorescence decay and impedance studies reveal that the PbSSe QDs and AuCu alloy NPs promote charge injection to the current collector and increase the photogenerated charges produced, which thus enables the TiO2 /PbSSe/CdS/AuCu cell to deliver the highest PCE of 5.26 % among all the various photoanode compositions used.

  19. Application of disorganized monolayer films on gold electrodes to the prevention of surfactant inhibition of the voltammetric detection of trace metals via anodic stripping of underpotential deposits: detection of copper.

    PubMed

    Herzog, Grégoire; Arrigan, Damien W M

    2003-01-15

    Development of an approach to prevention of electrode surface fouling by surfactants in samples is demonstrated. Spontaneously adsorbed monolayer systems employing short alkyl chains and bulky end groups are used to form porous disorganized monolayers on gold electrodes. Detection of copper by stripping of underpotential deposits formed at electrodes modified with disorganized films of mercaptoethanesulfonate (MES), mercaptopropanesulfonate, mercaptoacetic acid, and mercaptopropanoic acid was possible, and to a much lesser extent at aminoethanethiol and L-cysteine films. Use of short deposition times in conjunction with linear sweep anodic stripping voltammetry allowed detection of Cu2+ ions down to 1 x 10(-6) M in sulfuric acid solution, using underpotential deposition as the deposition step of the procedure. Calibration graphs were linear in the concentration range (1-80) x 10(-6) M Cu2+ using 15-s deposition at 0.00 V versus Ag/AgCl. The surfactants Tween 20, Tween 80, and Triton X-100 were found to have no affect on detection of Cu2+ ions in the calibration curve concentration range using MES-modified gold electrodes, whereas at unmodified gold electrodes very severe attenuation of the detection capability was manifested. The average slope for all calibration curves at the MES-modified electrode in the absence and presence of the surfactants at two different concentration levels was 0.0710 +/- 0.0024 microA microM(-1); in contrast, the slope of the calibration line at uncoated gold electrodes in the presence of surfactant was 0.0268 microA microM(-1). These results indicate the excellent ability of a disorganized, porous monolayer for prevention of fouling of the electrode surface by the surfactants.

  20. Ligand-modulated interactions between charged monolayer-protected Au144(SR)60 gold nanoparticles in physiological saline.

    PubMed

    Villarreal, Oscar D; Chen, Liao Y; Whetten, Robert L; Yacaman, Miguel J

    2015-02-07

    In order to determine how functionalized gold nanoparticles (AuNPs) interact in a near-physiological environment, we performed all-atom molecular dynamics simulations on the icosahedral Au144 nanoparticles each coated with a homogeneous set of 60 thiolates selected from one of these five (5) types: 11-mercapto-1-undecanesulfonate -SC11H22(SO3(-)), 5-mercapto-1-pentanesulfonate -SC5H10(SO3(-)), 5-mercapto-1-pentaneamine -SC5H10(NH3(+)), 4-mercapto-benzoate -SPh(COO(-)), or 4-mercapto-benzamide -SPh(CONH3(+)). These thiolates were selected to elucidate how the aggregation behavior of AuNPs depends on ligand parameters, including the charge of the terminal group (anionic vs. cationic), and its length and conformational flexibility. For this purpose, each functionalized AuNP was paired with a copy of itself, placed in an aqueous cell, neutralized by 120 Na(+)/Cl(-) counter-ions and salinated with a 150 mM concentration of NaCl, to form five (5) systems of like-charged AuNPs pairs in a saline. We computed the potential of mean force (the reversible work of separation) as a function of the intra-pair distance and, based on which, the aggregation affinities. We found that the AuNPs coated with negatively charged, short ligands have very high affinities. Structurally, a significant number of Na(+) counter-ions reside on a plane between the AuNPs, mediating the interaction. Each such ion forms a "salt bridge" (or "ionic bonds") to both of the AuNPs when they are separated by its diameter plus 0.2-0.3 nm. The positively charged AuNPs have much weaker affinities, as Cl(-) counter-ions form fewer and weaker salt bridges between the AuNPs. In the case of Au144(SC11H22(SO3(-)))60 pair, the flexible ligands fluctuate much more than the other four cases. The large fluctuations disfavor the forming of salt bridges between two AuNPs, but enable hydrophobic contact between the exposed hydrocarbon chains of the two AuNPs, which are subject to an effective attraction at a separation

  1. Ligand-modulated interactions between charged monolayer-protected Au144(SR)60 gold nanoparticles in physiological saline†

    PubMed Central

    Villarreal, Oscar D; Chen, Liao Y; Whetten, Robert L; Yacaman, Miguel J

    2015-01-01

    In order to determine how functionalized gold nanoparticles (AuNPs) interact in a near-physiological environment, we performed all-atom molecular dynamics simulations on the icosahedral Au144 nanoparticles each coated with a homogeneous set of 60 thiolates selected from one of these five (5) types: 11-mercapto-1-undecanesulfonate −SC11H22−(SO3−), 5-mercapto-1-pentanesulfonate −SC5H10(SO3−), 5-mercapto-1-pentaneamine −S+10H(NH3+), 4-mercapto-benzoate −SPh(COO−), or 4-mercapto-benzamide −SPh(CONH3+3). These thiolates were selected to elucidate how the aggregation behavior of AuNPs depends on ligand parameters, including the charge of the terminal group (anionic vs. cationic), and its length and conformational flexibility. For this purpose, each functionalized AuNP was paired with a copy of itself, placed in an aqueous cell, neutralized by 120 Na+/Cl− counter-ions and salinated with a 150 mM concentration of NaCl, to form five (5) systems of like-charged AuNPs pairs in a saline. We computed the potential of mean force (the reversible work of separation) as a function of the intra-pair distance and, based on which, the aggregation affinities. We found that the AuNPs coated with negatively charged, short ligands have very high affinities. Structurally, a significant number of Na+ counter-ions reside on a plane between the AuNPs, mediating the interaction. Each such ion forms a “salt bridge” (or “ionic bonds”) to both of the AuNPs when they are separated by its diameter plus 0.2~0.3 nm. The positively charged AuNPs have much weaker affinities, as Cl− counter-ions form fewer and weaker salt bridges between the AuNPs. In the case of Au144(SC11H22(SO3−))60 pair, the flexible ligands fluctuate much more than the other four cases. The large fluctuations disfavor the forming of salt bridges between two AuNPs, but enable hydrophobic contact between the exposed hydrocarbon chains of the two AuNPs, which are subject to an effective attraction at a

  2. AFM Study of Surface Nanobubbles on Binary Self-Assembled Monolayers on Ultraflat Gold with Identical Macroscopic Static Water Contact Angles and Different Terminal Functional Groups.

    PubMed

    Song, Bo; Chen, Kun; Schmittel, Michael; Schönherr, Holger

    2016-11-01

    All experimental findings related to surface nanobubbles, such as their pronounced stability and the striking differences of macroscopic and apparent nanoscopic contact angles, need to be addressed in any theory or model of surface nanobubbles. In this work we critically test a recent explanation of surface nanobubble stability and their consequences and contrast this with previously proposed models. In particular, we elucidated the effect of surface chemical composition of well-controlled solid-aqueous interfaces of identical roughness and defect density on the apparent nanoscopic contact angles. Expanding on a previous atomic force microscopy (AFM) study on the systematic variation of the macroscopic wettability using binary self-assembled monolayers (SAMs) on ultraflat template stripped gold (TSG), we assessed here the effect of different surface chemical composition for macroscopically identical static water contact angles. SAMs on TSG with a constant macroscopic water contact angle of 81 ± 2° were obtained by coadsorption of a methyl-terminated thiol and a second thiol with different terminal functional groups, including hydroxy, amino, and carboxylic acid groups. In addition, surface nanobubbles formed by entrainment of air on SAMs of a bromoisobutyrate-terminated thiol were analyzed by AFM. Despite the widely differing surface potentials and different functionality, such as hydrogen bond acceptor or donor, and different dipole moments and polarizability, the nanoscopic contact angles (measured through the condensed phase and corrected for AFM tip broadening effects) were found to be 145 ± 10° for all surfaces. Hence, different chemical functionalities at identical macroscopic static water contact angle do not noticeably influence the apparent nanoscopic contact angle of surface nanobubbles. This universal contact angle is in agreement with recent models that rely on contact line pinning and the equilibrium of gas outflux due to the Laplace pressure and

  3. Effects of intrusions on grades and contents of gold and other metals in volcanogenic massive sulfide deposits

    USGS Publications Warehouse

    Singer, D.A.; Berger, V.I.; Mosier, D.L.

    2011-01-01

    The reason some VMS deposits contain more gold or other metals than others might be due to the influence of intrusions. A new approach examining this possibility is based on examining the information about many VMS deposits to test statistically if those with associated intrusions have significantly different grades or amounts of metals. A set of 632 VMS deposits with reported grades, tonnages, and information about the observed presence or absence of subvolcanic or plutonic intrusive bodies emplaced at or after VMS mineralization is statistically analyzed. Deposits with syn-mineralization or post-mineralization intrusions nearby have higher tonnages than deposits without reported intrusions, but the differences are not statistically significant. When both kinds of intrusions are reported, VMS deposit sizes are significantly higher than in the deposits without any intrusions. Gold, silver, zinc, lead, and copper average grades are not significantly different in the VMS deposits with nearby intrusions compared to deposits without regardless of relative age of intrusive. Only zinc and copper contents are significantly higher in VMS deposits with both kinds of intrusive reported. These differences in overall metal content are due to significantly larger deposit sizes of VMS deposits where both intrusive kinds are observed and reported, rather than any difference in metal grades. ?? 2010.

  4. Polymer-assisted self-assembly of gold nanoparticle monolayers and their dynamical switching† †Electronic supplementary information (ESI) available: Reflection spectra of AuNP monolayer at the LLI, and repeatability; reflection spectra of different packing densities; scheme showing how the AuNPs actuate on the Si substrate. See DOI: 10.1039/c6nr05199e. The dataset of the figures in this paper can be found at http://dx.doi.org/10.17863/CAM.1194 Click here for additional data file.

    PubMed Central

    Rudrum, Adam W.; Herrmann, Lars O.; Turek, Vladimir

    2016-01-01

    Dynamic switching of plasmonic monolayers built of gold nanoparticles (AuNPs) is achieved using nano-coatings of poly(isopropyl acrylamide) (PNIPAM). The distance between AuNPs can be dynamically tuned through the repeatable expansion and contraction of the PNIPAM shells at different temperatures, which results in rapid switching of the optical properties of the AuNP monolayer. PMID:27546585

  5. Photoinduced electron transfer through peptide-based self-assembled monolayers chemisorbed on gold electrodes: directing the flow-in and flow-out of electrons through peptide helices.

    PubMed

    Venanzi, Mariano; Gatto, Emanuela; Caruso, Mario; Porchetta, Alessandro; Formaggio, Fernando; Toniolo, Claudio

    2014-08-21

    Photoinduced electron transfer (PET) experiments have been carried out on peptide self-assembled monolayers (SAM) chemisorbed on a gold substrate. The oligopeptide building block was exclusively formed by C(α)-tetrasubstituted α-aminoisobutyric residues to attain a helical conformation despite the shortness of the peptide chain. Furthermore, it was functionalized at the C-terminus by a pyrene choromophore to enhance the UV photon capture cross-section of the compound and by a lipoic group at the N-terminus for linking to gold substrates. Electron transfer across the peptide SAM has been studied by photocurrent generation experiments in an electrochemical cell employing a gold substrate modified by chemisorption of a peptide SAM as a working electrode and by steady-state and time-resolved fluorescence experiments in solution and on a gold-coated glass. The results show that the electronic flow through the peptide bridge is strongly asymmetric; i.e., PET from the C-terminus to gold is highly favored with respect to PET in the opposite direction. This effect arises from the polarity of the Au-S linkage (Au(δ+)-S(δ-), junction effect) and from the electrostatic field generated by the peptide helix.

  6. MICROPATTERNING OF GOLD SUBSTRATES BASED ON POLY(PROPYLENE SULFIDE-BL-ETHYLENE GLYCOL), (PPS-PEG) BACKGROUND PASSIVATION AND THE MOLECULAR-ASSEMBLY PATTERNING BY LIFT-OFF (MAPL) TECHNIQUE

    SciTech Connect

    Feller, L; Bearinger, J P; Wu, L; Hubbell, J A; Textor, M; Tosatti, S

    2007-11-13

    Poly(propylene sulfide-bl-ethylene glycol) (PPS-PEG) is an amphiphilic block copolymer that spontaneously adsorbs onto gold from solution. This results in the formation of a stable polymeric layer that renders the surface protein resistant when an appropriate architecture is chosen. The established molecular assembly patterning by lift-off (MAPL) technique can convert a prestructured resist film into a pattern of biointeractive chemistry and a noninteractive background. Employing the MAPL technique, we produced a micron-scale PPS-PEG pattern on a gold substrate, and then characterized the patterned structure with Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) and Atomic Force Microscopy (AFM). Subsequent exposure of the PPS-PEG/gold pattern to protein adsorption (full human serum) was monitored in situ; SPR-imaging shows a selective adsorption of proteins on gold, but not on PPS-PEG areas. Analysis shows a reduction of serum adsorption up to 93% on the PPS-PEG areas as compared to gold, in good agreement with previous analysis on homogeneously adsorbed PPS-PEG on gold. MAPL patterning of PPS-PEG block copolymers fast, versatile and reproducible, and allows for subsequent use of biosensor-based surface analysis methods.

  7. MICROPATTERNING OF GOLD SUBSTRATES BASED ON POLY(PROPYLENE SULFIDE-BL-ETHYLENE GLYCOL), (PPS-PEG) BACKGROUND PASSIVATION AND THE MOLECULAR-ASSEMBLY PATTERNING BY LIFT-OFF (MAPL) TECHNIQUE.

    PubMed

    Feller, L; Bearinger, J P; Wu, L; Hubbell, J A; Textor, M; Tosatti, S

    2008-07-01

    Poly(propylene sulfide-bl-ethylene glycol (PPS-PEG) is an amphiphilic block copolymer that spontaneously adsorbs onto gold from solution. This results in the formation of a stable polymeric layer that renders the surface protein resistant when an appropriate architecture is chosen. The established molecular assembly patterning by lift-off (MAPL) technique can convert a prestructured resist film into a pattern of biointeractive chemistry and a noninteractive background. Employing the MAPL technique, we produced a micron-scale PPS-PEG pattern on a gold substrate, and then characterized the patterned structure with Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) and Atomic Force Microscopy (AFM). Subsequent exposure of the PPS-PEG/gold pattern to protein adsorption (full human serum) was monitored in situ; SPR-imaging (i-SPR) shows a selective adsorption of proteins on gold, but not on PPS-PEG areas. Analysis shows a reduction of serum adsorption up to 93% on the PPS-PEG areas as compared to gold, in good agreement with previous analysis of homogenously adsorbed PPS-PEG on gold. MAPL patterning of PPS-PEG block copolymers is straightforward, versatile and reproducible, and may be incorporated into biosensor-based surface analysis methods.

  8. A ground electromagnetic survey used to map sulfides and acid sulfate ground waters at the abandoned Cabin Branch Mine, Prince William Forest Park, northern Virginia gold-pyrite belt

    USGS Publications Warehouse

    Wynn, Jeffrey C.

    2000-01-01

    INTRODUCTION AND BACKGROUND: Prince William Forest Park is situated at the northeastern end of the Virginia Gold-Pyrite belt northwest of the town of Dumfries, VA. The U. S. Marine Corps Reservation at Quantico borders the park on the west and south, and occupies part of the same watershed. Two abandoned mines are found within the park: the Cabin Branch pyrite mine, a historic source of acid mine drainage, and the Greenwood gold mine, a source of mercury contamination. Both are within the watershed of Quantico Creek (Fig.1). The Cabin Branch mine (also known as the Dumfries mine) lies about 2.4 km northwest of the town of Dumfries. It exploited a 300 meter-long, lens-shaped body of massive sulfide ore hosted by metamorphosed volcanic rocks; during its history over 200,000 tons of ore were extracted and processed locally. The site became part of the National Capitol Region of the National Park Service in 1940 and is currently managed by the National Park Service. In 1995 the National Park Service, in cooperation with the Virginia Department of Mines, Minerals, and Energy reclaimed the Cabin Branch site. The Virginia Gold-Pyrite belt, also known as the central Virginia volcanic-plutonic belt, is host to numerous abandoned metal mines (Pavlides and others, 1982), including the Cabin Branch deposit. The belt itself extends from its northern terminus near Cabin Branch, about 50 km south of Washington, D.C., approximately 175 km to the southwest into central Virginia. It is underlain by metamorphosed volcanic and clastic (non-carbonate) sedimentary rocks, originally deposited approximately 460 million years ago during the Ordovician Period (Horton and others, 1998). Three kinds of deposits are found in the belt: volcanic-associated massive sulfide deposits, low-sulfide quartz-gold vein deposits, and gold placer deposits. The massive sulfide deposits such as Cabin Branch were historically mined for their sulfur, copper, zinc, and lead contents, but also yielded byproduct

  9. Improved DET communication between cellobiose dehydrogenase and a gold electrode modified with a rigid self-assembled monolayer and green metal nanoparticles: The role of an ordered nanostructuration.

    PubMed

    Bollella, P; Mazzei, F; Favero, G; Fusco, G; Ludwig, R; Gorton, L; Antiochia, R

    2017-02-15

    Efficient direct electron transfer (DET) between cellobiose dehydrogenase from Corynascus thermophilus (CtCDH) and a novel gold electrode platform, obtained by covalent linking of green AuNPs and AgNPs modified with a dithiol self-assembled monolayer, consisting of biphenyl-4,4'-dithiol (BPDT), was presented. The green AuNPs and AgNPs were synthesized using quercetin as reducing agent at room temperature. TEM experiments showed that the AuNPs and AgNPs were circular in shape with an average diameter of 5 and 8nm, respectively. Cyclic voltammetry of CtCDH immobilized onto the AuNPs/BPDT/AuE and the AgNPs/BPDT/AuE electrode platforms were carried out and compared with naked AuE, BPDT/AuE, AuNPs/AuE, and AgNPs/AuE. A pair of well-defined redox waves in neutral pH solution due to efficient DET of CtCDH was present with both MNPs/BPDT/AuE platforms. No DET communication was found with platforms without MNPs linked to BPDT. The apparent heterogeneous electron transfer rate constants (kS) of CtCDH were calculated to be 21.5±0.8s(-1) and 10.3±0.7s(-1), for the AuNPs/BPDT/AuE and the AgNPs/BPDT/AuE platforms, respectively. The modified electrodes were successively used to develop an eco-friendly biosensor for lactose detection. The CtCDH/AuNPs/BPDT/AuE based biosensor showed the best analytical performances with an excellent stability, a detection limit of 3µM, a linear range between 5 and 400µM and a sensitivity of 27.5±2.5µAcm(-2)mM(-1). Such performances were favorably compared with other lactose biosensors reported in literature. The biosensor was successively tested to quantify lactose content in real milk and cream samples. No significant interference present in the sample matrices was observed.

  10. Tracking the Mineralogical Fate of Arsenic in Weathered Sulfides from the Empire Mine Gold-Quartz Vein Deposit by using Microbeam Analytical Techniques

    NASA Astrophysics Data System (ADS)

    Burlak, T.; Alpers, C. N.; Foster, A. L.; Brown, A.; Hammersley, L. C.; Petersen, E.

    2010-12-01

    Several complementary microbeam analytical techniques are being employed to determine the mineralogical fate of arsenic (As) released by weathering of primary sulfide minerals from waste rock at a California gold mine. Because of the known association of As with Fe-oxides, special attention was paid to the fate of Fe during weathering of arsenian pyrite [Fe(S,As)2], arsenopyrite (FeAsS), and ferroan dolomite [Ca(Mg,Fe)(CO3)2]. Samples were collected from waste rock dumps at the Empire Mine State Historic Park in Grass Valley, California, and polished thick (60-μm) sections were prepared for analysis. Micro-X-ray fluorescence (µXRF) investigations at the Stanford Synchrotron Radiation Lightsource (SSRL) involved mapping element distribution at the 100-μm pixel scale (beamline 10-2) and 2-µm pixel size (beamline 2-3) at four energies spanning the range of As valence states (11,867-11,890 eV). The maps provide spatial data on several elements (As, Ca, Fe, K, Mn, Ni, S, and Zn), but without standardization this information remains qualitative. Good correspondence was found between the results of principal component analysis of the maps and the distribution of the two main As valence states, As(III) and As(V). X-ray absorption fine structure (XAFS) spectra collected on beamline 2-3 at the As and Fe K-edges show reduced and oxidized species of both elements and no evidence for secondary arsenate phases such as scorodite (FeAsO4 ● 2H2O). Spectra of As(III) were rare, and not often mixed with As(V). The same thick sections were also analyzed by electron microbeam methods. Chemical and element analysis using a Cameca SX-100 microprobe quantified mineral compositions at selected spots in the sections by comparison to well-characterized reference materials. Concentrations of As in pyrite ranged from less than 0.01% to 3.1 wt. % and pyrite and was heterogeneous at the sub-µm scale. Arsenopyrite and ferroan dolomite were also found to be heterogeneous in composition

  11. Gold in minerals and the composition of native gold

    USGS Publications Warehouse

    Jones, Robert Sprague; Fleischer, Michael

    1969-01-01

    Gold occurs in nature mainly as the metal and as various alloys. It forms complete series of solid solutions with silver, copper, nickel, palladium, and platinum. In association with the platinum metals, gold occurs as free gold as well as in solid solution. The native elements contain the most gold, followed by the sulfide minerals. Several gold tellurides are known, but no gold selenides have been reported, and only one sulfide, the telluride-sulfide mineral nagyagite, is known. The nonmetallic minerals carry the least gold, and the light-colored minerals generally contain less gold than the dark minerals. Some conclusions in the literature are conflicting in regard to the relation of fineness of native gold to its position laterally and vertically within a lode, the nature of the country rocks, and the location and size of nuggets in a streambed, as well as to the variation of fineness within an individual nugget.

  12. Formation of Monolayers by the Coadsorption of Thiols on Gold: Variation in the Length of the Head Group, Tail Group, and Solvent

    DTIC Science & Technology

    1989-05-01

    oleophobic monolayer) and the other by a polar or polarizable group (yielding a hydrophilic or oleophilic monolayer). In these systems the contact...particular mechanism, and we prefer not to speculate further. Experimental Section Materials . Ethanol (U.S. Industrials Co.) was deoxygenated with nitrogen...8217 solution reacts violently with most organic materials and must be handled with extreme care. Adsorption solutions containing two thiols were prepared in

  13. Trace element distribution, with a focus on gold, in copper-rich and zinc-rich sulfide chimneys from Brothers submarine volcano, Kermadec arc

    NASA Astrophysics Data System (ADS)

    Berkenbosch, H. A.; de Ronde, C. E.; McNeill, A.; Goemann, K.; Gemmell, J. B.

    2012-12-01

    Brothers volcano is a dacitic volcano located along the Kermadec arc, New Zealand, and hosts the NW Caldera hydrothermal vent field perched on part of the steep caldera walls. The field strikes for ~600 m between depths of 1550 and 1700 m and includes numerous, active, high-temperature (max 302°C) chimneys and even more dead, sulfide-rich spires. Chimney samples collected from Brothers show distinct mineralogical zonation reflecting gradients in oxidation state, temperature, and pH from the inner walls in contact with hydrothermal fluids through to the outer walls in contact with seawater. Minerals deposited from hotter fluids (e.g., chalcopyrite) are located in the interior of the chimneys and are surrounded by an external zone of minerals deposited by cooler fluids (e.g., sulfates, sphalerite). Four chimneys types are identified at Brothers volcano based on the relative proportions of chalcopyrite and sulfate layers, and the presence or absence of anhydrite. Two are Cu-rich, i.e., chalcopyrite-rich and chalcopyrite-bornite-rich chimneys, and two are Zn-rich, i.e., sphalerite-rich and sphalerite-chalcopyrite-rich. Barite and anhydrite are common to both Cu-rich chimney types whereas Zn-rich chimneys contain barite only. The main mineral phases in all the chimneys are anhydrite, barite, chalcopyrite, pyrite/marcasite, and sphalerite. Trace minerals include galena, covellite, tennantite, realgar, chalcocite, bornite, hematite, goethite, Pb-As sulfosalts, and Bi- or Au-tellurides. The vast majority of tellurides are <5 μm in size and they commonly form in bands, cluster in patches, or occur along internal grain boundaries within chalcopyrite. In sulfate layers adjacent to the chalcopyrite zones tellurides can occur as inclusions in anhydrite, barite or pyrite and/or occupy void space within the chimney. The occurrence of specular hematite and Bi- or Au-tellurides associated with chalcopyrite are consistent with magmatic contributions to the NW Caldera vent site

  14. Selenium Sulfide

    MedlinePlus

    Selenium sulfide, an anti-infective agent, relieves itching and flaking of the scalp and removes the dry, ... Selenium sulfide comes in a lotion and is usually applied as a shampoo. As a shampoo, selenium ...

  15. Determination of self-exchange rate of alkanethiolates in self-assembled monolayers on gold using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

    PubMed

    Kang, Hyunook; Kim, Yongbin; Choi, Inseong; Chang, Rakwoo; Yeo, Woon-Seok

    2014-09-16

    In this paper, we describe a new method for determining the exchange rates of alkanethiolates in self-assembled monolayers (SAMs) on gold using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to analyze the compositions of the alkanethiolate in SAMs rapidly and directly. In particular, to investigate the self-exchange of alkanethiols, we prepared a deuterated alkanethiol that has the same molecular properties as the non-deuterated alkanethiol but a different molecular weight. SAMs consisting of deuterated alkanethiolates were immersed in a solution of the non-deuterated alkanethiol, and the influences of the immersion time, temperature, concentration, and solvent on the self-exchange rates were investigated. Furthermore, we assessed the exchange rates among alkanethiols with different carbon chain lengths and different size of ethylene glycol units. In addition, we performed molecular dynamics simulations using a model SAM system in order to understand the molecular mechanism of the exchange process.

  16. Equilibrating Nanoparticle Monolayers Using Wetting Films

    SciTech Connect

    Pontoni, D.; Alvine, K; Checco, A; Gang, O; Ocko, B; Pershan, P

    2009-01-01

    Monolayers of bimodal gold nanoparticles on silicon are investigated by a combination of microscopy (dry monolayers) and x-ray diffraction (dry and wet monolayers). In the presence of an excess of small particles, the nanoscale packing structure closely resembles the small-particle-rich scenario of the structural crossover transition that has been predicted and also observed with micron-scale hard-sphere colloids. Structural morphology is monitored in situ during monolayer dissolution and reassembly within the thin liquid wetting film. This approach allows investigation of size and solvent effects on nanoparticles in quasi-two-dimensional confinement.

  17. Improved protein crystallization by vapor diffusion from drops in contact with transparent, self-assembled monolayers on gold-coated glass coverslips

    NASA Astrophysics Data System (ADS)

    Ji, David; Arnold, Christine M.; Graupe, Michael; Beadle, Eric; Dunn, Robert V.; Phan, My N.; Villazana, Ramon J.; Benson, Ronald; Colorado, Ramon, Jr.; Randall Lee, T.; Friedman, Jonathan M.

    2000-09-01

    The surfaces of glass coverslips of the type typically used for protein crystallization were modified with four types of transparent, chemically distinct self-assembled monolayers (SAMs). The SAM-functionalized surfaces exhibit a much higher degree of order and chemical uniformity than silanized glass, as judged by contact angle measurements. These characteristics lead to a marked increase in the range of solution conditions under which large crystals of lysozyme, α-lactalbumin, ribonuclease, hemoglobin, thaumatin, and catalase are observed to form. The results are rationalized in terms of a marked reduction in the rate of non-productive nucleation relative to the rate of crystal growth.

  18. Hybrid nanostructures of well-organized arrays of colloidal quantum dots and a self-assembled monolayer of gold nanoparticles for enhanced fluorescence

    NASA Astrophysics Data System (ADS)

    Liu, Xiaoying; McBride, Sean P.; Jaeger, Heinrich M.; Nealey, Paul F.

    2016-07-01

    Hybrid nanomaterials comprised of well-organized arrays of colloidal semiconductor quantum dots (QDs) in close proximity to metal nanoparticles (NPs) represent an appealing system for high-performance, spectrum-tunable photon sources with controlled photoluminescence. Experimental realization of such materials requires well-defined QD arrays and precisely controlled QD-metal interspacing. This long-standing challenge is tackled through a strategy that synergistically combines lateral confinement and vertical stacking. Lithographically generated nanoscale patterns with tailored surface chemistry confine the QDs into well-organized arrays with high selectivity through chemical pattern directed assembly, while subsequent coating with a monolayer of close-packed Au NPs introduces the plasmonic component for fluorescence enhancement. The results show uniform fluorescence emission in large-area ordered arrays for the fabricated QD structures and demonstrate five-fold fluorescence amplification for red, yellow, and green QDs in the presence of the Au NP monolayer. Encapsulation of QDs with a silica shell is shown to extend the design space for reliable QD/metal coupling with stronger enhancement of 11 times through the tuning of QD-metal spatial separation. This approach provides new opportunities for designing hybrid nanomaterials with tailored array structures and multiple functionalities for applications such as multiplexed optical coding, color display, and quantum transduction.

  19. Perforated monolayers

    SciTech Connect

    Regen, S.L.

    1992-01-01

    Our research over this past grant period has focused on (1) developing methods for making in situ permeation measurements at the air-water interface, (2) defining the structural and conformational behavior of selected calix(4)arenes, (3) defining the metal complexation properties of certain upper-rim functionalized calix(4)arenes, and (4) synthesizing a broad series of polymerizable calixarenes, to be used for constructing perforated monolayers and multilayers.

  20. Electrochemical Deposition Of Thiolate Monolayers On Metals

    NASA Technical Reports Server (NTRS)

    Porter, Marc D.; Weissharr, Duane E.

    1995-01-01

    Electrochemical method devised for coating metal (usually, gold) surfaces with adherent thiolate monolayers. Affords greater control over location and amount of material deposited and makes it easier to control chemical composition of deposits. One important potential use for this method lies in fabrication of chemically selective thin-film resonators for microwave oscillators used to detect pollutants: monolayer formulated to bind selectively pollutant chemical species of interest, causing increase in mass of monolayer and corresponding decrease in frequency of resonance. Another important potential use lies in selective chemical derivatization for purposes of improving adhesion, lubrication, protection against corrosion, electrocatalysis, and electroanalysis.

  1. Monolayer-Protected Gold Nanoparticles as an Efficient Stationary Phase for Open Tubular Gas Chromatography using a Square Capillary Model for Chip-Based Gas Chromatography in Square Cornered Microfabricated Channels

    SciTech Connect

    Gross, Gwen M.; Grate, Jay W. ); Synovec, Robert E.

    2004-03-12

    The application of a dodecanethiol monolayer protected gold nanoparticle (MPN) stationary phase within a microchannel environment was explored using a square capillary column as a model for a high-speed, microfabricated gas chromatography (?GC). Successful deposition and evaluation of a dodecanethiol MPN phase within a 1.3 m long, 100?m by 100?m square capillary is reported. Depth of the MPN phase was evaluated using SEM analysis. An average thickness of 15 nm along the capillary walls was determined. While the film depth along the walls was very uniform, the corner depths were greater with the largest observed depth being 430 nm. Overall, an efficient chromatographic system was obtained with a minimum reduced plate height, hmin, of 1.2 for octane (k= 0.22). Characterization of the MPN column was completed using four compound classes (alkanes, alcohols, ketones, and aromatics) that were used to form a 7 component mixture with a 2 second separation. A mixture consisting of a nerve agent simulator in a sample containing analytes that may commonly interfere with detection was also separated in 2 seconds, much faster than a similar separation previously reported using a?GC system in 50 seconds. Application of the square capillary MPN column for a high-speed separation as the second column of a comprehensive two-dimensional gas chromatography system (GC x GC) was also explored. Comparison of the MPN stationary phase was compared to phases employed in previously reported?GC systems.

  2. Kinetic evaluation of highly active supported gold catalysts prepared from monolayer-protected clusters: an experimental Michaelis-Menten approach for determining the oxygen binding constant during CO oxidation catalysis.

    PubMed

    Long, Cormac G; Gilbertson, John D; Vijayaraghavan, Ganesh; Stevenson, Keith J; Pursell, Christopher J; Chandler, Bert D

    2008-08-06

    Thiol monolayer-protected Au clusters (MPCs) were prepared using dendrimer templates, deposited onto a high-surface-area titania, and then the thiol stabilizers were removed under H2/N2. The resulting Au catalysts were characterized with transmission electron microscopy, X-ray photoelectron spectroscopy, and infrared spectroscopy of adsorbed CO. The Au catalysts prepared via this route displayed minimal particle agglomeration during the deposition and activation steps. Structural data obtained from the physical characterization of the Au catalysts were comparable to features exhibited from a traditionally prepared standard Au catalyst obtained from the World Gold Council (WGC). A differential kinetic study of CO oxidation catalysis by the MPC-prepared Au and the standard WGC catalyst showed that these two catalyst systems have essentially the same reaction order and Arrhenius apparent activation energies (28 kJ/mol). However, the MPC-prepared Au catalyst shows 50% greater activity for CO oxidation. Using a Michaelis-Menten approach, the oxygen binding constants for the two catalyst systems were determined and found to be essentially the same within experimental error. To our knowledge, this kinetic evaluation is the first experimental determination of oxygen binding by supported Au nanoparticle catalysts under working conditions. The values for the oxygen binding equilibrium constant obtained from the Michaelis-Menten treatment (ca. 29-39) are consistent with ultra-high-vacuum measurements on model catalyst systems and support density functional theory calculations for oxygen binding at corner or edge atoms on Au nanoparticles and clusters.

  3. Model non-equilibrium molecular dynamics simulations of heat transfer from a hot gold surface to an alkylthiolate self-assembled monolayer.

    PubMed

    Zhang, Yue; Barnes, George L; Yan, Tianying; Hase, William L

    2010-05-07

    Model non-equilibrium molecular dynamics (MD) simulations are presented of heat transfer from a hot Au {111} substrate to an alkylthiolate self-assembled monolayer (H-SAM) to assist in obtaining an atomic-level understanding of experiments by Wang et al. (Z. Wang, J. A. Carter, A. Lagutchev, Y. K. Koh, N.-H. Seong, D. G. Cahill, and D. D. Dlott, Science, 2007, 317, 787). Different models are considered to determine how they affect the heat transfer dynamics. They include temperature equilibrated (TE) and temperature gradient (TG) thermostat models for the Au(s) surface, and soft and stiff S/Au(s) models for bonding of the S-atoms to the Au(s) surface. A detailed analysis of the non-equilibrium heat transfer at the heterogeneous interface is presented. There is a short time temperature gradient within the top layers of the Au(s) surface. The S-atoms heat rapidly, much faster than do the C-atoms in the alkylthiolate chains. A high thermal conductivity in the H-SAM, perpendicular to the interface, results in nearly identical temperatures for the CH(2) and CH(3) groups versus time. Thermal-induced disorder is analyzed for the Au(s) substrate, the S/Au(s) interface and the H-SAM. Before heat transfer occurs from the hot Au(s) substrate to the H-SAM, there is disorder at the S/Au(s) interface and within the alkylthiolate chains arising from heat-induced disorder near the surface of hot Au(s). The short-time rapid heating of the S-atoms enhances this disorder. The increasing disorder of H-SAM chains with time results from both disorder at the Au/S interface and heat transfer to the H-SAM chains.

  4. Perforated monolayers

    SciTech Connect

    Regen, S.L.

    1992-12-01

    Goal of this research program is to create ultrathin organic membranes that possess uniform and adjustable pores ( < 7[angstrom] diameter). Such membranes are expected to possess high permeation selectivity (permselectivity) and high permeability, and to provide the basis for energy-efficient methods of molecular separation. Work carried out has demonstrated feasibility of using perforated monolayer''-based composites as molecular sieve membranes. Specifically, composite membranes derived from Langmuir-Blodgett multilayers of the calix[6]arene-based surfactant shown below plus poly[l-(trimethylsilyl)-l-propyne] (PTMSP) were found to exhibit sieving behavior towards He, N[sub 2] and SF[sub 6]. Results of derivative studies that have also been completed are also described in this report.

  5. Dynamic in-plane potential gradients for actively controlling electrochemical reactions: Part I. Characterization of 1- and 2-component alkanethiol monolayer gradients on thin gold films. Part II. Applications of in-plane potential gradients

    NASA Astrophysics Data System (ADS)

    Balss, Karin Maria

    The research contained in this thesis is focused on the formation and characterization of surface composition gradients on thin gold films that are formed by applications of in-plane potential gradients. Injecting milliamp currents into thin Au films yields significant in-plane voltage drops so that, rather than assuming a single value of potential, an in-plane potential gradient is imposed on the film which depends on the resistivity of the film, the cross sectional area and the magnitude of the potential drop. Furthermore, the in-plane electric potential gradient means that, relative to a solution reference couple, electrochemical reactions occurs at defined spatial positions corresponding to the local potential, V(x) ˜ E0. The spatial gradient in electrochemical potential can then produce spatially dependent electrochemistry. Surface-chemical potential gradients can be prepared by arranging the spread of potentials to span an electrochemical wave mediating redox-associated adsorption or desorption. Examples of reactions that can be spatially patterned include the electrosorption of alkanethiols and over-potential metal deposition. The unique advantage of this method for patterning spatial compositions is the control of surface coverage in both space and time. The thesis is organized into two parts. In Part I, formation and characterization of 1- and 2-component alkanethiol monolayer gradients is investigated. Numerous surface science tools are employed to examine the distribution in coverage obtained by application of in-plane potential gradients. Macroscopic characterization was obtained by sessile water drop contact angle measurements and surface plasmon resonance imaging. Gradients were also imaged on micron length scales with pulsed-force mode atomic force microscopy. Direct chemical evidence of surface compositions in aromatic thiol surface coverage was obtained by surface-enhanced Raman spectroscopy. In Part II, the applications of in-plane potential

  6. Mimicking protein-protein electron transfer: voltammetry of Pseudomonas aeruginosa azurin and the Thermus thermophilus Cu(A) domain at omega-derivatized self-assembled-monolayer gold electrodes.

    PubMed

    Fujita, Kyoko; Nakamura, Nobufumi; Ohno, Hiroyuki; Leigh, Brian S; Niki, Katsumi; Gray, Harry B; Richards, John H

    2004-11-03

    Well-defined voltammetric responses of redox proteins with acidic-to-neutral pI values have been obtained on pure alkanethiol as well as on mixed self-assembled-monolayer (SAM) omega-derivatized alkanethiol/gold bead electrodes. Both azurin (P. aeruginosa) (pI = 5.6) and subunit II (Cu(A) domain) of ba(3)-type cytochrome c oxidase (T. thermophilus) (pI = 6.0) exhibit optimal voltammetric responses on 1:1 mixtures of [H(3)C(CH(2))(n)()SH + HO(CH(2))(n)()SH] SAMs. The electron transfer (ET) rate vs distance behavior of azurin and Cu(A) is independent of the omega-derivatized alkanethiol SAM headgroups. Strikingly, only wild-type azurin and mutants containing Trp48 give voltammetric responses: based on modeling, we suggest that electronic coupling with the SAM headgroup (H(3)C- and/or HO-) occurs at the Asn47 side chain carbonyl oxygen and that an Asn47-Cys112 hydrogen bond promotes intramolecular ET to the copper. Inspection of models also indicates that the Cu(A) domain of ba(3)-type cytochrome c oxidase is coupled to the SAM headgroup (H(3)C- and/or HO-) near the main chain carbonyl oxygen of Cys153 and that Phe88 (analogous to Trp143 in subunit II of cytochrome c oxidase from R. sphaeroides) is not involved in the dominant tunneling pathway. Our work suggests that hydrogen bonds from hydroxyl or other proton-donor groups to carbonyl oxygens potentially can facilitate intermolecular ET between physiological redox partners.

  7. Multifunctional self-assembled monolayers

    SciTech Connect

    Zawodzinski, T.; Bar, G.; Rubin, S.; Uribe, F.; Ferrais, J.

    1996-06-01

    This is the final report of at three year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The specific goals of this research project were threefold: to develop multifunctional self-assembled monolayers, to understand the role of monolayer structure on the functioning of such systems, and to apply this knowledge to the development of electrochemical enzyme sensors. An array of molecules that can be used to attach electrochemically active biomolecules to gold surfaces has been synthesized. Several members of a class of electroactive compounds have been characterized and the factors controlling surface modification are beginning to be characterized. Enzymes have been attached to self-assembled molecules arranged on the gold surface, a critical step toward the ultimate goal of this project. Several alternative enzyme attachment strategies to achieve robust enzyme- modified surfaces have been explored. Several means of juxtaposing enzymes and mediators, electroactive compounds through which the enzyme can exchange electrons with the electrode surface, have also been investigated. Finally, the development of sensitive biosensors based on films loaded with nanoscale-supported gold particles that have surface modified with the self-assembled enzyme and mediator have been explored.

  8. Determination of the platinum - Group elements (PGE) and gold (Au) in manganese nodule reference samples by nickel sulfide fire-assay and Te coprecipitation with ICP-MS

    USGS Publications Warehouse

    Balaram, V.; Mathur, R.; Banakar, V.K.; Hein, J.R.; Rao, C.R.M.; Gnaneswara, Rao T.; Dasaram, B.

    2006-01-01

    Platinum group elements (PGE) and Au data in polymetallic oceanic ferromanganese nodule reference samples and crust samples obtained by inductively coupled plasma mass spectrometry (ICP-MS), after separation and pre-concentration by nickel sulfide fire-assay and Te coprecipitation, are presented. By optimizing several critical parameters such as flux composition, matrix matching calibration, etc., best experimental conditions were established to develop a method suitable for routine analysis of manganese nodule samples for PGE and Au. Calibrations were performed using international PGE reference materials, WMG-1 and WMS-1. This improved procedure offers extremely low detection limits in the range of 0.004 to 0.016 ng/g. The results obtained in this study for the reference materials compare well with previously published data wherever available. New PGE data arc also provided on some international manganese nodule reference materials. The analytical methodology described here can be used for the routine analysis of manganese nodule and crust samples in marine geochemical studies.

  9. Carbonyl sulfide

    Integrated Risk Information System (IRIS)

    Carbonyl sulfide ; CASRN 463 - 58 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  10. Selenium sulfide

    Integrated Risk Information System (IRIS)

    Selenium sulfide ; CASRN 7446 - 34 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  11. Hydrogen sulfide

    Integrated Risk Information System (IRIS)

    EPA / 635 / R - 03 / 005 www.epa.gov / iris TOXICOLOGICAL REVIEW OF HYDROGEN SULFIDE ( CAS No . 7783 - 06 - 4 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) June 2003 U.S . Environmental Protection Agency Washington , DC DISCLAIMER This document has been revie

  12. Bioaccumulation of gold by sulfate-reducing bacteria cultured in the presence of gold(I)-thiosulfate complex

    NASA Astrophysics Data System (ADS)

    Lengke, Maggy; Southam, Gordon

    2006-07-01

    A sulfate-reducing bacterial (SRB) enrichment, from the Driefontein Consolidated Gold Mine, Witwatersrand Basin, Republic of South Africa, was able to destabilize gold(I)-thiosulfate complex (Au(SO)23-) and precipitate elemental gold. The precipitation of gold was observed in the presence of active (live) SRB due to the formation and release of hydrogen sulfide as an end-product of metabolism, and occurred by three possible mechanisms involving iron sulfide, localized reducing conditions, and metabolism. The presence of biogenic iron sulfide caused significant removal of gold from solutions by adsorption and reduction processes on the iron sulfide surfaces. The presence of gold nanoparticles within and immediately surrounding the bacterial cell envelope highlights the presence of localized reducing conditions produced by the bacterial electron transport chain via energy generating reactions within the cell. Specifically, the decrease in redox conditions caused by the release of hydrogen sulfide from the bacterial cells destabilized the Au(SO)23- solutions. The presence of gold as nanoparticles (<10 nm) inside a sub-population of SRB suggests that the reduction of gold was a part of metabolic process. In late stationary phase or death phase, gold nanoparticles that were initially precipitated inside the bacterial cells, were released from the cells and deposited in the bulk solution as addition of gold nanoparticles that already precipitated in the solution. Ultimately, the formation of micrometer-scale sub-octahedral and octahedral gold and spherical aggregates containing octahedral gold was observed.

  13. Sulfide chemiluminescence detection

    DOEpatents

    Spurlin, S.R.; Yeung, E.S.

    1985-11-26

    A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

  14. Sulfide chemiluminescence detection

    DOEpatents

    Spurlin, Stanford R.; Yeung, Edward S.

    1985-01-01

    A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

  15. Native gold in Hawaiian alkalic magma

    USGS Publications Warehouse

    Sisson, T.W.

    2003-01-01

    Native gold found in fresh basanite glass from the early submarine phase of Kilauea volcano, Hawaii, may be the first documented case of the transport of gold as a distinct precious metal phase in a mantle-derived magma. The gold-bearing glass is a grain in bedded volcanic glass sandstone (Japan Marine Science and Technology Center (JAMSTEC) sample S508-R3) collected by the submersible Shinkai 6500 at 3879 m depth off Kilauea's south flank. Extensive outcrops there expose debris-flow breccias and sandstones containing submarine-erupted alkalic rock fragments and glasses from early Kilauea. Precipitation of an immiscible gold liquid resulted from resorption of magmatic sulfides during crystallization-differentiation, with consequent liberation of sulfide-hosted gold. Elevated whole-rock gold concentrations (to 36 ppb) for fresh lavas and clasts from early Kilauea further show that some magmas erupted at the beginning stages of Hawaiian shield volcanoes were distinctly gold rich, most likely owing to limited residual sulfide in their mantle source. Alkalic magmas at other ocean islands may also be gold rich, and oceanic hot-spot provinces may contain underappreciated gold resources.

  16. SULFIDE MINERALS IN SEDIMENTS

    EPA Science Inventory

    The formation processes of metal sulfides in sediments, especially iron sulfides, have been the subjects of intense scientific research because of linkages to the global biogeochemical cycles of iron, sulfur, carbon, and oxygen. Transition metal sulfides (e.g., NiS, CuS, ZnS, Cd...

  17. Cadmium sulfide membranes

    DOEpatents

    Spanhel, Lubomir; Anderson, Marc A.

    1991-10-22

    A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.

  18. Cadmium sulfide membranes

    DOEpatents

    Spanhel, Lubomir; Anderson, Marc A.

    1992-07-07

    A method is described for the creation of novel q-effect cadmium sulfide membranes. The membranes are made by first creating a dilute cadmium sulfide colloid in aqueous suspension and then removing the water and excess salts therefrom. The cadmium sulfide membrane thus produced is luminescent at room temperature and may have application in laser fabrication.

  19. Integrated thin film cadmium sulfide solar cell module

    NASA Technical Reports Server (NTRS)

    Mickelsen, R. A.; Abbott, D. D.

    1971-01-01

    The design, development, fabrication and tests of flexible integrated thin-film cadmium sulfide solar cells and modules are discussed. The development of low cost and high production rate methods for interconnecting cells into large solar arrays is described. Chromium thin films were applied extensively in the deposited cell structures as a means to: (1) achieve high adherence between the cadmium sulfide films and the vacuum-metallized copper substrates, (2) obtain an ohmic contact to the cadmium sulfide films, and (3) improve the adherence of gold films as grids or contact areas.

  20. Assembly of designed protein scaffolds into monolayers for nanoparticle patterning.

    PubMed

    Mejias, Sara H; Couleaud, Pierre; Casado, Santiago; Granados, Daniel; Garcia, Miguel Angel; Abad, Jose M; Cortajarena, Aitziber L

    2016-05-01

    The controlled assembly of building blocks to achieve new nanostructured materials with defined properties at different length scales through rational design is the basis and future of bottom-up nanofabrication. This work describes the assembly of the idealized protein building block, the consensus tetratricopeptide repeat (CTPR), into monolayers by oriented immobilization of the blocks. The selectivity of thiol-gold interaction for an oriented immobilization has been verified by comparing a non-thiolated protein building block. The physical properties of the CTPR protein thin biomolecular films including topography, thickness, and viscoelasticity, are characterized. Finally, the ability of these scaffolds to act as templates for inorganic nanostructures has been demonstrated by the formation of well-packed gold nanoparticles (GNPs) monolayer patterned by the CTPR monolayer.

  1. A facile electrochemical route to the preparation of uniform and monoatomic copper shells for gold nanoparticles.

    PubMed

    Gründer, Y; Ramasse, Q M; Dryfe, R A W

    2015-02-28

    Copper on gold forms a monolayer deposit via underpotential deposition. For gold particles adsorbed at a liquid-liquid interface this results in a uniform one monolayer thick shell. This approach offers a new route for the uniform functionalisation of nanoparticles and presents a way to probe fundamental processes that underlie nanoparticle synthesis.

  2. Gold Rush!

    ERIC Educational Resources Information Center

    Brahier, Daniel J.

    1997-01-01

    Describes a mathematical investigation of gold--how it is weighed, stored, used, and valued. For grades 3-4, children estimate the value of treasure chests filled with gold coins and explore the size and weight of gold bars. Children in grades 5-6 explore how gold is mined and used, and how the value of gold changes over time. (PVD)

  3. Diamondoid monolayers as electron emitters

    DOEpatents

    Yang, Wanli; Fabbri, Jason D.; Melosh, Nicholas A.; Hussain, Zahid; Shen, Zhi-Xun

    2013-10-29

    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.

  4. Diamondoid monolayers as electron emitters

    DOEpatents

    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.

  5. Enhancement of gold recovery using bioleaching from gold concentrate

    NASA Astrophysics Data System (ADS)

    Choi, S. H.; Cho, K. H.; Kim, B. J.; Choi, N. C.; Park, C. Y.

    2012-04-01

    The gold in refractory ores is encapsulated as fine particles (sometimes at a molecular level) in the crystal structure of the sulfide (typically pyrite with or without arsenopyrite) matrix. This makes it impossible to extract a significant amount of refractory gold by cyanidation since the cyanide solution cannot penetrate the pyrite/arsenopyrite crystals and dissolve gold particles, even after fine grinding. To effectively extract gold from these ores, an oxidative pretreatment is necessary to break down the sulfide matrix. The most popular methods of pretreatment include nitric acid oxidation, roasting, pressure oxidation and biological oxidation by microorganisms. This study investigated the bioleaching efficiency of Au concentrate under batch experimental conditions (adaptation cycles and chemical composition adaptation) using the indigenous acidophilic bacteria collected from gold mine leachate in Sunsin gold mine, Korea. We conducted the batch experiments at two different chemical composition (CuSO4 and ZnSO4), two different adaptation cycles 1'st (3 weeks) and 2'nd (6 weeks). The results showed that the pH in the bacteria inoculating sample decreased than initial condition and Eh increased. In the chemical composition adaptation case, the leached accumulation content of Fe and Pb was exhibited in CuSO4 adaptation bacteria sample more than in ZnSO4 adaptation bacteria samples, possibly due to pre-adaptation effect on chalcopyrite (CuFeS2) in gold concentrate. And after 21 days on the CuSO4 adaptation cycles case, content of Fe and Pb was appeared at 1'st adaptation bacteria sample(Fe - 1.82 and Pb - 25.81 times per control sample) lower than at 2'nd adaptation bacteria sample(Fe - 2.87 and Pb - 62.05 times per control sample). This study indicates that adaptation chemical composition and adaptation cycles can play an important role in bioleaching of gold concentrate in eco-/economic metallurgy process.

  6. Nano-scale characterization of binary self-assembled monolayers under an ambient condition with STM and TERS.

    PubMed

    Horimoto, Noriko N; Tomizawa, Shigeru; Fujita, Yasuhiko; Kajimoto, Shinji; Fukumura, Hiroshi

    2014-09-07

    Gold surfaces were modified by benzyl-mercaptan (BM) and then partly replaced with benzenethiol (BT), which formed binary self-assembled monolayers (SAM). Initially BT randomly replaced BM in the monolayer, but at long exchange times >15 nm radius domains were observed with specific relative composition of BT and BM.

  7. Sulfide Mineralogy and Geochemistry

    NASA Astrophysics Data System (ADS)

    Dilles, John

    2007-02-01

    Reviews in Mineralogy and Geochemistry Series, Volume 61 David J. Vaughan, Editor Geochemical Society and Mineralogical Society of America; ISBN 0-939950-73-1 xiii + 714 pp.; 2006; $40. Sulfide minerals as a class represent important minor rock-forming minerals, but they are generally known as the chief sources of many economic metallic ores. In the past two decades, sulfide research has been extended to include important roles in environmental geology of sulfide weathering and resultant acid mine drainage, as well as in geomicrobiology in which bacteria make use of sulfides for metabolic energy sources. In the latter respect, sulfides played an important role in early evolution of life on Earth and in geochemical cycling of elements in the Earth's crust and hydrosphere.

  8. Using self-assembled monolayers to model the extracellular matrix.

    PubMed

    Mrksich, Milan

    2009-03-01

    The extracellular matrix is an insoluble aggregate of large proteins and glycosoaminoglycans that comprises the microenvironment of cells in tissue. The matrix displays a host of ligands that interact with cell-surface receptors to mediate the attachment and spreading of cells and regulate signaling processes. Studies of cell-matrix interactions and downstream signaling processes commonly employ substrates having an adsorbed layer of protein and are challenged by the difficulty in controlling the structure and activity of the immobilized protein. Significant effort has been directed towards the development of model substrates that present adhesion ligands in defined densities, orientations and environments. Among these approaches, self-assembled monolayers of alkanethiolates on gold offer a high level of control over the molecular structure of the surface and are well-suited to studies of cell adhesion. This review describes the design and use of monolayers for applications in cell biology, including the use of monolayers to evaluate the roles of peptide and protein ligands in cell-matrix interactions, the development of methods to pattern ligands on monolayers and applications to cell biology, the development of dynamic monolayers that can switch the activities of ligands presented to an adherent cell, and the rewiring of interactions between a cell and its substrate. These examples illustrate the flexibility inherent to monolayers for applications in cell biology.

  9. Constraints of mineralogical characterization of gold ore: Implication for genesis, controls and evolution of gold from Kundarkocha gold deposit, eastern India

    NASA Astrophysics Data System (ADS)

    Sahoo, P. R.; Venkatesh, A. S.

    2015-01-01

    Gold mineralization in Kundarkocha gold deposit occurs in the eastern Indian Craton that is hosted by sheared quartz-carbonate-sulfide veins emplaced within the graphitic schist, carbonaceous phyllite and talc-chlorite-serpentine schist belongs to Gorumahisani-Badampahar schist belt of Iron Ore Group. Gold mineralization exhibits both lithological and structural controls in the study area, albeit the stratigraphic control is more ubiquitously observed. Detailed mineralogical characterization coupled with electron probe microanalysis of the sulfide phases reveal the occurrences of gold in three distinct forms (i) as lattice-bound form within sulfides especially enriched in arsenopyrite, loellingite, pyrite, pyrrhotite and chalcopyrite in decreasing order of abundance; (ii) as micro inclusions or nano-scale gold inclusions within pyrite and arsenopyrite especially along the growth zones and micro-fractures as substrates and (iii) as free milling nugget gold grains either along the grain boundaries of sulfides or within the host rocks. Three generations of pyrite (Py-I, Py-II and Py-III) and arsenopyrite (Asp-I, Asp-II, Asp-III) have been identified based on textural, morphological characteristics and mineral chemistry. The lattice-bound gold content in pyrite and arsenopyrite varies from 600 to 2700 ppm and 900 to 3600 ppm respectively and increase in concentration of such refractory gold is seen in the order of chalcopyrite > pyrrhotite > pyrite > loellingite/arsenopyrite. The evolutionary stages of different forms of gold include remobilization of the lattice-bound grains in pyrite and arsenopyrite (Py-I and Asp-I) and re-concentration along the zoned-pyrite and arsenopyrite (Py-II and Asp-II) and ultimately as native gold/nuggets surrounding the sulfides as well as within the main mineralized zone. Lattice-bound gold distribution could have resulted due to metamorphic devolatilization reactions which are further aided by the influx of hydrothermal fluids. These

  10. Formation of gold mineralization in ultramafic alkalic magmatic complexes

    NASA Astrophysics Data System (ADS)

    Ryabchikov, I. D.; Kogarko, L. N.; Sazonov, A. M.; Kononkova, N. N.

    2016-06-01

    Study of mineral inclusions within alluvial gold particles of the Guli Complex (East Siberia) and findings of lode gold in rocks of the same intrusion have demonstrated that gold mineralization occurs in interstitions of both early high-magnesium rocks (dunite) and later alkalic and carbonatite rocks. In dunite the native gold occurs in association with Fe-Ni sulfides (monosulfide solid solution, pentlandite, and heazlewoodite). Formation of the gold-bearing alloys took place under a low oxygen potential over a broad range of temperatures: from those close to 600°C down to below 400°C.

  11. Novel Organo-Soluble Optically Tunable Chiral Hybrid Gold Nanorods

    DTIC Science & Technology

    2014-12-04

    AFRL-OSR-VA-TR-2014-0334 NOVEL ORGANO-SOLUBLE OPTICALLY TUNABLE CHIRAL HYBRID GOLD NANORODS Quan Li KENT STATE UNIV OH Final Report 12/04/2014...Prescribed by ANSI Std. Z39.18 1 FINAL REPORT Title: Novel Organo-Soluble Optically Tunable Chiral Hybrid Gold Nanorods AFOSR...Now this project has accomplished all the proposed objectives and beyond. Organo-soluble chiral azo thiol monolayer-protected gold nanorods, the

  12. Controlled electrodeposition of Au monolayer film on ionic liquid

    NASA Astrophysics Data System (ADS)

    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.

  13. Interstellar hydrogen sulfide.

    NASA Technical Reports Server (NTRS)

    Thaddeus, P.; Kutner, M. L.; Penzias, A. A.; Wilson, R. W.; Jefferts, K. B.

    1972-01-01

    Hydrogen sulfide has been detected in seven Galactic sources by observation of a single line corresponding to the rotational transition from the 1(sub 10) to the 1(sub 01) levels at 168.7 GHz. The observations show that hydrogen sulfide is only a moderately common interstellar molecule comparable in abundance to H2CO and CS, but somewhat less abundant than HCN and much less abundant than CO.

  14. Precipitation of gold by the reaction of aqueous gold(III)-chloride with cyanobacteria at 25-80{degrees}C, studied by x-ray absorption spectroscopy.

    SciTech Connect

    Lengke, M. F.; Ravel, B.; Fleet, M. E.; Wanger, G.; Gordon, R. A.; Southam, G.; Univ. of Western Ontario; Simon Fraser Univ.

    2007-10-01

    The mechanisms of gold precipitation by the interaction of cyanobacteria (Plectonema boryanum UTEX 485) and gold(III) chloride aqueous solutions (7.6 mmol/L final gold) have been studied at 25, 60, and 80 C, using both laboratory and real-time synchrotron radiation absorption spectroscopy experiments. Addition of aqueous gold(III) chloride to the cyanobacterial culture initially promoted the precipitation of amorphous gold(I) sulfide at the cell walls and finally caused the formation of octahedral (111) platelets (<1 to 6 {micro}m) of gold metal near cell surfaces and in solutions. X-ray absorption spectroscopy results confirmed that the reduction mechanism of gold(III) chloride to elemental gold by cyanobacteria involves the formation of an intermediate Au(I) species, gold(I) sulfide, with sulfur originating from cyanobacterial proteins, presumably cysteine or methionine. Although the bioreduction of gold(III) chloride to gold(I) sulfide was relatively rapid at all temperatures, the reaction rate increased with the increase in temperature. At the completion of the experiments, elemental gold was the major species present at all temperatures.

  15. Biointerfaces on indium-tin oxide prepared from organophosphonic acid self-assembled monolayers.

    PubMed

    Chockalingam, Muthukumar; Magenau, Astrid; Parker, Stephen G; Parviz, Maryam; Vivekchand, S R C; Gaus, Katharina; Gooding, J Justin

    2014-07-22

    Herein we show the development of biointerfaces on indium-tin oxide (ITO) surfaces prepared from organophosphonate self-assembled monolayers. The interfaces were prepared in a stepwise fabrication procedure containing a base monolayer modified with oligo(ethylene oxide) species to which biological recognition ligands were attached. The density of ligands was controlled by varying the ratio of two oligo(ethylene oxide) species such that only one is compatible with further coupling. The final biointerface on ITO was assessed using cell adhesion studies, which showed that the biointerfaces prepared on ITO performed similarly to equivalent monolayers on gold or silicon.

  16. Gold in the mantle: The role of pyroxenites

    NASA Astrophysics Data System (ADS)

    Saunders, J. Edward; Pearson, Norman J.; O'Reilly, Suzanne Y.; Griffin, William L.

    2016-02-01

    Mantle pyroxenites are the crystallised products of mafic silicate melts, which are commonly invoked as metasomatic agents in the upper mantle. This study has analysed the trace elements of sulfides, with a specific focus on gold, hosted in a suite of mantle pyroxenite xenoliths from Qilin in the Cathaysia Block, southeast China. These are compared with sulfides hosted in peridotite xenoliths from the same locality to assess the difference in the abundances of Au, and a suite of siderophile and chalcophile elements between the sulfides hosted in mobile melts in the upper mantle and their host "wall" rocks. Both the peridotite- and pyroxenite-hosted sulfides show a wide spectrum of trace element contents. The pyroxenite-hosted sulfides typically have PGE and Au concentrations that are an order of magnitude or more below those measured in the peridotite-hosted sulfides (lherzolite-hosted sulfides: total PGE = 95 ± 118 ppm, Au = 1.4 ± 2.6 ppm; pyroxenite-hosted sulfides: total PGE = 0.25 ± 0.70 ppm, Au = 0.14 ± 0.39 ppm). Furthermore, the Ir group PGE (Ir, Os and Ru) are present in lower concentrations than the Pd-group PGE (Pd, Pt and Rh). This may lead to a distinct signature if the melts from which these sulfides crystallise interact with lherzolitic sulfides. The overall low abundances of these elements within the pyroxenites suggests that the parent melts are an inefficient medium for enriching any of these elements in the upper mantle.

  17. Scanning tunneling microscopy studies of mixed self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Raigoza, Annette Fernandez

    This thesis examines the formation of multicomponent self-assembled mono-layers (SAMs) on the Au(111) surface using scanning tunneling microscopy. Two methods, sequential adsorption and coadsorption, are used to create these mixed SAMs. In the sequential adsorption experiments, a clean Au(111)-on-mica sub-strate is exposed to the first molecular species and then this adsorbate-covered sample is exposed to the second molecular species. Alternately, in the coadsorption experiments, a gold surface is exposed to both adsorbates simultaneously. Exposing a coronene- or dithiocarbamate-covered surface to excess thiol in the vapor phase results in a drastic restructuring of the initial surface. This is primarily driven by the kinetics of the octanethiol monolayer formation process, but the extent to which this happens is dependent on the molecule-molecule and molecule-surface interactions of the adsorbate due to the initial coverage and order of the monolayer. An octanethiolate monolayer is also substantially modified when immersed in a solution containing dithiocarbamate (DTC). Defects in the octanethiol monolayer are prime sites for molecular exchange. A surplus of DTC in the solution drives substitution that can lead to the complete removal of thiol from the surface. When a Au(111) surface is exposed to solutions containing both octanethiol and dithiocarbamate (DTC), both molecular species compete for available ad- sorption sites. At equal octanethiol-to-DTC ratios, molecular exchange hinders octanethiol monolayer formation. Higher octanethiol concentration in solution results in the incorporation of thiol into the resulting monolayer, with a strong dependence on the chain length of the DTC molecules.

  18. Multi-dimensional modeling of atmospheric copper-sulfidation corrosion on non-planar substrates.

    SciTech Connect

    Chen, Ken Shuang

    2004-11-01

    This report documents the author's efforts in the deterministic modeling of copper-sulfidation corrosion on non-planar substrates such as diodes and electrical connectors. A new framework based on Goma was developed for multi-dimensional modeling of atmospheric copper-sulfidation corrosion on non-planar substrates. In this framework, the moving sulfidation front is explicitly tracked by treating the finite-element mesh as a pseudo solid with an arbitrary Lagrangian-Eulerian formulation and repeatedly performing re-meshing using CUBIT and re-mapping using MAPVAR. Three one-dimensional studies were performed for verifying the framework in asymptotic regimes. Limited model validation was also carried out by comparing computed copper-sulfide thickness with experimental data. The framework was first demonstrated in modeling one-dimensional copper sulfidation with charge separation. It was found that both the thickness of the space-charge layers and the electrical potential at the sulfidation surface decrease rapidly as the Cu{sub 2}S layer thickens initially but eventually reach equilibrium values as Cu{sub 2}S layer becomes sufficiently thick; it was also found that electroneutrality is a reasonable approximation and that the electro-migration flux may be estimated by using the equilibrium potential difference between the sulfidation and annihilation surfaces when the Cu{sub 2}S layer is sufficiently thick. The framework was then employed to model copper sulfidation in the solid-state-diffusion controlled regime (i.e. stage II sulfidation) on a prototypical diode until a continuous Cu{sub 2}S film was formed on the diode surface. The framework was also applied to model copper sulfidation on an intermittent electrical contact between a gold-plated copper pin and gold-plated copper pad; the presence of Cu{sub 2}S was found to raise the effective electrical resistance drastically. Lastly, future research needs in modeling atmospheric copper sulfidation are discussed.

  19. Titration of gold nanoparticles in phase extraction.

    PubMed

    Cheng, Han-Wen; Schadt, Mark J; Zhong, Chuan-Jian

    2015-12-07

    In the organic-aqueous phase transfer process of gold nanoparticles, there are two types of distinctive interfaces involving hydrophilic and hydrophobic ligands, the understanding of which is important for the design of functional nanomaterials for analytical/bioanalytical applications and the control over the nanoparticles' nanoactivity and nanotoxicity in different phases. This report describes new findings of an investigation of the quantitative aspect of ligand ion pairing at the capping monolayer structure that drives the phase extraction of gold nanoparticles. Alkanethiolate-capped gold nanoparticles of 8 nm diameter with high size monodispersity (RSD ∼ 5%) were first derivatized by a ligand place exchange reaction with 11-mercaptoundecanoic acid to form a mixed monolayer shell consisting of both hydrophobic (-CH3) and hydrophilic (-COOH) groups. It was followed by quantitative titration of the resulting nanoparticles with a cationic species (-NR4(+)) in a toluene phase, yielding ion pairing of -NR4(+) and -COO(-) on part of the capping monolayer. Analysis of the phase extraction allowed a quantitative determination of the percentage of ion pairing and structural changes in the capping monolayer on the nanoparticles. The results, along with morphological characterization, are discussed in terms of the interfacial structural changes and their implications on the rational design of surface-functionalized nanoparticles and fine tuning of the interfacial reactivity.

  20. Self-assembly of 4-ferrocene thiophenol capped electroactive gold nanoparticles onto gold electrode

    NASA Astrophysics Data System (ADS)

    Li, Di; Li, Jinghong

    2003-01-01

    Gold nanoparticles capped by 4-ferrocene thiophenol with an average core size of 2.5 nm and surface plasmon absorbance at 522 nm were place-exchanged with 1,8-octanedithiol, and then self-assembled onto the gold electrode via tail SH group. The self-assembly was characterized by X-ray photoelectron spectroscopy. Cyclic voltammograms examined the coverage fraction of the self-assembled monolayers of the electroactive gold nanoparticles and the formal potential of the indicated SAMs. Further experiments exhibited that the electrode process was controlled by surface confined faradic reactions.

  1. SULFIDE METHOD PLUTONIUM SEPARATION

    DOEpatents

    Duffield, R.B.

    1958-08-12

    A process is described for the recovery of plutonium from neutron irradiated uranium solutions. Such a solution is first treated with a soluble sullide, causing precipitation of the plutoniunn and uraniunn values present, along with those impurities which form insoluble sulfides. The precipitate is then treated with a solution of carbonate ions, which will dissolve the uranium and plutonium present while the fission product sulfides remain unaffected. After separation from the residue, this solution may then be treated by any of the usual methods, such as formation of a lanthanum fluoride precipitate, to effect separation of plutoniunn from uranium.

  2. The gold-sulfur interface at the nanoscale.

    PubMed

    Häkkinen, Hannu

    2012-05-22

    Thiolate-protected gold surfaces and interfaces, relevant for self-assembled monolayers of organic molecules on gold, for passivated gold nanoclusters and for molecule-gold junctions, are archetypal systems in various fields of current nanoscience research, materials science, inorganic chemistry and surface science. Understanding this interface at the nanometre scale is essential for a wide range of potential applications for site-specific bioconjugate labelling and sensing, drug delivery and medical therapy, functionalization of gold surfaces for sensing, molecular recognition and molecular electronics, and gold nanoparticle catalysis. During the past five years, considerable experimental and theoretical advances have furthered our understanding of the molecular structure of the gold-sulfur interface in these systems. This Review discusses the recent progress from the viewpoint of theory and computations, with connections to relevant experiments.

  3. The gold-sulfur interface at the nanoscale

    NASA Astrophysics Data System (ADS)

    Häkkinen, Hannu

    2012-06-01

    Thiolate-protected gold surfaces and interfaces, relevant for self-assembled monolayers of organic molecules on gold, for passivated gold nanoclusters and for molecule-gold junctions, are archetypal systems in various fields of current nanoscience research, materials science, inorganic chemistry and surface science. Understanding this interface at the nanometre scale is essential for a wide range of potential applications for site-specific bioconjugate labelling and sensing, drug delivery and medical therapy, functionalization of gold surfaces for sensing, molecular recognition and molecular electronics, and gold nanoparticle catalysis. During the past five years, considerable experimental and theoretical advances have furthered our understanding of the molecular structure of the gold-sulfur interface in these systems. This Review discusses the recent progress from the viewpoint of theory and computations, with connections to relevant experiments.

  4. A kuroko-type polymetallic sulfide deposit in a submarine silicic caldera

    PubMed

    Iizasa; Fiske; Ishizuka; Yuasa; Hashimoto; Ishibashi; Naka; Horii; Fujiwara; Imai; Koyama

    1999-02-12

    Manned submersible studies have delineated a large and actively growing Kuroko-type volcanogenic massive sulfide deposit 400 kilometers south of Tokyo in Myojin Knoll submarine caldera. The sulfide body is located on the caldera floor at a depth of 1210 to 1360 meters, has an area of 400 by 400 by 30 meters, and is notably rich in gold and silver. The discovery of a large Kuroko-type polymetallic sulfide deposit in this arc-front caldera raises the possibility that the numerous unexplored submarine silicic calderas elsewhere might have similar deposits.

  5. Zinc sulfide liquefaction catalyst

    DOEpatents

    Garg, Diwakar

    1984-01-01

    A process for the liquefaction of carbonaceous material, such as coal, is set forth wherein coal is liquefied in a catalytic solvent refining reaction wherein an activated zinc sulfide catalyst is utilized which is activated by hydrogenation in a coal derived process solvent in the absence of coal.

  6. Electronic-Magnetic Properties of Monolayers of Chiral Bio-organic Molecules

    NASA Astrophysics Data System (ADS)

    Carmeli, Itai; Skakalova, Viera; Naaman, Ron; Vager, Zeev

    2002-10-01

    Measurements of the spin-correlated transmission of electrons through organized monolayers of polypeptide helices, absorbed on gold substrate, show high spin selectivity. The direction of the magnetic moment of the layer depends on the handedness of the helix molecule and on the direction of their dipole moment with respect to the metal substrate.

  7. Self-Assembled Monolayers: a Molecular Resolution STM Study

    NASA Astrophysics Data System (ADS)

    Dhirani, Al-Amin

    Building on studies of self-assembled monolayers (SAMs) based on the (CH_3(CH _2)_{rm n{-}1}SH) + Au(111) prototype, we have designed and constructed a high impedance STM to consider the formation and properties of new SAM systems with molecular resolution. On Au-, Ag-, and Pt-(111), the monolayer structures of n-decanethiol were found to be (1) ordered on gold and silver but not platinum (2) strongly correlated with the structures formed by simpler sulfur components. In addition the potential formation and properties of new molecular classes of ordered SAMs were considered by studying monolayers of H(C _6H_4Cequiv C)_{rm n}C _6H_4SH (n = 0 - 2) (1a - c) on Au(111). An increase in order with chain length as well as the formation of an ordered SAM by 1c were observed. Finally, current-voltage (I-V) measurements of 1 monolayers displayed an increasing nonlinearity with chain length and an asymmetry for 1c. The electrical behavior is consistent with a model based on a semi-classical tunneling formalism using the barrier height and molecular polarizability of 1.

  8. High-density monolayers of metal complexes: preparation and catalysis.

    PubMed

    Hara, Kenji; Sawamura, Masaya; Fukuoka, Atsushi

    2014-10-01

    Catalysts are one of the key materials for realizing a sustainable society. However, we may encounter problematic cases where conventional catalyst systems cannot provide effective solutions. We thus believe that the establishment of novel methods of catalyst preparation is currently necessary. Utilization of high-density monolayers of molecular metal complexes is our strategy, and we expect that this methodology will enable facile and systematic screening of unique and efficient catalysts. This Personal Account describes our challenges to establish such an immature method in catalyst preparation as well as the related background and perspective. Preparation and catalysis by high-density monolayers of Rh complexes with N-heterocyclic carbene, structurally compact phosphine and diisocyanide ligands on gold surfaces are presented. The catalytic application of a high-density Pd-bisoxazoline complex prepared on a single-crystal silicon surface is also shown. Uniquely high catalyst turnover numbers and high chemoselectivities were observed with these catalyst systems.

  9. Nanosecond laser ablation of gold nanoparticle films

    SciTech Connect

    Ko, Seung H.; Choi, Yeonho; Hwang, David J.; Grigoropoulos, Costas P.; Chung, Jaewon; Poulikakos, Dimos

    2006-10-02

    Ablation of self-assembled monolayer protected gold nanoparticle films on polyimide was explored using a nanosecond laser. When the nanoparticle film was ablated and subsequently thermally sintered to a continuous film, the elevated rim structure by the expulsion of molten pool could be avoided and the ablation threshold fluence was reduced to a value at least ten times lower than the reported threshold for the gold film. This could be explained by the unusual properties of nanoparticle film such as low melting temperature, weak bonding between nanoparticles, efficient laser energy deposition, and reduced heat loss. Finally, submicron lines were demonstrated.

  10. Tailoring nanoparticle surface monolayers for biomolecular recognition and delivery applications

    NASA Astrophysics Data System (ADS)

    Agasti, Sarit S.

    Engineering the interfaces between biomolecules and nanomaterials is central to the creation of materials for diverse areas of biomedical applications, including therapy, sensing and imaging. The goal of this research has been oriented toward the tailoring of the interfaces through the atomic level control provided by the organic synthesis. By employing a synergistic approach in the research, combining colloids, surface science, organic synthesis and biology, gold nanoparticles with tailored monolayers have been developed for bio-applications. This thesis illustrates the design and synthesis of these surface functionalized gold nanoparticles and their use in protein surface recognition and delivery systems for therapeutic applications. For protein surface recognition, we have fabricated gold nanoparticles bearing a diversity of amino acids termini and studied their interactions with proteins to elucidate the parameters affecting their interactions and catalytic behavior. In therapeutic applications, we have demonstrated the use of organically tailored nanoparticles for the creation of delivery systems featuring tunable stability and regulated drug release. Additionally, gold nanoparticles functionalized with molecular recognition motif have been used to demonstrate host-guest chemistry inside the living cells for the activation of therapeutic gold nanoparticles.

  11. Geothermal hydrogen sulfide removal

    SciTech Connect

    Urban, P.

    1981-04-01

    UOP Sulfox technology successfully removed 500 ppM hydrogen sulfide from simulated mixed phase geothermal waters. The Sulfox process involves air oxidation of hydrogen sulfide using a fixed catalyst bed. The catalyst activity remained stable throughout the life of the program. The product stream composition was selected by controlling pH; low pH favored elemental sulfur, while high pH favored water soluble sulfate and thiosulfate. Operation with liquid water present assured full catalytic activity. Dissolved salts reduced catalyst activity somewhat. Application of Sulfox technology to geothermal waters resulted in a straightforward process. There were no requirements for auxiliary processes such as a chemical plant. Application of the process to various types of geothermal waters is discussed and plans for a field test pilot plant and a schedule for commercialization are outlined.

  12. Biotreatment of refinery spent sulfidic caustics

    SciTech Connect

    Sublette, K.L.; Rajganesh, B.; Woolsey, M.; Plato, A.

    1995-12-31

    Caustics are used in petroleum refinering to remove hydrogen sulfide from various hydrocarbon streams. Spent sulfidic caustics from two Conoco refineries have been successfully biotreated on bench and pilot scale, resulting in neutralization and removal of active sulfides. Sulfides were completely oxidized to sulfate by Thiobacillus denitrificans. Microbial oxidation of sulfide produced acid, which at least partially neutralized the caustic.

  13. Phenomenological Modeling for Langmuir Monolayers

    NASA Astrophysics Data System (ADS)

    Baptiste, Dimitri; Kelly, David; Safford, Twymun; Prayaga, Chandra; Varney, Christopher N.; Wade, Aaron

    Experimentally, Langmuir monolayers have applications in molecular optical, electronic, and sensor devices. Traditionally, Langmuir monolayers are described by a rigid rod model where the rods interact via a Leonard-Jones potential. Here, we propose effective phenomenological models and utilize Monte Carlo simulations to analyze the phase behavior and compare with experimental isotherms. Research reported in this abstract was supported by UWF NIH MARC U-STAR 1T34GM110517-01.

  14. Suicide with hydrogen sulfide.

    PubMed

    Sams, Ralph Newton; Carver, H Wayne; Catanese, Charles; Gilson, Thomas

    2013-06-01

    This presentation will address the recent rise of suicide deaths resulting from the asphyxiation by hydrogen sulfide (H2S) gas.Hydrogen sulfide poisoning has been an infrequently encountered cause of death in medical examiner practice. Most H2S deaths that have been reported occurred in association with industrial exposure.More recently, H2S has been seen in the commission of suicide, particularly in Japan. Scattered reports of this phenomenon have also appeared in the United States.We have recently observed 2 intentional asphyxial deaths in association with H2S. In both cases, the decedents committed suicide in their automobiles. They generated H2S by combining a sulfide-containing tree spray with toilet bowl cleaner (with an active ingredient of hydrogen chloride acid). Both death scenes prompted hazardous materials team responses because of notes attached to the victims' car windows indicating the presence of toxic gas. Autopsy findings included discoloration of lividity and an accentuation of the gray matter of the brain. Toxicology testing confirmed H2S exposure with the demonstration of high levels of thiosulfate in blood.In summary, suicide with H2S appears to be increasing in the United States.

  15. Reflectivity and microhardness of sulfide minerals as genetic information source (case study: pyrite and arsenopyrite)

    NASA Astrophysics Data System (ADS)

    Sinkina, E. A.; Korovkin, M. V.; Savinova, O. V.; Makarova, A. A.

    2016-03-01

    Reflectivity and microhardness of pyrite and arsenopyrite of black shale gold-ore deposits in Chertovo Koryto (Patom upland) were studied. It was found that sulfides of different generations are characterized by different values of above-mentioned parameters which is associated mechanical and isomorphic impurities.

  16. Mineralogical and geochemical features of promising types of gold mineralization in the western Altai-Sayany folded region (Russia)

    NASA Astrophysics Data System (ADS)

    Chernykh, Alexandr

    2013-04-01

    The western Altai-Sayany folded region is one of the oldest mining regions of Russia. Typical gold deposits are quartz-viens and skarns, which formation is associated with intrusion of island-arc and collision granitoids. Due to the fact that the traditional gold ore base of the region has already been largely worked out, the necessity of prospecting for new gold deposits has arisen. On the basis of available data, one may state that the outlook for the development of gold-mining industry of the Altai-Sayany region is concerned with gold mineralization in weathering crusts, epithermal gold-silver, gold-porhyry and gold-sulfide formations. The total gold resource potential of these object types is estimated by us at the level of 2000 t. The gold mineralization of epithermal gold-silver formation is confined to Early-Middle Devonian volcanic-plutonic belt. Here, gold-bearing zones of beresitization, argillization, sulfidization and silicification are discovered among volcanites. Maximum contents of noble metals are found in quartz-sulfide veins among sulfidized (arsenic pyrite, pyrite, galenite, sphalerite and fahlore, etc.) and silicified volcanic and subvolcanic rocks. Ore zones are marked by anomalously high content of Au, Ag, Pb, Zn, As, Sb, Hg not only in bedrocks, but also in haloes of dispersion in loose deposits. Gold-sulfide mineralization in terrigenous carbonaceous strata is confined to Late Riphean, Early Cambrian and Devonian metamorphosed complexes. This rocks were formed in the marginal sea basins. Metamorphism and repeated tectono-magmatic activation in the region resulted in redistribution and accumulation of gold. Gold-ore zones are marked by intensive silicification and sulfidization and are characterized mostly by occurrences of multiple generations of pyrite and arsenic pyrite. Gold occurs both in free state and in sulphides. Geochemistry of gold-ore zones can be characterized by associated elevated content of As, Ag, Sb, Cu, Hg. Gold-sulfide

  17. Method of epitaxially depositing cadmium sulfide

    NASA Technical Reports Server (NTRS)

    Hawrylo, Frank Z. (Inventor)

    1980-01-01

    A single crystal layer of either cadmium sulfide or an alloy of cadmium sulfide and indium phosphide is epitaxially deposited on a substrate of cadmium sulfide by liquid phase epitaxy using indium as the solvent.

  18. Magnetism induced by the organization of self-assembled monolayers

    NASA Astrophysics Data System (ADS)

    Carmeli, I.; Leitus, G.; Naaman, R.; Reich, S.; Vager, Z.

    2003-06-01

    Unique occurrence of magnetism is shown, in which magnetism appears ex nihilo, when organic molecules are self-assembled as monolayers on gold substrate. The molecules as well as the substrate, when they stand alone, are diamagnetic. Using a superconducting quantum interference device type magnetometer we obtained direct evidence that close-packed organized thio-organic films adsorbed on gold substrates possess magnetic properties at room temperature. The films studied show very high specific magnetization, up to many tens Bohr magnetons per adsorbed molecule, with a very small hysteresis. It is highly anisotropic and shows almost no temperature dependence. The magnetism observed is related to charge transfer between the organic layer and the metal substrate. Yet, the uniqueness here is that many spins are polarized per adsorbed molecules. The magnetic effect is related to the two dimensional organization of the organic molecules on the metal substrate which might explain the high anisotropy.

  19. Gold, base-metal, and related deposits of North Carolina

    USGS Publications Warehouse

    Luttrell, Gwendolyn Werth

    1978-01-01

    Gold, silver, copper, lead, zinc, pyrite, tin, cobalt, molybdenum, tungsten, barite, and rare-earths have been mined in North Carolina. Gold, with by-product silver, occurs in veins and mineralized shear zones in metamorphic rocks of the Piedmont province and in placers derived from these deposits. Copper occurs with complex sulfide ores in quartz veins in the metamorphic rocks of the Piedmont province and in massive pyrrhotite-pyrite deposits in crystalline rocks west of the Blue Ridge. Lead and zinc occur in complex ores of gold, copper, lead, zinc, and silver in veins and replacements in metamorphic rocks. Pyrite occurs in crystalline metamorphic rocks. Tin occurs in pegmatite and placer deposits in crystalline rocks near Kings Mountain. Cobalt minerals with ores of iron or gold have been reported in a few areas in the Piedmont. Molybdenum occurs along the borders of a granite body in Halifax County. Tungsten minerals occur with copper sulfide ores in Cabarrus and Vance Counties. Barite occurs in quartz veins and associated with sulfide minerals in Orange, Madison, Cleveland, and Gaston Counties. Ore-earths occur with sulfides in vein deposits in Cabarrus County.

  20. Enantiomeric interactions between liquid crystals and organized monolayers of tyrosine-containing dipeptides.

    PubMed

    Bai, Yiqun; Abbott, Nicholas L

    2012-01-11

    We have examined the orientational ordering of nematic liquid crystals (LCs) supported on organized monolayers of dipeptides with the goal of understanding how peptide-based interfaces encode intermolecular interactions that are amplified into supramolecular ordering. By characterizing the orientations of nematic LCs (4-cyano-4'-pentylbiphenyl and TL205 (a mixture of mesogens containing cyclohexane-fluorinated biphenyls and fluorinated terphenyls)) on monolayers of l-cysteine-l-tyrosine, l-cysteine-l-phenylalanine, or l-cysteine-l-phosphotyrosine formed on crystallographically textured films of gold, we conclude that patterns of hydrogen bonds generated by the organized monolayers of dipeptides are transduced via macroscopic orientational ordering of the LCs. This conclusion is supported by the observation that the ordering exhibited by the achiral LCs is specific to the enantiomers used to form the dipeptide-based monolayers. The dominant role of the -OH group of tyrosine in dictating the patterns of hydrogen bonds that orient the LCs was also evidenced by the effects of phosphorylation of the tyrosine on the ordering of the LCs. Overall, these results reveal that crystallographic texturing of gold films can direct the formation of monolayers of dipeptides with long-range order, thus unmasking the influence of hydrogen bonding, chirality, and phosphorylation on the macroscopic orientational ordering of LCs supported on these surfaces. These results suggest new approaches based on supramolecular assembly for reporting the chemical functionality and stereochemistry of synthetic and biological peptide-based molecules displayed at surfaces.

  1. Structure and self-assembly of sequentially adsorbed coronene/octanethiol monolayers

    NASA Astrophysics Data System (ADS)

    Raigoza, Annette F.; Villalba, D. Andres; Kautz, Natalie A.; Kandel, S. Alex

    2010-09-01

    Scanning tunneling microscopy is used to investigate the structure of sequentially adsorbed coronene/octanethiol monolayers on Au(111). In these experiments, coronene-covered gold surfaces are exposed to octanethiol vapor. The resulting mixed monolayers are covered by close-packed octanethiol domains with clusters of coronene located within octanethiol domain boundaries. For these systems, the positions of coronene on the surface are determined by the kinetics of octanethiol monolayer formation and the local structure of the gold. The initial coverage and order of the coronene-covered surface influence the final structure of the mixed coronene/alkanethiol monolayer: deposition of coronene from the vapor phase, which creates a relatively lower coverage and higher degree of order than solution-based deposition, results in smaller coronene clusters. Statistical analysis of the locations of clusters of coronene shows that depending on the deposition parameters, coronene clusters are repelled in varying degree by upward-going and downward-going steps or are attracted to the top edges of surface step defects. In contrast to clusters, isolated coronene molecules are observed in the middle of close-packed octanethiol domains, but also appear to have an affinity for the edge of downward-going steps. We compare these results to mixed monolayers composed of C 70 and octanethiol.

  2. Nanoscale Phase Segregation of Mixed Thiolates on Gold Nanoparticles

    PubMed Central

    Harkness, Kellen M.; Balinski, Andrzej

    2012-01-01

    Phase segregation and domain formation is observed within the protecting monolayer of gold nanoparticles (AuNPs) using ion mobility-mass spectrometry, a two-dimensional gas-phase separation technique. Experimental data is compared to a theoretical model that represents a randomly distributed ligand mixture. Deviations from this model provide evidence for nanophase separation resulting in anisotropic AuNPs. PMID:21882306

  3. Sulfide bonded atomic radii

    NASA Astrophysics Data System (ADS)

    Gibbs, G. V.; Ross, N. L.; Cox, D. F.

    2017-03-01

    The bonded radius, r b(S), of the S atom, calculated for first- and second-row non-transition metal sulfide crystals and third-row transition metal sulfide molecules and crystals indicates that the radius of the sulfur atom is not fixed as traditionally assumed, but that it decreases systematically along the bond paths of the bonded atoms with decreasing bond length as observed in an earlier study of the bonded radius of the oxygen atom. When bonded to non-transition metal atoms, r b(S) decreases systematically with decreasing bond length from 1.68 Å when the S atom is bonded to the electropositive VINa atom to 1.25 Å when bonded to the more electronegative IVP atom. In the case of transition metal atoms, rb(S) likewise decreases with decreasing bond length from 1.82 Å when bonded to Cu and to 1.12 Å when bonded to Fe. As r b(S) is not fixed at a given value but varies substantially depending on the bond length and the field strength of the bonded atoms, it is apparent that sets of crystal and atomic sulfide atomic radii based on an assumed fixed radius for the sulfur atom are satisfactory in that they reproduce bond lengths, on the one hand, whereas on the other, they are unsatisfactory in that they fail to define the actual sizes of the bonded atoms determined in terms of the minima in the electron density between the atoms. As such, we urge that the crystal chemistry and the properties of sulfides be studied in terms of the bond lengths determined by adding the radii of either the atomic and crystal radii of the atoms but not in terms of existing sets of crystal and atomic radii. After all, the bond lengths were used to determine the radii that were experimentally determined, whereas the individual radii were determined on the basis of an assumed radius for the sulfur atom.

  4. Gold Coating

    NASA Technical Reports Server (NTRS)

    1997-01-01

    Epner Technology Inc. responded to a need from Goddard Space Flight Center for the ultimate in electroplated reflectivity needed for the Mars Global Surveyor Mars Orbiter Laser Altimeter (MOLA). Made of beryllium, the MOLA mirror was coated by Epner Technology Laser Gold process, specially improved for the project. Improved Laser Gold- coated reflectors have found use in an epitaxial reactor built for a large semiconductor manufacturer as well as the waveguide in Braun-Thermoscan tympanic thermometer and lasing cavities in various surgical instruments.

  5. Monolayer coated aerogels and method of making

    DOEpatents

    Zemanian, Thomas Samuel; Fryxell, Glen; Ustyugov, Oleksiy A.

    2006-03-28

    Aerogels having a monolayer coating are described. The aerogel and a monolayer forming precursor are provided in a supercritical fluid, whereupon the aerogel and the monolayer forming precursor are reacted in said supercritical fluid to form a covalent bond between the aerogel and the monolayer forming precursor. Suitable aerogels are ceramic oxides such as silica, alumina, aluminosilicate, and combinations thereof. Suitable monolayer forming precursors include alkyl silanes, chlorosilanes, boranes, chloroboranes, germanes, and combinations thereof. The method may also include providing a surface preparation agent such as water, or hydroetching an aerogel to enhance the coating of the monolayer.

  6. Ferrocene-based monolayers: Self-assembly via rigid bidentate anchor groups

    NASA Astrophysics Data System (ADS)

    Weidner, Tobias; Krohn, Bianca; Trojtza, Marta; Bruhn, Clemens; Rother, Dag; Siemeling, Ulrich; Träger, Frank

    2006-02-01

    Self-assembled monolayers of the bidentate ferrocene containing ligands diisocyanoferrocene (1), bis(diphenylphosphanyl) ferrocene (2), and diisothiocyanatoferrocene (3) have been prepared and their adsorption kinetics on gold films were characterized with optical second-harmonic generation and ellipsometry. As opposed to ferrocenylfunctionalized ligands used in earlier studies, the redox-active moieties discussed here carry two anchor groups to "pin" them to the substrate in a well-defined orientation and distance to the surface. 1 and 3 show monolayer film formation that follows first order, while film assembly of 2 is best described by a second order Langmuir kinetics.

  7. Gold Nanoantennas

    SciTech Connect

    2012-01-01

    An array of gold nanoantennas laced into an artificial membrane enhances the fluorescence intensity of three different molecules when they pass through plasmonic hot spots in the array. Watch for the blue, green and red flashes. The photobleaching at the end of each fluorescence event (white flashes) is indicative of single molecule observations.

  8. Electromelting of confined monolayer ice.

    PubMed

    Qiu, Hu; Guo, Wanlin

    2013-05-10

    In sharp contrast to the prevailing view that electric fields promote water freezing, here we show by molecular dynamics simulations that monolayer ice confined between two parallel plates can melt into liquid water under a perpendicularly applied electric field. The melting temperature of the monolayer ice decreases with the increasing strength of the external field due to the field-induced disruption of the water-wall interaction induced well-ordered network of the hydrogen bond. This electromelting process should add an important new ingredient to the physics of water.

  9. Geology and mineralization at the Ishmas Kabir gold prospect, Ishmas gold district, Kingdom of Saudi Arabia

    USGS Publications Warehouse

    Walker, B.M.; Ben Talib, Majed; El Komi, Mohamed; Hussain, M.A.; Christian, R.P.

    1990-01-01

    Quartz veins intersected by drill holes are surrounded by mylonite schist. Quartz and carbonate veins less than 5 mm thick are boudined, whereas thick quartz veins (£ 1.2 m) have disrupted and brecciated margins; mylonitized country rock envelops quartz-vein fragments. Sulfide mineralization associated with vein formation predates this rock-deformation event. Contemporaneous brittle and ductile deformation of quartz veins and country rocks occurred during the Nabitah orogeny. Supergene gold enrichment took place much later.

  10. Anti-fouling chemistry of chiral monolayers: enhancing biofilm resistance on racemic surface.

    PubMed

    Bandyopadhyay, Debjyoti; Prashar, Deepali; Luk, Yan-Yeung

    2011-05-17

    This work reports the resistance to protein adsorption and bacterial biofilm formation by chiral monolayers of polyol-terminated alkanethiols surrounding micrometer-sized patterns of methyl-terminated alkanethiols on gold films. We discover that patterned surfaces surrounded by chiral polyol monolayers can distinguish different stages of biofilm formation. After inoculation on the surfaces, bacteria first reversibly attached on the chiral polyol monolayers. Over time, the bacteria detached from the polyol surfaces, and attached on the hydrophobic micropatterns to form biofilms. Interestingly, while both enantiomers of gulitol- and mannonamide-terminated monolayer resisted adsorption of proteins (bovine serum albumin, lysozyme, and fibrinogen) and confined biofilms formed on the micropatterns, the monolayers formed by the racemic mixture of either pair of enantiomers exhibited stronger antifouling chemistry against both protein adsorption and biofilm formation than monolayers formed by one enantiomer alone. These results reveal the different chemistries that separate the different stages of biofilm formation, and the stereochemical influence on resisting biofoulings at a molecular-level.

  11. Characterization of charge transfer processes inself-assembled monolayers by high-pressure electrochemical techniques

    SciTech Connect

    Cruanes, M.T.; Drickamer, H.G.; Faulkner, L.R.

    1995-10-01

    Here we report the first high-pressure investigation of redox processes in surface-confined monolayers. We have explored the electrochemical behavior of ferrocene-terminated self-assembled monolayers (SAMs) on gold electrodes immersed in aqueous solutions containing 1M NaClO{sub 4}. Electron-transfer reaction for ferrocene in the monolayer is restricted with the application of pressure, whereas the same reaction for ferrocene in solution is not. The dependence of the cyclic voltammetric peak redox potentials on pressure reveals that the oxidation of the ferrocene within the monolayer becomes thermodynamically and kinetically more difficult at high pressures. At pressures above 1-2 kbar, positive volumes of reaction are associated with the oxidation process, indicating that the oxidation step involves an increase in volume. Different monolayer samples, exhibiting different voltammetric responses, appear to impose different volume constraints on the charge transfer reaction and, therefore, present different pressure responses within a general common trend. These results point out the importance of structural and environmental effects, via steric constraints, on electron transfer processes in surface-confined monolayer assemblies. 36 refs., 7 figs., 6 tabs.

  12. Gold deposits of the Carolina Slate Belt, southeastern United States--Age and origin of the major gold producers

    USGS Publications Warehouse

    Foley, Nora K.; Ayuso, Robert A.

    2012-01-01

    Gold- and iron sulfide-bearing deposits of the southeastern United States have distinctive mineralogical and geochemical features that provide a basis for constructing models of ore genesis for exploration and assessment of gold resources. The largest (historic) deposits, in approximate million ounces of gold (Moz Au), include those in the Haile (~ 4.2 Moz Au), Ridgeway (~1.5 Moz Au), Brewer (~0.25 Moz Au), and Barite Hill (0.6 Moz Au) mines. Host rocks are Late Proterozoic to early Paleozoic (~553 million years old) metaigneous and metasedimentary rocks of the Carolina Slate Belt that share a geologic affinity with the classic Avalonian tectonic zone. The inferred syngenetic and epithermal-subvolcanic quartz-porphyry settings occur stratigraphically between sequences of metavolcanic rocks of the Persimmon Fork and Uwharrie Formations and overlying volcanic and epiclastic rocks of the Tillery and Richtex Formations (and regional equivalents). The Carolina Slate Belt is highly prospective for many types of gold ore hosted within quartz-sericite-pyrite altered volcanic rocks, juvenile metasedimentary rocks, and in associated shear zones. For example, sheared and deformed auriferous volcanogenic massive sulfide deposits at Barite Hill, South Carolina, and in the Gold Hill trend, North Carolina, are hosted primarily by laminated mudstone and felsic volcanic to volcaniclastic rocks. The high-sulfidation epithermal style of gold mineralization at Brewer and low-sulfidation gold ores of the Champion pit at Haile occur in breccias associated with subvolcanic quartz porphyry and within crystal-rich tuffs, ash flows, and subvolcanic rhyolite. The Ridgeway and Haile deposits are primarily epithermal replacements and feeder zones within (now) metamorphosed crystal-rich tuffs, volcaniclastic sediments, and siltstones originally deposited in a marine volcanic-arc basinal setting. Recent discoveries in the region include (1) extensions of known deposits, such as at Haile where

  13. Determination of the concentration and the average number of gold atoms in a gold nanoparticle by osmotic pressure.

    PubMed

    Lu, Yan; Wang, Lixia; Chen, Dejun; Wang, Gongke

    2012-06-26

    For an ideal solution, an analytical expression for the macromolecule concentration, electrolyte concentration, and solution osmotic pressure is obtained on the basis of the van't Hoff equation and the Donnan equilibrium. The expression was further applied to a colloid solution of about 3 nm glutathione-stabilized gold nanoparticles. The concentration of the colloid solution and the average net ion charge number for each gold nanoparticle were determined with the measured osmotic pressure data. Meanwhile, the gold contents of the solutions were analyzed by means of atomic absorption spectrophotometry, and the results were combined with the determined concentration of gold nanoparticle colloids to determine that the average number of gold atoms per 3 nm gold nanoparticle is 479, which is 1/1.7 times the number of atoms in bulk metallic gold of the same size. The same proportion also occurred in the 2 nm 4-mercaptobenzoic acid monolayer-protected gold nanoparticles prepared by Ackerson et al., who utilized the quantitative high-angle annular dark-field scanning transmission electron microscope to determine the average number of gold atoms per nanoparticle (Ackerson, C. J.; Jadzinsky, P. D.; Sexton J. Z.; Bushnell, D. A.; Kornberg, R. D. Synthesis and Bioconjugation of 2 and 3 nm-Diameter Gold Nanoparticles. Bioconjugate Chem. 2010, 21, 214-218).

  14. Volcanogenic Massive Sulfide Deposit Density

    USGS Publications Warehouse

    Mosier, Dan L.; Singer, Donald A.; Berger, Vladimir I.

    2007-01-01

    A mineral-deposit density model for volcanogenic massive sulfide deposits was constructed from 38 well-explored control areas from around the world. Control areas contain at least one exposed volcanogenic massive sulfide deposit. The control areas used in this study contain 150 kuroko, 14 Urals, and 25 Cyprus massive sulfide subtypes of volcanogenic massive sulfide deposits. For each control area, extent of permissive rock, number of exposed volcanogenic massive sulfide deposits, map scale, deposit age, and deposit density were determined. The frequency distribution of deposit densities in these 38 control areas provides probabilistic estimates of the number of deposits for tracts that are permissive for volcanogenic massive sulfide deposits-90 percent of the control areas have densities of 100 or more deposits per 100,000 square kilometers, 50 percent of the control areas have densities of 700 or more deposits per 100,000 square kilometers, and 10 percent of the control areas have densities of 3,700 or more deposits per 100,000 square kilometers. Both map scale and the size of the control area are shown to be predictors of deposit density. Probabilistic estimates of the number of volcanogenic massive sulfide deposits can be made by conditioning the estimates on sizes of permissive area. The model constructed for this study provides a powerful tool for estimating the number of undiscovered volcanogenic massive sulfide deposits when conducting resource assessments. The value of these deposit densities is due to the consistency of these models with the grade and tonnage and the descriptive models. Mineral-deposit density models combined with grade and tonnage models allow reasonable estimates of the number, size, and grades of volcanogenic massive sulfide deposits to be made.

  15. Biomineralization of gold: biofilms on bacterioform gold.

    PubMed

    Reith, Frank; Rogers, Stephen L; McPhail, D C; Webb, Daryl

    2006-07-14

    Bacterial biofilms are associated with secondary gold grains from two sites in Australia. 16S ribosomal DNA clones of the genus Ralstonia that bear 99% similarity to the bacterium Ralstonia metallidurans-shown to precipitate gold from aqueous gold(III) tetrachloride-were present on all DNA-positive gold grains but were not detected in the surrounding soils. These results provide evidence for the bacterial contribution to the authigenic formation of secondary bacterioform gold grains and nuggets.

  16. Sulfides and oxides in comets

    NASA Technical Reports Server (NTRS)

    Rietmeijer, Frans J. M.

    1988-01-01

    Metal abundances associated with Sun-grazing P/comet Ikeya-Seki 1965f, the mineralogy of chrondritic interplanetary dust particles and cosmochemical affinities of Co, V, Cr, and Ni in extraterrestrial materials and probable vaporization data for nonsilicate minerals are used to evaluate the putative dearth of nonsilicates in short-period comets. It is concluded that sulfides and oxides are common, albeit minor, constituents of these comets. Sulfides and oxides can form in situ during perihelion passage in the nucleus of active short-period comets by sulfidation of Mg, Fe-silicates.

  17. Oxidation state of gold and arsenic in gold-bearing arsenian pyrite

    SciTech Connect

    Simon, G.; Huang, H.; Penner-Hahn, J.E.; Kesler, S.E.; Kao, L.S.

    1999-07-01

    XANES measurements on gold-bearing arsenian pyrite from the Twin Creeks Carlin-type gold deposits show that gold is present as both Au{sup 0} and Au{sup 1+} and arsenic is present as As{sup 1{minus}}. Au{sup 0} is attributed to sub-micrometer size inclusions of free gold, whereas Au{sup 1+} is attributed to gold in the lattice of the arsenian pyrite. STEM observations suggest that As{sup 1{minus}} is probably concentrated in angstrom-scale, randomly distributed layers with a marcasite or arsenopyrite structure. Ionic gold (Au{sup 1+}) could be concentrated in these layers as well, and is present in both twofold- and fourfold-coordinated forms, with fourfold-coordinated Au{sup 1+} more abundant. Twofold-coordinated Au{sup 1+} is similar to gold in Au{sub 2}S in which it is linearly coordinated to two sulfur atoms. The nature of fourfold-coordinated Au{sup 1+} is not well understood, although it might be present as an Au-As-S compound where gold is bonded in fourfold coordination to sulfur and arsenic atoms, or in vacancy positions on a cation site in the arsenian pyrite. Au{sup 1+} was probably incorporated into arsenian pyrite by adsorption onto pyrite surfaces during crystal growth. The most likely compound in the case of twofold-coordinated Au{sup 1+} was probably a tri-atomic surface complex such as S{sub pyrite}-Au{sup 1+}-S{sub bi-sulfide}H or Au{sup 1+}-S-Au{sup 1+}. The correlation between gold and arsenic might be related to the role of arsenic in enhancing the adsorption of gold complexes of this type on pyrite surfaces, possibly through semiconductor effects.

  18. Apparatus for use in sulfide chemiluminescence detection

    DOEpatents

    Spurlin, S.R.; Yeung, E.S.

    1987-01-06

    A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

  19. Apparatus for use in sulfide chemiluminescence detection

    DOEpatents

    Spurlin, Stanford R.; Yeung, Edward S.

    1987-01-01

    A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

  20. Prevention of sulfide oxidation in sulfide-rich waste rock

    NASA Astrophysics Data System (ADS)

    Nyström, Elsa; Alakangas, Lena

    2015-04-01

    The ability to reduce sulfide oxidation in waste rock after mine closure is a widely researched area, but to reduce and/or inhibit the oxidation during operation is less common. Sulfide-rich (ca 30 % sulfur) waste rock, partially oxidized, was leached during unsaturated laboratory condition. Trace elements such as As and Sb were relatively high in the waste rock while other sulfide-associated elements such as Cu, Pb and Zn were low compared to common sulfide-rich waste rock. Leaching of unsaturated waste rock lowered the pH, from around six down to two, resulting in continuously increasing element concentrations during the leaching period of 272 days. The concentrations of As (65 mg/L), Cu (6.9 mg/L), Sb (1.2 mg/L), Zn (149 mg/L) and S (43 g/L) were strongly elevated at the end of the leaching period. Different alkaline industrial residues such as slag, lime kiln dust and cement kiln dust were added as solid or as liquid to the waste rock in an attempt to inhibit sulfide oxidation through neo-formed phases on sulfide surfaces in order to decrease the mobility of metals and metalloids over longer time scale. This will result in a lower cost and efforts of measures after mine closure. Results from the experiments will be presented.

  1. Donor/Acceptor Mixed Self-Assembled Monolayers for Realising a Multi-Redox-State Surface.

    PubMed

    Casado-Montenegro, Javier; Marchante, Elena; Crivillers, Núria; Rovira, Concepció; Mas-Torrent, Marta

    2016-06-17

    Mixed molecular self-assembled monolayers (SAMs) on gold, based on two types of electroactive molecules, that is, electron-donor (ferrocene) and electron-acceptor (anthraquinone) molecules, are prepared as an approach to realise surfaces exhibiting multiple accessible redox states. The SAMs are investigated in different electrolyte media. The nature of these media has a strong impact on the types of redox processes that take place and on the redox potentials. Under optimised conditions, surfaces with three redox states are achieved. Such states are accessible in a relatively narrow potential window in which the SAMs on gold are stable. This communication elucidates the key challenges in fabricating bicomponent SAMs as electrochemical switches.

  2. Pit Formation during the Self-Assembly of Dithiol Monolayers on Au(111)

    NASA Astrophysics Data System (ADS)

    Macdairmid, A. R.; Cappello, M. L.; Keeler, W. J.; Banks, J. T.; Gallagher, M. C.

    2000-03-01

    The formation of pits one gold atom deep during the growth of alkanethiol monolayers on Au(111), has been observed previously by others. Explanations for pit formation include etching of the substrate, or mass transport of gold atom + thiol molecule on the surface, due to changes in surface energy^1. We have investigated the structure of dithiothreitol (DTT) SAMs on Au(111). Ex situ STM measurements indicate similar pitting occurs during formation of the dithiol monolayer. The degree of pitting depends on exposure time, sample temperature during formation, and subsequent annealing of the sample. Pitting is enhanced considerasbly when DTT is coordinated with Ti, in fact DTT/Ti films exhibit considerable pit motion during STM imaging. ^1 F. Teran et al. Electrochimica Acta 44, 1053 (1998).

  3. Nanopattern formation in self-assembled monolayers of thiol-capped Au nanocrystals

    NASA Astrophysics Data System (ADS)

    Banerjee, R.; Hazra, S.; Banerjee, S.; Sanyal, M. K.

    2009-11-01

    The structure and the stability of the transferred monolayers of gold-thiol nanoparticles, formed at air-water interface at different surface pressure, on to silicon surface have been studied using two complementary techniques, x-ray reflectivity and atomic force microscopy (AFM). Networklike nanopatterns, observed through AFM, of the in-plane aggregated nanoparticles can be attributed to the late stage drying of the liquid trapped in the islands formed by nanoparticles. During drying process the trapped liquid leaves pinholes in the islands which by the process of nucleation and growth carry the mobile nanoparticles on their advancing fronts such that the nanoparticles are trapped at the boundaries of similar adjacent holes. This process continues bringing about in-plane as well as out-of-plane restructuring in the monolayer until the liquid evaporates completely rendering a patterned structure to the islands and instability in the monolayer is then stabilized.

  4. Is It Real Gold?

    ERIC Educational Resources Information Center

    Harris, Harold H.

    1999-01-01

    Features acid tests for determining whether jewelry is "real" gold or simply gold-plated. Describes the carat system of denoting gold content and explains how alloys are used to create various shades of gold jewelry. Addresses the question of whether gold jewelry can turn a wearer's skin green by considering various oxidation reactions.…

  5. Hydrogen sulfide in signaling pathways.

    PubMed

    Olas, Beata

    2015-01-15

    For a long time hydrogen sulfide (H₂S) was considered a toxic compound, but recently H₂S (at low concentrations) has been found to play an important function in physiological processes. Hydrogen sulfide, like other well-known compounds - nitric oxide (NO) and carbon monoxide (CO) is a gaseous intracellular signal transducer. It regulates the cell cycle, apoptosis and the oxidative stress. Moreover, its functions include neuromodulation, regulation of cardiovascular system and inflammation. In this review, I focus on the metabolism of hydrogen sulfide (including enzymatic pathways of H₂S synthesis from l- and d-cysteine) and its signaling pathways in the cardiovascular system and the nervous system. I also describe how hydrogen sulfide may be used as therapeutic agent, i.e. in the cardiovascular diseases.

  6. Platinum metals magmatic sulfide ores.

    PubMed

    Naldrett, A J; Duke, J M

    1980-06-27

    Platinum-group elements (PGE) are mined predominantly from deposits that have formed by the segregation of molten iron-nickel-copper sulfides from silicate magmas. The absolute concentrations of PGE in sulfides from different deposits vary over a range of five orders of magnitude, whereas those of other chalcophile elements vary by factors of only 2 to 100. However, the relative proportions of the different PGE in a given deposit are systematically related to the nature of the parent magma. The absolute and relative concentrations of PGE in magmatic sulfides are explained in terms of the degree of partial melting of mantle peridotite required to produce the parent magma and the processes of batch equilibration and fractional segregation of sulfides. The Republic of South Africa and the U.S.S.R. together possess more than 97 percent of the world PGE reserves, but significant undeveloped resources occur in North America. The Stillwater complex in Montana is perhaps the most important example.

  7. Mechanical and Electrical Properties of Palladium-Coated Copper Wires with Flash Gold

    NASA Astrophysics Data System (ADS)

    Chang, Chia-Yun; Hung, Fei-Yi; Lui, Truan-Sheng

    2017-03-01

    Palladium-coated copper wire with flash gold (PCA) is a fine wire with an oxidation resistance layer. A new sulfidation test has been assessed in this work, confirming that PCA wires show better sulfidation corrosion resistance than either palladium-coated or bare copper wires. The sulfided surface of PCA was analyzed, along with its bonding strength and electrical properties. The metallurgic mechanism for formation of free air balls during the electric flame-off (EFO) process was identified. The flash gold layer of PCA wires can improve certain shortcomings, including: (1) efficiently promoting sulfidation corrosion resistance, (2) solving the problem of palladium segregation during the EFO process, (3) reducing the starting voltage, and (4) stabilizing the electrical resistivity of the bonding interface.

  8. Thermoelectric Properties of Lanthanum Sulfide

    NASA Technical Reports Server (NTRS)

    Wood, C.; Lockwood, R.; Parker, J. B.; Zoltan, A.; Zoltan, L. D.; Danielson, L.; Raag, V.

    1987-01-01

    Report describes measurement of Seebeck coefficient, electrical resistivity, thermal conductivity, and Hall effect in gamma-phase lanthanum sulfide with composition of La3-x S4. Results of study, part of search for high-temperature thermoelectric energy-conversion materials, indicate this sulfide behaves like extrinsic semiconductor over temperature range of 300 to 1,400 K, with degenerate carrier concentration controlled by stoichiometric ratio of La to S.

  9. Recognition tunneling measurement of the conductance of DNA bases embedded in self-assembled monolayers.

    PubMed

    Huang, Shuo; Chang, Shuai; He, Jin; Zhang, Peiming; Liang, Feng; Tuchband, Michael; Li, Shengqing; Lindsay, Stuart

    2010-12-09

    The DNA bases interact strongly with gold electrodes, complicating efforts to measure the tunneling conductance through hydrogen-bonded Watson Crick base pairs. When bases are embedded in a self-assembled alkane-thiol monolayer to minimize these interactions, new features appear in the tunneling data. These new features track the predictions of density-functional calculations quite well, suggesting that they reflect tunnel conductance through hydrogen-bonded base pairs.

  10. Self-assembled monolayers improve protein distribution on holey carbon cryo-EM supports

    PubMed Central

    Meyerson, Joel R.; Rao, Prashant; Kumar, Janesh; Chittori, Sagar; Banerjee, Soojay; Pierson, Jason; Mayer, Mark L.; Subramaniam, Sriram

    2014-01-01

    Poor partitioning of macromolecules into the holes of holey carbon support grids frequently limits structural determination by single particle cryo-electron microscopy (cryo-EM). Here, we present a method to deposit, on gold-coated carbon grids, a self-assembled monolayer whose surface properties can be controlled by chemical modification. We demonstrate the utility of this approach to drive partitioning of ionotropic glutamate receptors into the holes, thereby enabling 3D structural analysis using cryo-EM methods. PMID:25403871

  11. Enhancement in sensitivity of copper sulfide thin film ammonia gas sensor: Effect of swift heavy ion irradiation

    SciTech Connect

    Sagade, Abhay Abhimanyu; Sharma, Ramphal; Sulaniya, Indra

    2009-02-15

    The studies are carried out on the effect of swift heavy ion (SHI) irradiation on surface morphology and electrical properties of copper sulfide (Cu{sub x}S) thin films with three different chemical compositions (x values). The irradiation experiments have been carried out on Cu{sub x}S films with x=1.4, 1.8, and 2 by 100 MeV gold heavy ions at room temperature. These as-deposited and irradiated thin films have been used to detect ammonia gas at room temperature (300 K). The SHI irradiation treatment on x=1.4 and 1.8 copper sulfide films enhances the sensitivity of the gas sensor. The results are discussed considering high electronic energy deposition by 100 MeV gold heavy ions in a matrix of copper sulfide.

  12. Modeling Stimuli-Responsive Nanoparticle Monolayer

    NASA Astrophysics Data System (ADS)

    Yong, Xin

    2015-03-01

    Using dissipative particle dynamics (DPD), we model a monolayer formed at the water-oil interface, which comprises stimuli-responsive nanoparticles. The solid core of the nanoparticle encompasses beads arranged in an fcc lattice structure and its surface is uniformly grafted with stimuli-responsive polymer chains. The surface-active nanoparticles adsorb to the interface from the suspension to minimize total energy of the system and create a monolayer covering the interface. We investigate the monolayer formation by characterizing the detailed adsorption kinetics. We explore the microstructure of the monolayer at different surface coverage, including the particle crowding and ordering, and elucidate the response of monolayer to external stimuli. The collective behavior of the particles within the monolayer is demonstrated quantitatively by vector-vector autocorrelation functions. This study provides a fundamental understanding of the interfacial behavior of stimuli-responsive nanoparticles.

  13. Electron transfer through a self-assembled monolayer of a double-helix peptide with linking the terminals by ferrocene.

    PubMed

    Okamoto, Shinpei; Morita, Tomoyuki; Kimura, Shunsaku

    2009-03-03

    A unique molecular structure, a double-helix peptide, was self-assembled on gold, and the electron transfer through the monolayer was studied. The double-helix peptide consists of two 9mer 3(10)-helical peptide chains having a disulfide group at each N terminal and being linked by a ferrocene dicarboxylic acid between the C terminals. Each helical peptide chain has three naphthyl groups in a linear arrangement along the helix. The monolayer properties and the electron transfer from the ferrocene unit to gold were studied with reference peptides with a similar double helix but without naphthyl groups, a single helix with a dicarboxylic ferrocene unit, and a single helix with a monocarboxylic ferrocene unit. It was demonstrated that the naphthyl groups on the side chains had no effect on electron transfer, and the electron-transfer rate in the double-helix monolayer was not promoted, despite the two electron pathways in the molecule. We propose that in the double-helix monolayer, molecular motions are suppressed, possibly by its rigid structure tethered by the two linkers on gold to cancel out acceleration effects of the 2-fold electron pathways and the ferrocene substitution number. The factors that affect the electron-transfer reaction across the helical peptide SAMs are discussed in depth.

  14. Structure and shear response of lipid monolayers

    SciTech Connect

    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.

  15. A Reaction Involving Oxygen and Metal Sulfides.

    ERIC Educational Resources Information Center

    Hill, William D. Jr.

    1986-01-01

    Describes a procedure for oxygen generation by thermal decomposition of potassium chlorate in presence of manganese dioxide, reacted with various sulfides. Provides a table of sample product yields for various sulfides. (JM)

  16. Sulfide Stability of Planetary Basalts

    NASA Technical Reports Server (NTRS)

    Caiazza, C. M.; Righter, K.; Gibson, E. K., Jr.; Chesley, J. T.; Ruiz, J.

    2004-01-01

    The isotopic system, 187Re 187Os, can be used to determine the role of crust and mantle in magma genesis. In order to apply the system to natural samples, we must understand variations in Re/Os concentrations. It is thought that low [Os] and [Re] in basalts can be attributed to sulfide (FeS) saturation, as Re behaves incompatibly to high degrees of evolution until sulfide saturation occurs [1]. Previous work has shown that lunar basalts are sulfide under-saturated, and mid-ocean ridge, ocean-island and Martian (shergottites) basalts are saturated [2,3]. However, little is known about arc basalts. In this study, basaltic rocks were analyzed across the Trans-Mexican Volcanic Belt.

  17. A self assembled monolayer based microfluidic sensor for urea detection

    NASA Astrophysics Data System (ADS)

    Srivastava, Saurabh; Solanki, Pratima R.; Kaushik, Ajeet; Ali, Md. Azahar; Srivastava, Anchal; Malhotra, B. D.

    2011-07-01

    Urease (Urs) and glutamate dehydrogenase (GLDH) have been covalently co-immobilized onto a self-assembled monolayer (SAM) comprising of 10-carboxy-1-decanthiol (CDT) via EDC-NHS chemistry deposited onto one of the two patterned gold (Au) electrodes for estimation of urea using poly(dimethylsiloxane) based microfluidic channels (2 cm × 200 μm × 200 μm). The CDT/Au and Urs-GLDH/CDT/Au electrodes have been characterized using Fourier transform infrared (FTIR) spectroscopy, contact angle (CA), atomic force microscopy (AFM) and electrochemical cyclic voltammetry (CV) techniques. The electrochemical response measurement of a Urs-GLDH/CDT/Au bioelectrode obtained as a function of urea concentration using CV yield linearity as 10 to 100 mg dl-1, detection limit as 9 mg dl-1 and high sensitivity as 7.5 μA mM-1 cm-2.

  18. Effects of irradiated biodegradable polymer in endothelial cell monolayer formation

    NASA Astrophysics Data System (ADS)

    Arbeitman, Claudia R.; del Grosso, Mariela F.; Behar, Moni; García Bermúdez, Gerardo

    2013-11-01

    In this work we study cell adhesion, proliferation and cell morphology of endothelial cell cultured on poly-L-lactide acid (PLLA) modified by heavy ion irradiation. Thin films of PLLA samples were irradiated with sulfur (S) at energies of 75 MeV and gold (Au) at 18 MeV ion-beams. Ion beams were provided by the Tandar (Buenos Aires, Argentina) and Tandetron (Porto Alegre, Brazil) accelerators, respectively. The growth of a monolayer of bovine aortic endothelial cells (BAEC) onto unirradiated and irradiated surfaces has been studied by in vitro techniques in static culture. Cell viability and proliferation increased on modified substrates. But the results on unirradiated samples, indicate cell death (necrosis/apoptosis) with the consequent decrease in proliferation. We analyzed the correlation between irradiation parameters and cell metabolism and morphology.

  19. Speciation of surface gold in pressure oxidized carbonaceous gold ores by TOF-SIMS and TOF-LIMS

    NASA Astrophysics Data System (ADS)

    Dimov, S. S.; Chryssoulis, S. L.; Sodhi, R. N.

    2003-01-01

    To the best of our knowledge, this is the first attempt ever to speciate gold preg-robbed by carbonaceous matter using a surface sensitive microbeam technique. This approach enables the direct determination of gold species sorbed on carbonaceous particulates thus providing a new tool in understanding the chemistry of gold sorption on carbon. The reasoning behind this effort was to study the detrimental effect chloride ions have on gold recovery by pressure oxidation of carbonaceous sulfide ores, a technology largely used by the mining industry. The characterization of the sorbed gold species involved three surface sensitive microbeam analytical techniques (TOF-SIMS, TOF-LIMS and XPS) providing confirmatory results for better accuracy. Optimum conditions for detection of gold compounds with minimum fragmentation by TOF-SIMS and TOF-LIMS mass spectrometers have been determined. A reference library of 16 major gold complexes with halogen, thiosulfate, cyanide and thiocyanate groups relevant to the gold recovery processes has been established. The most suitable of the microbeam techniques tested was found to be negative (-ve) ion TOF-LIMS, offering best sensitivity and a small analytical spot size.

  20. Solvent-dependent assembly of terphenyl- and quaterphenyldithiol on gold and gallium arsenide.

    PubMed

    Krapchetov, Dmitry A; Ma, Hong; Jen, Alex K Y; Fischer, Daniel A; Loo, Yueh-Lin

    2005-06-21

    The assembly of terphenyldithiol (TPDT) and quaterphenyldithiol (QPDT) on gold and gallium arsenide from ethanol (EtOH), tetrahydrofuran (THF), and solutions consisting of both solvents has been characterized by near-edge X-ray absorption fine structure spectroscopy. The surface coverage and the average orientation of both TPDT and QPDT on gold are solvent-independent. These molecules readily form monolayers on gold with an ensemble-average backbone tilt of 30 degrees +/- 3 degrees from the substrate normal. In sharp contrast, the assembly of TPDT and QPDT on gallium arsenide is extremely solvent-sensitive. At high ethanol fractions, both molecules form monolayers with an ensemble-average orientation that is indistinguishable from those on gold substrates. At low ethanol fractions and in pure THF, however, these molecules are disordered on gallium arsenide and the surface coverage is poor.

  1. Dewetting of a solid monolayer.

    PubMed

    Pierre-Louis, O; Chame, Anna; Saito, Yukio

    2007-09-28

    We report on the dewetting of a monolayer on a solid substrate, where mass transport occurs via surface diffusion. For a wide range of parameters, a labyrinthine pattern of bilayer islands is formed. An irreversible regime and a thermodynamic regime are identified. In both regimes, the velocity of a dewetting front, the wavelength of the bilayer island pattern, and the rate of nucleation of dewetted zones are obtained. We also point out the existence of a scaling behavior, which is analyzed by means of a geometrical model.

  2. Sulfur radical species form gold deposits on Earth

    PubMed Central

    Pokrovski, Gleb S.; Kokh, Maria A.; Guillaume, Damien; Borisova, Anastassia Y.; Gisquet, Pascal; Hazemann, Jean-Louis; Lahera, Eric; Del Net, William; Proux, Olivier; Testemale, Denis; Haigis, Volker; Jonchière, Romain; Seitsonen, Ari P.; Ferlat, Guillaume; Vuilleumier, Rodolphe; Saitta, Antonino Marco; Boiron, Marie-Christine; Dubessy, Jean

    2015-01-01

    Current models of the formation and distribution of gold deposits on Earth are based on the long-standing paradigm that hydrogen sulfide and chloride are the ligands responsible for gold mobilization and precipitation by fluids across the lithosphere. Here we challenge this view by demonstrating, using in situ X-ray absorption spectroscopy and solubility measurements, coupled with molecular dynamics and thermodynamic simulations, that sulfur radical species, such as the trisulfur ion S3−, form very stable and soluble complexes with Au+ in aqueous solution at elevated temperatures (>250 °C) and pressures (>100 bar). These species enable extraction, transport, and focused precipitation of gold by sulfur-rich fluids 10–100 times more efficiently than sulfide and chloride only. As a result, S3− exerts an important control on the source, concentration, and distribution of gold in its major economic deposits from magmatic, hydrothermal, and metamorphic settings. The growth and decay of S3− during the fluid generation and evolution is one of the key factors that determine the fate of gold in the lithosphere. PMID:26460040

  3. Sulfur radical species form gold deposits on Earth.

    PubMed

    Pokrovski, Gleb S; Kokh, Maria A; Guillaume, Damien; Borisova, Anastassia Y; Gisquet, Pascal; Hazemann, Jean-Louis; Lahera, Eric; Del Net, William; Proux, Olivier; Testemale, Denis; Haigis, Volker; Jonchière, Romain; Seitsonen, Ari P; Ferlat, Guillaume; Vuilleumier, Rodolphe; Saitta, Antonino Marco; Boiron, Marie-Christine; Dubessy, Jean

    2015-11-03

    Current models of the formation and distribution of gold deposits on Earth are based on the long-standing paradigm that hydrogen sulfide and chloride are the ligands responsible for gold mobilization and precipitation by fluids across the lithosphere. Here we challenge this view by demonstrating, using in situ X-ray absorption spectroscopy and solubility measurements, coupled with molecular dynamics and thermodynamic simulations, that sulfur radical species, such as the trisulfur ion S3(-), form very stable and soluble complexes with Au(+) in aqueous solution at elevated temperatures (>250 °C) and pressures (>100 bar). These species enable extraction, transport, and focused precipitation of gold by sulfur-rich fluids 10-100 times more efficiently than sulfide and chloride only. As a result, S3(-) exerts an important control on the source, concentration, and distribution of gold in its major economic deposits from magmatic, hydrothermal, and metamorphic settings. The growth and decay of S3(-) during the fluid generation and evolution is one of the key factors that determine the fate of gold in the lithosphere.

  4. Nanostructured metal sulfides for energy storage

    NASA Astrophysics Data System (ADS)

    Rui, Xianhong; Tan, Huiteng; Yan, Qingyu

    2014-08-01

    Advanced electrodes with a high energy density at high power are urgently needed for high-performance energy storage devices, including lithium-ion batteries (LIBs) and supercapacitors (SCs), to fulfil the requirements of future electrochemical power sources for applications such as in hybrid electric/plug-in-hybrid (HEV/PHEV) vehicles. Metal sulfides with unique physical and chemical properties, as well as high specific capacity/capacitance, which are typically multiple times higher than that of the carbon/graphite-based materials, are currently studied as promising electrode materials. However, the implementation of these sulfide electrodes in practical applications is hindered by their inferior rate performance and cycling stability. Nanostructures offering the advantages of high surface-to-volume ratios, favourable transport properties, and high freedom for the volume change upon ion insertion/extraction and other reactions, present an opportunity to build next-generation LIBs and SCs. Thus, the development of novel concepts in material research to achieve new nanostructures paves the way for improved electrochemical performance. Herein, we summarize recent advances in nanostructured metal sulfides, such as iron sulfides, copper sulfides, cobalt sulfides, nickel sulfides, manganese sulfides, molybdenum sulfides, tin sulfides, with zero-, one-, two-, and three-dimensional morphologies for LIB and SC applications. In addition, the recently emerged concept of incorporating conductive matrices, especially graphene, with metal sulfide nanomaterials will also be highlighted. Finally, some remarks are made on the challenges and perspectives for the future development of metal sulfide-based LIB and SC devices.

  5. Nanostructured metal sulfides for energy storage.

    PubMed

    Rui, Xianhong; Tan, Huiteng; Yan, Qingyu

    2014-09-07

    Advanced electrodes with a high energy density at high power are urgently needed for high-performance energy storage devices, including lithium-ion batteries (LIBs) and supercapacitors (SCs), to fulfil the requirements of future electrochemical power sources for applications such as in hybrid electric/plug-in-hybrid (HEV/PHEV) vehicles. Metal sulfides with unique physical and chemical properties, as well as high specific capacity/capacitance, which are typically multiple times higher than that of the carbon/graphite-based materials, are currently studied as promising electrode materials. However, the implementation of these sulfide electrodes in practical applications is hindered by their inferior rate performance and cycling stability. Nanostructures offering the advantages of high surface-to-volume ratios, favourable transport properties, and high freedom for the volume change upon ion insertion/extraction and other reactions, present an opportunity to build next-generation LIBs and SCs. Thus, the development of novel concepts in material research to achieve new nanostructures paves the way for improved electrochemical performance. Herein, we summarize recent advances in nanostructured metal sulfides, such as iron sulfides, copper sulfides, cobalt sulfides, nickel sulfides, manganese sulfides, molybdenum sulfides, tin sulfides, with zero-, one-, two-, and three-dimensional morphologies for LIB and SC applications. In addition, the recently emerged concept of incorporating conductive matrices, especially graphene, with metal sulfide nanomaterials will also be highlighted. Finally, some remarks are made on the challenges and perspectives for the future development of metal sulfide-based LIB and SC devices.

  6. 30 CFR 250.808 - Hydrogen sulfide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 2 2013-07-01 2013-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or...

  7. 30 CFR 250.808 - Hydrogen sulfide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 2 2014-07-01 2014-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or...

  8. 30 CFR 250.808 - Hydrogen sulfide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 2 2011-07-01 2011-07-01 false Hydrogen sulfide. 250.808 Section 250.808... Safety Systems § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown, as defined in § 250.490 of this...

  9. 30 CFR 250.504 - Hydrogen sulfide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.504 Section 250.504... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Completion Operations § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or...

  10. 30 CFR 250.604 - Hydrogen sulfide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.604 Section 250.604... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Well-Workover Operations § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or...

  11. 30 CFR 250.604 - Hydrogen sulfide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 2 2011-07-01 2011-07-01 false Hydrogen sulfide. 250.604 Section 250.604...-Workover Operations § 250.604 Hydrogen sulfide. When a well-workover operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined...

  12. 30 CFR 250.808 - Hydrogen sulfide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false Hydrogen sulfide. 250.808 Section 250.808... OPERATIONS IN THE OUTER CONTINENTAL SHELF Oil and Gas Production Safety Systems § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of...

  13. 30 CFR 250.808 - Hydrogen sulfide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 2 2012-07-01 2012-07-01 false Hydrogen sulfide. 250.808 Section 250.808 Mineral Resources BUREAU OF SAFETY AND ENVIRONMENTAL ENFORCEMENT, DEPARTMENT OF THE INTERIOR OFFSHORE OIL... § 250.808 Hydrogen sulfide. Production operations in zones known to contain hydrogen sulfide (H2S) or...

  14. 30 CFR 250.504 - Hydrogen sulfide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 2 2011-07-01 2011-07-01 false Hydrogen sulfide. 250.504 Section 250.504...-Completion Operations § 250.504 Hydrogen sulfide. When a well-completion operation is conducted in zones known to contain hydrogen sulfide (H2S) or in zones where the presence of H2S is unknown (as defined...

  15. Scanning Electrochemical Microscopy of DNA Monolayers Modified with Nile Blue

    PubMed Central

    Gorodetsky, Alon A.; Hammond, William J.; Hill, Michael G.; Slowinski, Krzysztof; Barton, Jacqueline K.

    2009-01-01

    Scanning electrochemical microscopy (SECM) is used to probe long-range charge transport (CT) through DNA monolayers containing the redox-active Nile Blue (NB) intercalator covalently affixed at a specific location in the DNA film. At substrate potentials negative of the formal potential of covalently attached NB, the electrocatalytic reduction of Fe(CN)63− generated at the SECM tip is observed only when NB is located at the DNA/solution interface; for DNA films containing NB in close proximity to the DNA/electrode interface, the electrocatalytic effect is absent. This behavior is consistent with both rapid DNA-mediated CT between the NB intercalator and the gold electrode as well as a rate-limiting electron transfer between NB and the solution phase Fe(CN)63−. The DNA-mediated nature of the catalytic cycle is confirmed through sequence-specific and localized detection of attomoles of TATA-binding protein, a transcription factor that severely distorts DNA upon binding. Importantly, the strategy outlined here is general and allows for the local investigation of the surface characteristics of DNA monolayers both in the absence and in the presence of DNA binding proteins. These experiments highlight the utility of DNA-modified electrodes as versatile platforms for SECM detection schemes that take advantage of CT mediated by the DNA base pair stack. PMID:19053641

  16. Geology, sulfide geochemistry and supercritical venting at the Beebe Hydrothermal Vent Field, Cayman Trough

    NASA Astrophysics Data System (ADS)

    Webber, Alexander P.; Roberts, Stephen; Murton, Bramley J.; Hodgkinson, Matthew R. S.

    2015-09-01

    The Beebe Vent Field (BVF) is the world's deepest known hydrothermal system, at 4960 m below sea level. Located on the Mid-Cayman Spreading Centre, Caribbean, the BVF hosts high temperature (˜401°C) "black smoker" vents that build Cu, Zn and Au-rich sulfide mounds and chimneys. The BVF is highly gold-rich, with Au values up to 93 ppm and an average Au:Ag ratio of 0.15. Gold precipitation is directly associated with diffuse flow through "beehive" chimneys. Significant mass-wasting of sulfide material at the BVF, accompanied by changes in metal content, results in metaliferous talus and sediment deposits. Situated on very thin (2-3 km thick) oceanic crust, at an ultraslow spreading centre, the hydrothermal system circulates fluids to a depth of ˜1.8 km in a basement that is likely to include a mixture of both mafic and ultramafic lithologies. We suggest hydrothermal interaction with chalcophile-bearing sulfides in the mantle rocks, together with precipitation of Au in beehive chimney structures, has resulted in the formation of a Au-rich volcanogenic massive sulfide (VMS) deposit. With its spatial distribution of deposit materials and metal contents, the BVF represents a modern day analogue for basalt hosted, Au-rich VMS systems.

  17. Influence of buried hydrogen-bonding groups within monolayer films on gas-surface energy exchange and accommodation.

    PubMed

    Ferguson, M K; Lohr, J R; Day, B S; Morris, J R

    2004-02-20

    Self-assembled monolayers (SAMs) of carbonyl-containing alkanethiols on gold are employed to explore the influence of hydrogen-bonding interactions on gas-surface energy exchange and accommodation. H-bonding, COOH-terminated SAMs are found to produce more impulsive scattering and less thermal accommodation than non-H-bonding, COOCH3-terminated monolayers. For carbamate-functionalized SAMs of the form Au/S(CH2)16OCONH(CH2)(n-1)CH3, impulsive scattering decreases and accommodation increases as the H-bonding group is positioned farther below the terminal CH3.

  18. Stilling Waves with Ordered Molecular Monolayers

    ERIC Educational Resources Information Center

    Vitz, Ed

    2008-01-01

    A demonstration of the damping effect of an oil monolayer on water waves is described. The history of this remarkable demonstration--with a 2000 (or more) year span--and a brief explanation in terms of the properties of water and the monolayer are presented. If a layer of olive oil, one molecule thick (about one-ten millionth of a centimeter), is…

  19. Transition metal sulfide loaded catalyst

    DOEpatents

    Maroni, V.A.; Iton, L.E.; Pasterczyk, J.W.; Winterer, M.; Krause, T.R.

    1994-04-26

    A zeolite-based catalyst is described for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C[sub 2]+ hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

  20. Transition metal sulfide loaded catalyst

    DOEpatents

    Maroni, Victor A.; Iton, Lennox E.; Pasterczyk, James W.; Winterer, Markus; Krause, Theodore R.

    1994-01-01

    A zeolite based catalyst for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C.sub.2 + hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

  1. p-Chlorophenyl methyl sulfide

    Integrated Risk Information System (IRIS)

    p - Chlorophenyl methyl sulfide ; CASRN 123 - 09 - 1 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for N

  2. Geochemical studies of rare earth elements in the Portuguese pyrite belt, and geologic and geochemical controls on gold distribution

    USGS Publications Warehouse

    Grimes, David J.; Earhart, Robert L.; de Carvalho, Delfim; Oliveira, Vitor; Oliveira, Jose T.; Castro, Paulo

    1998-01-01

    This report describes geochemical and geological studies which were conducted by the U.S. Geological Survey (USGS) and the Servicos Geologicos de Portugal (SPG) in the Portuguese pyrite belt (PPB) in southern Portugal. The studies included rare earth element (REE) distributions and geological and geochemical controls on the distribution of gold. Rare earth element distributions were determined in representative samples of the volcanic rocks from five west-trending sub-belts of the PPB in order to test the usefulness of REE as a tool for the correlation of volcanic events, and to determine their mobility and application as hydrothermal tracers. REE distributions in felsic volcanic rocks show increases in the relative abundances of heavy REE and a decrease in La/Yb ratios from north to south in the Portuguese pyrite belt. Anomalous amounts of gold are distributed in and near massive and disseminated sulfide deposits in the PPB. Gold is closely associated with copper in the middle and lower parts of the deposits. Weakly anomalous concentrations of gold were noted in exhalative sedimentary rocks that are stratigraphically above massive sulfide deposits in a distal manganiferous facies, whereas anomalously low concentrations were detected in the barite-rich, proximal-facies exhalites. Altered and pyritic felsic volcanic rocks locally contain highly anomalous concentrations of gold, suggesting that disseminated sulfide deposits and the non-ore parts of massive sulfide deposits should be evaluated for their gold potential.

  3. A novel 'Gold on Gold' biosensing scheme for an on-fiber immunoassay

    NASA Astrophysics Data System (ADS)

    Punjabi, N.; Satija, J.; Mukherji, S.

    2015-05-01

    In this paper, we propose a novel „gold on gold‟ biosensing scheme for absorbance based fiber-optic biosensor. First, a self-assembled monolayer of gold nanoparticles is formed at the sensing region of the fiber-optic probe by incubating an amino-silanized probe in a colloidal gold solution. Thereafter, the receptor moieties, i.e. Human immunoglobulin G (HIgG) were immobilized by using standard alkanethiol and classic carbodiimide coupling chemistry. Finally, biosensing experiments were performed with different concentrations of gold nanoparticle-tagged analyte, i.e. Goat anti- Human immunoglobulin G (Nanogold-GaHIgG). The sensor response was observed to be more than five-fold compared to the control bioassay, in which the sensor matrix was devoid of gold nanoparticle film. Also, the response was found to be ~10 times higher compared to the FITC-tagged scheme and ~14.5 times better compared to untagged scheme. This novel scheme also demonstrated the potential in improving the limit of detection for the fiber-optic biosensors.

  4. Nonlinear light scattering by a dipole monolayer

    NASA Astrophysics Data System (ADS)

    Averbukh, B. B.; Averbukh, I. B.

    2013-08-01

    Scattering of a strong p-polarized monochromatic field by a dipole monolayer is considered. It is shown that a triplet should be observed at incident angles (between the wave vector of the incident wave and the normal to the monolayer surface) not too close to π/2 in the spectrum of the scattered radiation. For grazing incidence of a strong field on the monolayer, waves with frequencies of the strong field and the high-frequency component of the triplet scatter forward and backward. In this case, radiation with frequency of the low-frequency component of the triplet propagates in the form of two inhomogeneous waves along the monolayer on both sides of it, exponentially decaying with distance from the monolayer.

  5. Major brazilian gold deposits - 1982 to 1999

    USGS Publications Warehouse

    Thorman, C.H.; Dewitt, E.; Maron, M.A.; Ladeira, E.A.

    2001-01-01

    Brazil has been a major but intermittent producer of gold since its discovery in 1500. Brazil led the world in gold production during the 18th and early 19th centuries. From the late 19th century to the late 20th century, total mining company and garimpeiro production was small and relatively constant at about 5 to 8 t/year. The discovery of alluvial deposits in the Amazon by garimpeiros in the 1970s and the opening of eight mines by mining companies from 1983 to 1990 fueled a major boom in Brazil's gold production, exceeding 100 t/year in 1988 and 1989. However, garimpeiro alluvial production decreased 'rapidly in the 1990s, to about 10 t/year by 1999. Company production increased about tenfold from about 4 t/year in 1982 to 40 t in 1992. Production from 1992 to the present remained relatively stable, even though several mines were closed or were in the process of closing and no new major mines were put into production during that period. Based on their production history from 1982-1999, 17 gold mines are ranked as major (> 20 t) and minor (3-8 t) mines. From 1982-1999, deposits hosted in Archean rocks produced 66% of the gold in Brazil, whereas deposits in Paleoproterozoic and Neoproterozoic rocks accounted for 19% and 15%, respectively. Deposits in metamorphosed sedimentary rocks, especially carbonate-rich rocks and carbonate iron-formation, yielded the great bulk of the gold. Deposits in igneous rocks were of much less importance. The Archean and Paleoproterozoic terranes of Brazil largely lack base-metal-rich volcanogenic massive sulfide deposits, porphyry deposits, and polymetallic veins and sedimentary exhalative deposits. An exception to this is in the Caraja??s Mineral Province.

  6. Biogeochemistry of dissolved hydrogen sulfide species and carbonyl sulfide in the western North Atlantic Ocean

    NASA Astrophysics Data System (ADS)

    Radford-Knȩry, Joël; Cutter, Gregory A.

    1994-12-01

    The biogeochemistry of total sulfide dissolved in the open ocean is a poorly understood component of the global sulfur cycle. Here, the cycling of total sulfide was examined in the western North Atlantic Ocean using specially developed sampling and analytical methods. Total sulfide (particulate + dissolved sulfide) concentrations ranged from <2-550 pmol/L; concentrations were highest in the mixed layer and decreased with depth. Significant levels (up to 19 pmol/L) of free sulfide (uncomplexed sulfide) were determined in the top 50 m of the water column. Sources of total sulfide were examined. In particular, the rate of carbonyl sulfide (OCS) hydrolysis was redetermined under oceanographic conditions, and the depth distribution of OCS was examined. The patterns of near-surface enrichment (up to 150 pmol/L) and depletion at depth observed in OCS depth profiles suggest in situ production of OCS. To quantify the sources and sinks of total sulfide in the mixed layer of the Sargasso Sea, a budget was constructed. The rate of total sulfide production was 5.5 pmol L-1 h-1 (OCS hydrolysis + atmospheric input), and total sulfide removal rate was 115 pmol L -1 h-1 (oxidation + particulate sinking). The significant difference between the known sources and sinks indicates that other processes are important for the cycling of sulfide. Similarities in the depth distribution of total sulfide and chlorophyll a, and results from recent laboratory experiments argue strongly in favor of biological involvement in the production of total sulfide in the open ocean.

  7. Water oxidation using a cobalt monolayer prepared by underpotential deposition.

    PubMed

    Marsh, David A; Yan, Wenbo; Liu, Yu; Hemminger, John C; Penner, Reginald M; Borovik, A S

    2013-11-26

    Development of electrocatalysts for the conversion of water to dioxygen is important in a variety of chemical applications. Despite much research in this field, there are still several fundamental issues about the electrocatalysts that need to be resolved. Two such problems are that the catalyst mass loading on the electrode is subject to large uncertainties and the wetted surface area of the catalyst is often unknown and difficult to determine. To address these topics, a cobalt monolayer was prepared on a gold electrode by underpotential deposition and used to probe its efficiency for the oxidation of water. This electrocatalyst was characterized by atomic force microscopy, grazing-incidence X-ray diffraction, and X-ray photoelectron spectroscopy at various potentials to determine if changes occur on the surface during catalysis. An enhancement of current was observed upon addition of PO4(3-) ions, suggesting an effect from surface-bound ligands on the efficiency of water oxidation. At 500 mV overpotential, current densities of 0.20, 0.74, and 2.4 mA/cm(2) for gold, cobalt, and cobalt in PO4(3-) were observed. This approach thus provided electrocatalysts whose surface areas and activity can be accurately determined.

  8. Ultralow effective work function surfaces using diamondoid monolayers

    NASA Astrophysics Data System (ADS)

    Narasimha, Karthik Thimmavajjula; Ge, Chenhao; Fabbri, Jason D.; Clay, William; Tkachenko, Boryslav A.; Fokin, Andrey A.; Schreiner, Peter R.; Dahl, Jeremy E.; Carlson, Robert M. K.; Shen, Z. X.; Melosh, Nicholas A.

    2016-03-01

    Electron emission is critical for a host of modern fabrication and analysis applications including mass spectrometry, electron imaging and nanopatterning. Here, we report that monolayers of diamondoids effectively confer dramatically enhanced field emission properties to metal surfaces. We attribute the improved emission to a significant reduction of the work function rather than a geometric enhancement. This effect depends on the particular diamondoid isomer, with [121]tetramantane-2-thiol reducing gold's work function from ∼5.1 eV to 1.60 ± 0.3 eV, corresponding to an increase in current by a factor of over 13,000. This reduction in work function is the largest reported for any organic species and also the largest for any air-stable compound. This effect was not observed for sp3-hybridized alkanes, nor for smaller diamondoid molecules. The magnitude of the enhancement, molecule specificity and elimination of gold metal rearrangement precludes geometric factors as the dominant contribution. Instead, we attribute this effect to the stable radical cation of diamondoids. Our computed enhancement due to a positively charged radical cation was in agreement with the measured work functions to within ±0.3 eV, suggesting a new paradigm for low-work-function coatings based on the design of nanoparticles with stable radical cations.

  9. First principles study of metal contacts to monolayer black phosphorous

    SciTech Connect

    Chanana, Anuja; Mahapatra, Santanu

    2014-11-28

    Atomically thin layered black phosphorous (BP) has recently appeared as an alternative to the transitional metal dichalcogenides for future channel material in a metal-oxide-semiconductor transistor due to its lower carrier effective mass. Investigation of the electronic property of source/drain contact involving metal and two-dimensional material is essential as it impacts the transistor performance. In this paper, we perform a systematic and rigorous study to evaluate the Ohmic nature of the side-contact formed by the monolayer BP (mBP) and metals (gold, titanium, and palladium), which are commonly used in experiments. Employing the Density Functional Theory, we analyse the potential barrier, charge transfer and atomic orbital overlap at the metal-mBP interface in an optimized structure to understand how efficiently carriers could be injected from metal contact to the mBP channel. Our analysis shows that gold forms a Schottky contact with a higher tunnel barrier at the interface in comparison to the titanium and palladium. mBP contact with palladium is found to be purely Ohmic, where as titanium contact demonstrates an intermediate behaviour.

  10. Glycosylated Self-Assembled Monolayers for Arrays and Surface Analysis

    PubMed Central

    Cheng, Fang; Ratner, Daniel M.

    2013-01-01

    Over the past few decades, carbohydrates (glycans) have received growing attention for their many roles in biological systems, including pathogenesis, receptor-ligand interactions, and cell signaling. To unravel the biology of this important category of biomolecules, a host of new tools have been developed for glycomics investigation. At the forefront is the carbohydrate microarray, developed to immobilize functional glycans on a solid substrate to rapidly screen a variety of potential binding partners (carbohydrates, proteins, nucleic acids, cells, and viruses). The essential role played by surface modification on glycan microarray performance requires new methods to rigorously characterize glycan surface chemistries. Due to their highly reproducible nature and well-studied properties, self-assembled monolayers (SAMs) on gold are powerful models for presenting glycans on a solid substrate, engineering biomimetic microenvironments and exploring the bioactivity of immobilized carbohydrates via surface plasmon resonance (SPR). However, it can be challenging to prepare high quality glycosylated SAMs (glyco-SAMs) that retain their biological function following surface immobilization. Herein, a selection of versatile methods for the preparation of glyco-SAMs using natural and chemically modified glycans is described. This chapter will highlight the following three immobilization techniques: (1) direct self assembly using thiolated glycosides onto gold, (2) tethering aminated glycosides onto amine-reactive SAMs, and (3) conjugating natural glycan onto divinyl sulfone-activated SAMs. PMID:22057519

  11. Characterization of self-assembled monolayers (SAMs) on silicon substrate comparative with polymer substrate for Escherichia coli O157:H7 detection

    NASA Astrophysics Data System (ADS)

    Moldovan, Carmen; Mihailescu, Carmen; Stan, Dana; Ruta, Lavinia; Iosub, Rodica; Gavrila, Raluca; Purica, Munizer; Vasilica, Schiopu

    2009-08-01

    This article presents the characterization of two substrates, silicon and polymer coated with gold, that are functionalized by mixed self-assembled monolayers (SAMs) in order to efficiently immobilize the anti- Escherichia coli O157:H7 polyclonal purified antibody. A biosurface functionalized by SAMs (self-assembled monolayers) technique has been developed. Immobilization of goat anti- E. coli O157:H7 antibody was performed by covalently bonding of thiolate mixed self-assembled monolayers (SAMs) realized on two substrates: polymer coated with gold and silicon coated with gold. The F(ab') 2 fragments of the antibodies have been used for eliminating nonspecific bindings between the Fc portions of antibodies and the Fc receptor on cells. The properties of the monolayers and the biofilm formatted with attached antibody molecules were analyzed at each step using infrared spectroscopy (FTIR-ATR), atomic force microscopy (AFM), scanning electron microscopy (SEM) and cyclic voltammetry (CV). In our study the gold-coated silicon substrates approach yielded the best results. These experimental results revealed the necessity to investigate each stage of the immobilization process taking into account in the same time the factors that influence the chemistry of the surface and the further interactions as well and also provide a solid basis for further studies aiming at elaborating sensitive and specific immunosensor or a microarray for the detection of E. coli O157:H7.

  12. Coulomb excitations of monolayer germanene

    NASA Astrophysics Data System (ADS)

    Shih, Po-Hsin; Chiu, Yu-Huang; Wu, Jhao-Ying; Shyu, Feng-Lin; Lin, Ming-Fa

    2017-01-01

    The feature-rich electronic excitations of monolayer germanene lie in the significant spin-orbit coupling and the buckled structure. The collective and single-particle excitations are diversified by the magnitude and direction of transferred momentum, the Fermi energy and the gate voltage. There are four kinds of plasmon modes, according to the unique frequency- and momentum-dependent phase diagrams. They behave as two-dimensional acoustic modes at long wavelength. However, for the larger momenta, they might change into another kind of undamped plasmons, become the seriously suppressed modes in the heavy intraband e–h excitations, keep the same undamped plasmons, or decline and then vanish in the strong interband e–h excitations. Germanene, silicene and graphene are quite different from one another in the main features of the diverse plasmon modes.

  13. Coulomb excitations of monolayer germanene

    PubMed Central

    Shih, Po-Hsin; Chiu, Yu-Huang; Wu, Jhao-Ying; Shyu, Feng-Lin; Lin, Ming-Fa

    2017-01-01

    The feature-rich electronic excitations of monolayer germanene lie in the significant spin-orbit coupling and the buckled structure. The collective and single-particle excitations are diversified by the magnitude and direction of transferred momentum, the Fermi energy and the gate voltage. There are four kinds of plasmon modes, according to the unique frequency- and momentum-dependent phase diagrams. They behave as two-dimensional acoustic modes at long wavelength. However, for the larger momenta, they might change into another kind of undamped plasmons, become the seriously suppressed modes in the heavy intraband e–h excitations, keep the same undamped plasmons, or decline and then vanish in the strong interband e–h excitations. Germanene, silicene and graphene are quite different from one another in the main features of the diverse plasmon modes. PMID:28091555

  14. Thermoelectric transport in monolayer phosphorene

    NASA Astrophysics Data System (ADS)

    Zare, Moslem; Rameshti, Babak Zare; Ghamsari, Farnood G.; Asgari, Reza

    2017-01-01

    We apply the generalized Boltzmann theory to describe thermoelectric transport properties of monolayer phosphorene in the presence of short- and long-range charged impurity interactions. First, we propose a low-energy Hamiltonian to explore the accurate electronic band structure of phosphorene in comparison with those results obtained by density-functional simulations. We explain the effect of the coupling between the conduction and valence bands on the thermoelectric properties. We show that the electric conductivity of phosphorene is highly anisotropic, while the Seebeck coefficient and figure of merit, without being influenced via either the presence or absence of the coupling term, are nearly isotropic. Furthermore, we demonstrate that the conductivity for the n type of doping is more influenced by the coupling term than that of the p type. Along with thermopower sign change, profound thermoelectric effects can be achieved.

  15. Early Yellowstone hotspot magmatism and gold metallogeny

    NASA Astrophysics Data System (ADS)

    Hames, Willis; Unger, Derick; Saunders, James; Kamenov, George

    2009-11-01

    High-grade epithermal gold deposits in the Northern Great Basin have long been associated with regional Miocene basaltic to rhyolitic volcanism. Previous models for the low-sulfidation epithermal gold ores in this region have generally portrayed the bimodal magmas as a source of heat to drive large-scale convection of meteoritic water that leached gold from crustal sources and deposited it in hydrothermal vein systems, or required that the gold evolve from fractionated silicic magmas. New data of the present study indicate a more direct genetic link to the plume-related basaltic magmas of the region. Laser 40Ar/ 39Ar incremental heating plateau ages for single crystals of adularia from several of these low-sulfidation epithermal gold deposits range from 16.6 Ma to 15.5 Ma. Adularia from the Jumbo deposit yields three concordant plateau ages with a combined statistical result of 16.54 ± 0.04 Ma (95% confidence level, MSWD = 0.23). Plateau ages for adularia from other deposits in the region, and from gold-bearing veins in the Owyhee Mountains of southwestern Idaho, yield similar ages up to ~16.5 Ma, however some veins are as young as ca. 15.5 Ma and the grain-to-grain ages for a given sample can vary by up to ca. 0.5 Ma. Observed variations in age among the adularia crystals of a given rock sample indicate varying amounts of extraneous argon, and also loss of radiogenic 40Ar, among the population of grains for a particular sample. The single-crystal results are interpreted to indicate a 16.5-15.5 Ma interval for formation of gold-bearing adularia veins in the region. The initiation and duration of this gold-forming event appears contemporaneous (within uncertainties) with the basaltic volcanism at the Steens Mountain section and an ensuing one-million-year episode of basaltic volcanism from multiple centers in the region ( Brueseke et al., 2007). Trace amounts of lead are alloyed with gold in the deposits studied. The isotopic compositions of this lead are not

  16. Highly doped silicon nanowires by monolayer doping.

    PubMed

    Veerbeek, Janneke; Ye, Liang; Vijselaar, Wouter; Kudernac, Tibor; van der Wiel, Wilfred G; Huskens, Jurriaan

    2017-02-23

    Controlling the doping concentration of silicon nanostructures is challenging. Here, we investigated three different monolayer doping techniques to obtain silicon nanowires with a high doping dose. These routes were based on conventional monolayer doping, starting from covalently bound dopant-containing molecules, or on monolayer contact doping, in which a source substrate coated with a monolayer of a carborane silane was the dopant source. As a third route, both techniques were combined to retain the benefits of conformal monolayer formation and the use of an external capping layer. These routes were used for doping fragile porous nanowires fabricated by metal-assisted chemical etching. Differences in porosity were used to tune the total doping dose inside the nanowires, as measured by X-ray photoelectron spectroscopy and secondary ion mass spectrometry measurements. The higher the porosity, the higher was the surface available for dopant-containing molecules, which in turn led to a higher doping dose. Slightly porous nanowires could be doped via all three routes, which resulted in highly doped nanowires with (projected areal) doping doses of 10(14)-10(15) boron atoms per cm(2) compared to 10(12) atoms per cm(2) for a non-porous planar sample. Highly porous nanowires were not compatible with the conventional monolayer doping technique, but monolayer contact doping and the combined route resulted for these highly porous nanowires in tremendously high doping doses up to 10(17) boron atoms per cm(2).

  17. Target-induced nanocatalyst deactivation facilitated by core@shell nanostructures for signal-amplified headspace-colorimetric assay of dissolved hydrogen sulfide.

    PubMed

    Gao, Zhuangqiang; Tang, Dianyong; Tang, Dianping; Niessner, Reinhard; Knopp, Dietmar

    2015-10-06

    Colorimetric assay platforms for dissolved hydrogen sulfide (H2S) have been developed for more than 100 years, but most still suffer from relatively low sensitivity. One promising route out of this predicament relies on the design of efficient signal amplification methods. Herein, we rationally designed an unprecedented H2S-induced deactivation of (gold core)@(ultrathin platinum shell) nanocatalysts (Au@TPt-NCs) as a highly efficient signal amplification method for ultrasensitive headspace-colorimetric assay of dissolved H2S. Upon target introduction, Au@TPt-NCs were deactivated to different degrees dependent on H2S levels, and the degrees could be indicated by using a Au@TPt-NCs-triggered catalytic system as a signal amplifier, thus paving a way for H2S sensing. The combination of experimental studies and density functional theory (DFT) studies revealed that the Au@TPt-NCs with only 2-monolayer equivalents of Pt (θPt = 2) were superior for H2S-induced nanocatalyst deactivation owing to their enhanced peroxidase-like catalytic activity and deactivation efficiency stemmed from the unique synergistic structural/electronic effects between Au nanocores and ultrathin Pt nanoshells. Importantly, our analytical results showed that the designed method was indeed highly sensitive for sensing H2S with a wide linear range of 10-100 nM, a slope of 0.013 in the regression equation, and a low detection limit of 7.5 nM. Also the selectivity, reproducibility, and precision were excellent. Furthermore, the method was validated for the analysis of H2S-spiked real samples, and the recovery in all cases was 91.6-106.7%. With the merits of high sensitivity and selectivity, simplification, low cost, and visual readout with the naked eye, the colorimetric method has the potential to be utilized as an effective detection kit for point-of-care testing.

  18. Monolayer contact doping of silicon surfaces and nanowires using organophosphorus compounds.

    PubMed

    Hazut, Ori; Agarwala, Arunava; Subramani, Thangavel; Waichman, Sharon; Yerushalmi, Roie

    2013-12-02

    Monolayer Contact Doping (MLCD) is a simple method for doping of surfaces and nanostructures(1). MLCD results in the formation of highly controlled, ultra shallow and sharp doping profiles at the nanometer scale. In MLCD process the dopant source is a monolayer containing dopant atoms. In this article a detailed procedure for surface doping of silicon substrate as well as silicon nanowires is demonstrated. Phosphorus dopant source was formed using tetraethyl methylenediphosphonate monolayer on a silicon substrate. This monolayer containing substrate was brought to contact with a pristine intrinsic silicon target substrate and annealed while in contact. Sheet resistance of the target substrate was measured using 4 point probe. Intrinsic silicon nanowires were synthesized by chemical vapor deposition (CVD) process using a vapor-liquid-solid (VLS) mechanism; gold nanoparticles were used as catalyst for nanowire growth. The nanowires were suspended in ethanol by mild sonication. This suspension was used to dropcast the nanowires on silicon substrate with a silicon nitride dielectric top layer. These nanowires were doped with phosphorus in similar manner as used for the intrinsic silicon wafer. Standard photolithography process was used to fabricate metal electrodes for the formation of nanowire based field effect transistor (NW-FET). The electrical properties of a representative nanowire device were measured by a semiconductor device analyzer and a probe station.

  19. Monolayer Contact Doping of Silicon Surfaces and Nanowires Using Organophosphorus Compounds

    PubMed Central

    Hazut, Ori; Agarwala, Arunava; Subramani, Thangavel; Waichman, Sharon; Yerushalmi, Roie

    2013-01-01

    Monolayer Contact Doping (MLCD) is a simple method for doping of surfaces and nanostructures1. MLCD results in the formation of highly controlled, ultra shallow and sharp doping profiles at the nanometer scale. In MLCD process the dopant source is a monolayer containing dopant atoms. In this article a detailed procedure for surface doping of silicon substrate as well as silicon nanowires is demonstrated. Phosphorus dopant source was formed using tetraethyl methylenediphosphonate monolayer on a silicon substrate. This monolayer containing substrate was brought to contact with a pristine intrinsic silicon target substrate and annealed while in contact. Sheet resistance of the target substrate was measured using 4 point probe. Intrinsic silicon nanowires were synthesized by chemical vapor deposition (CVD) process using a vapor-liquid-solid (VLS) mechanism; gold nanoparticles were used as catalyst for nanowire growth. The nanowires were suspended in ethanol by mild sonication. This suspension was used to dropcast the nanowires on silicon substrate with a silicon nitride dielectric top layer. These nanowires were doped with phosphorus in similar manner as used for the intrinsic silicon wafer. Standard photolithography process was used to fabricate metal electrodes for the formation of nanowire based field effect transistor (NW-FET). The electrical properties of a representative nanowire device were measured by a semiconductor device analyzer and a probe station. PMID:24326774

  20. Electroactive self-assembled monolayers of unique geometric structures by using rigid norbornylogous bridges.

    PubMed

    Darwish, Nadim; Eggers, Paul K; Da Silva, Paulo; Zhang, Yi; Tong, Yujin; Ye, Shen; Gooding, J Justin; Paddon-Row, Michael N

    2012-01-02

    Herein, we describe the synthesis of straight (S) and L-shaped (L) norbornylogous bridges (NBs) with an anthraquinone moiety at the distal end as the redox-active head group and two thiol feet at the proximal end, by which the molecules assemble on gold surfaces. The NB molecules were shown to form self-assembled monolayers (SAMs) with a well-behaved surface redox process. The SAMs were characterized by using in situ IR spectroscopy, cyclic voltammetry, scanning tunnelling microscopy and electrochemical impedance spectroscopy. The surface selection rules associated with the IR band intensities allowed the estimation of the position of the anthraquinone moiety with respect to the surface and the tilt of the bridge with respect to the surface normal, both in pure and diluted monolayers. It is shown that the S- and L-NBs hold the plane of the anthraquinone moiety close to the surface normal or the surface tangent, respectively. Neither NB molecule changes its orientation if spaced by diluents on the surface. The difference in the structure of the S- and L-NB SAMs provides a suitable framework for the investigation of factors that govern electron transfer of anthraquinone moieties across self-assembled monolayers with limited structural ambiguity, as compared with the commonly used structurally flexible alkanethiol monolayers.

  1. Thioaromatic DNA monolayers for target-amplification-free electrochemical sensing of environmental pathogenic bacteria.

    PubMed

    Miranda-Castro, Rebeca; Sánchez-Salcedo, Raquel; Suárez-Álvarez, Beatriz; de-Los-Santos-Álvarez, Noemí; Miranda-Ordieres, Arturo J; Jesús Lobo-Castañón, María

    2017-06-15

    Genosensing technology has mostly based on mixed self-assembled monolayers (SAMs) of thiol-modified oligonucleotides and alkanethiols on gold surfaces. However, the typical backfilling approach, which incorporates the alkanethiol in a second step, gives rise to a heterogeneous distribution of oligonucleotide probes on the surface, negatively affecting to both hybridization efficiency and surface stability. Despite aromatic thiols present a remarkably different behavior from alkanethiols, with higher rigidity and stronger intermolecular interactions, they have been scarcely explored for the fabrication of DNA sensing platforms. We have investigated different approaches involving SAMs of aromatic thiols, namely p-mercaptobenzoic acid (p-MBA) and p-aminothiophenol (p-ATP), to yield DNA sensing layers for sequence-specific detection of target oligonucleotides. The studied monolayers were evaluated by DNA surface coverage and further information was obtained by determining their functionality in a sandwich hybridization assay with enzymatic amplification of the electrochemical read-out. The insertion of thiol-oligonucleotides into p-ATP monolayers previously oxidized, and the covalent binding of amino-oligonucleotides to pure p-MBA monolayers give rise to increased storage stability and better analytical performance. The quantification of RNA from Legionella pneumophila cellular lysates was successfully performed, illustrating the usefulness of these sensing architectures for detecting pathogenic bacteria.

  2. Discrete quantum dot like emitters in monolayer MoSe2: Spatial mapping, magneto-optics, and charge tuning

    NASA Astrophysics Data System (ADS)

    Branny, Artur; Wang, Gang; Kumar, Santosh; Robert, Cedric; Lassagne, Benjamin; Marie, Xavier; Gerardot, Brian D.; Urbaszek, Bernhard

    2016-04-01

    Transition metal dichalcogenide monolayers such as MoSe2, MoS2, and WSe2 are direct bandgap semiconductors with original optoelectronic and spin-valley properties. Here we report on spectrally sharp, spatially localized emission in monolayer MoSe2. We find this quantum dot-like emission in samples exfoliated onto gold substrates and also suspended flakes. Spatial mapping shows a correlation between the location of emitters and the existence of wrinkles (strained regions) in the flake. We tune the emission properties in magnetic and electric fields applied perpendicular to the monolayer plane. We extract an exciton g-factor of the discrete emitters close to -4, as for 2D excitons in this material. In a charge tunable sample, we record discrete jumps on the meV scale as charges are added to the emitter when changing the applied voltage.

  3. Inhibition of Sulfide Mineral Oxidation by Surface Coating Agents: Batch

    NASA Astrophysics Data System (ADS)

    Choi, J.; Ji, M. K.; Yun, H. S.; Park, Y. T.; Gee, E. D.; Lee, W. R.; Jeon, B.-H.

    2012-04-01

    Mining activities and mineral industries have impacted on rapid oxidation of sulfide minerals such as pyrite (FeS2) which leads to Acid Mine Drainage (AMD) formation. Some of the abandoned mines discharge polluted water without proper environmental remediation treatments, largely because of financial constraints in treating AMD. Magnitude of the problem is considerable, especially in countries with a long history of mining. As metal sulfides become oxidized during mining activities, the aqueous environment becomes acid and rich in many metals, including iron, lead, mercury, arsenic and many others. The toxic heavy metals are responsible for the environmental deterioration of stream, groundwater and soils. Several strategies to remediate AMD contaminated sites have been proposed. Among the source inhibition and prevention technologies, microencapsulation (coating) has been considered as a promising technology. The encapsulation is based on inhibition of O2 diffusion by surface coating agent and is expected to control the oxidation of pyrite for a long time. Potential of several surface coating agents for preventing oxidation of metal sulfide minerals from both Young-Dong coal mine and Il-Gwang gold mine were examined by conducting batch experiments and field tests. Powdered pyrite as a standard sulfide mineral and rock samples from two mine outcrops were mixed with six coating agents (KH2PO4, MgO and KMnO4 as chemical agents, and apatite, cement and manganite as mineral agents) and incubated with oxidizing agents (H2O2 or NaClO). Batch experiments with Young-Dong coal mine samples showed least SO42- production in presence of KMnO4 (16% sulfate production compared to no surface coating agents) or cement (4%) within 8 days. In the case of Il-Gwang mine samples, least SO42- production was observed in presence of KH2PO4 (8%) or cement (2%) within 8 days. Field-scale pilot tests at Il-Gwang site also showed that addition of KH2PO4 decreased sulfate production from 200 to

  4. Theoretical Study of Monolayer and Double-Layer Waveguide Love Wave Sensors for Achieving High Sensitivity.

    PubMed

    Li, Shuangming; Wan, Ying; Fan, Chunhai; Su, Yan

    2017-03-22

    Love wave sensors have been widely used for sensing applications. In this work, we introduce the theoretical analysis of the monolayer and double-layer waveguide Love wave sensors. The velocity, particle displacement and energy distribution of Love waves were analyzed. Using the variations of the energy repartition, the sensitivity coefficients of Love wave sensors were calculated. To achieve a higher sensitivity coefficient, a thin gold layer was added as the second waveguide on top of the silicon dioxide (SiO₂) waveguide-based, 36 degree-rotated, Y-cut, X-propagating lithium tantalate (36° YX LiTaO₃) Love wave sensor. The Love wave velocity was significantly reduced by the added gold layer, and the flow of wave energy into the waveguide layer from the substrate was enhanced. By using the double-layer structure, almost a 72-fold enhancement in the sensitivity coefficient was achieved compared to the monolayer structure. Additionally, the thickness of the SiO₂ layer was also reduced with the application of the gold layer, resulting in easier device fabrication. This study allows for the possibility of designing and realizing robust Love wave sensors with high sensitivity and a low limit of detection.

  5. Theoretical Study of Monolayer and Double-Layer Waveguide Love Wave Sensors for Achieving High Sensitivity

    PubMed Central

    Li, Shuangming; Wan, Ying; Fan, Chunhai; Su, Yan

    2017-01-01

    Love wave sensors have been widely used for sensing applications. In this work, we introduce the theoretical analysis of the monolayer and double-layer waveguide Love wave sensors. The velocity, particle displacement and energy distribution of Love waves were analyzed. Using the variations of the energy repartition, the sensitivity coefficients of Love wave sensors were calculated. To achieve a higher sensitivity coefficient, a thin gold layer was added as the second waveguide on top of the silicon dioxide (SiO2) waveguide–based, 36 degree–rotated, Y-cut, X-propagating lithium tantalate (36° YX LiTaO3) Love wave sensor. The Love wave velocity was significantly reduced by the added gold layer, and the flow of wave energy into the waveguide layer from the substrate was enhanced. By using the double-layer structure, almost a 72-fold enhancement in the sensitivity coefficient was achieved compared to the monolayer structure. Additionally, the thickness of the SiO2 layer was also reduced with the application of the gold layer, resulting in easier device fabrication. This study allows for the possibility of designing and realizing robust Love wave sensors with high sensitivity and a low limit of detection. PMID:28327504

  6. Marine diagenesis of hydrothermal sulfide

    SciTech Connect

    Moammar, M.O.

    1985-01-01

    An attempt is made to discuss the artificial and natural oxidation and hydrolysis of hydrothermal sulfide upon interaction with normal seawater. Synthetic and natural ferrosphalerite particles used in kinetic oxidation and hydrolysis studies in seawater develop dense, crystalline coatings consisting of ordered and ferrimagnetic delta-(Fe, Zn)OOH. Due to the formation of this reactive diffusion barrier, the release of Zn into solution decreases rapidly, and sulfide oxidation is reduced to a low rate determined by the diffusion of oxygen through the oxyhydroxide film. This also acts as an efficient solvent for ions such as Zn/sup 2 +/, Ca/sup 2 +/, and possibly Cd/sup 2 +/, which contribute to the stabilization of the delta-FeOOH structure. The oxidation of sulfide occurs in many seafloor spreading areas, such as 21/sup 0/N on the East Pacific Ridge. In these areas the old surface of the sulfide chimneys are found to be covered by an orange stain, and sediment near the base of nonactive vents is also found to consist of what has been referred to as amorphous iron oxide and hydroxide. This thesis also discusses the exceedingly low solubility of zinc in seawater, from delta-(Fe, Zn)OOH and the analogous phase (zinc-ferrihydroxide) and the zinc exchange minerals, 10-A manganate and montmorillonite. The concentrations of all four are of the same magnitude (16, 36.4, and 12 nM, respectively) as the zinc concentration in deep ocean water (approx. 10 nM), which suggests that manganates and montmorillonite with iron oxyhydroxides control zinc concentration in the deep ocean.

  7. Highly oriented, self-assembled alkanephosphate monolayers on tantalum(V) oxide surfaces

    SciTech Connect

    Brovelli, D.; Haehner, G.; Ruiz, L.

    1999-06-22

    Octadecyl phosphoric acid ester has been found to produce oriented, well-ordered monolayers on a flat tantalum(V) oxide surface, via self-assembly from a heptane/propan-2-ol solution. By means of contact angle, optical waveguide lightmode spectroscopy (OWLS), near-edge X-ray absorption fine structure spectroscopy (NEXASFS), and X-ray photoelectron spectroscopy (XPS) measurements, it has been shown that these layers closely resemble those formed by the corresponding thiol-gold system, with respect to packing density, inclination, and order. The system shows promise as an approach to functionalizing oxide surfaces with well-ordered organic monolayers, with potential applications in the fields of biochemical analysis and sensors.

  8. Scanning tunneling microscope observation of the phosphatidylserine domains in the phosphatidylcholine monolayer.

    PubMed

    Matsunaga, Soichiro; Yamada, Taro; Kobayashi, Toshihide; Kawai, Maki

    2015-05-19

    A mixed monolayer of 1,2-dihexanoyl-sn-glycero-3-phospho-l-serine (DHPS) and 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC) on an 1-octanethiol-modified gold substrate was visualized on the nanometer scale using in situ scanning tunneling microscopy (STM) in aqueous solution. DHPS clusters were evident as spotty domains. STM enabled us to distinguish DHPS molecules from DHPC molecules depending on their electronic structures. The signal of the DHPS domains was abolished by neutralization with Ca(2+). The addition of the PS + Ca(2+)-binding protein of annexin V to the Ca(2+)-treated monolayer gave a number of spots corresponding to a single annexin V molecule.

  9. Metal monolayer deposition by replacement of metal adlayers on electrode surfaces

    NASA Astrophysics Data System (ADS)

    Brankovic, S. R.; Wang, J. X.; Adžić, R. R.

    2001-03-01

    A new metal deposition method is demonstrated by deposition of a submonolayer of Pt, a monolayer of Pd and a bilayer of Ag on Au(1 1 1) surfaces by using a Cu adlayer as a template. The deposition of these metals occurs as a spontaneous irreversible redox process in which a Cu adlayer, obtained by underpotential deposition, is oxidized by more noble metal cations, which are reduced and simultaneously deposited. The Pt deposit is a two-dimensional submonolayer consisting of partially interconnected nano-clusters of monoatomic height. Pd forms a uniform, but textured monolayer, while Ag forms a bilayer. The deposit of each metal uniformly covers the entire gold surface without preferential deposition along the step edges. This method provides surface adlayer-controlled growth, as compared to the current distribution controlled growth in conventional electrodeposition.

  10. Electronic transport in arrays of gold nanocrystals

    NASA Astrophysics Data System (ADS)

    Parthasarathy, Raghuveer

    We examine electronic transport through two-dimensional arrays of gold nanocrystals. Recently developed techniques of particle synthesis and array self-assembly provide ordered (and disordered) monolayers of six-nanometer diameter gold nanocrystals on substrates with in-plane electrodes. These well-characterized superlattices allow investigation of basic questions about electronic conduction in metal quantum dot assemblies, answers to which have previously remained elusive. We first address the relation between current and voltage. Central to transport is the Coulomb blockade, the energetic cost of adding a single electron to a nanocrystal. Theoretical studies suggest power-law scaling of current beyond a threshold voltage in Coulomb blockade dominated systems. In ordered arrays, our data follow a power-law form, but with a scaling exponent significantly higher than the theoretical prediction. In disordered arrays, power-law scaling is violated; we explain that disorder disturbs the branching of current-carrying paths responsible for power-law conduction. Second, we examine the effect of temperature on transport. We find a large low-temperature regime (up to about 100 K) in which thermal energy acts only to linearly suppress the threshold voltage, leaving the current scale unaffected. We provide a simple, analytic model of thermally assisted tunneling which quantitatively describes the data. Third, we develop a simple and novel technique to tune the interparticle electronic couplings of the arrays---deposition of small amounts of germanium on the monolayers. The germanium dopant lowers the voltage threshold, and also increases conductivity. It also increases the temperature dependence of transport, suggesting the introduction of trapped states between the gold nanocrystal cores.

  11. Geology of the Barite Hill gold-silver deposit in the southern Carolina slate belt

    USGS Publications Warehouse

    Clark, S.H.B.; Gray, K.J.; Back, J.M.

    1999-01-01

    Barite Hill is a stratiform gold-silver deposit associated with base metal sulfides and barite in greenschist facies rocks. The deposit, southernmost of four recently mined gold deposits in the Carolina slate belt, is located in the Lincolnton-McCormick district of Georgia and South Carolina, which includes several known gold-silver and base metal deposits in a Kuroko-type geological setting along with deposits of kyanite and manganese. Approximately 1,835,000 g of gold was produced mainly from oxidized ores in the Main and Rainsford pits from 1990 until their closing in 1994. Ore is hosted by sericitically altered felsic metavolcanic and metasedimentary rocks of the Late Proterozoic Persimmon Fork Formation. The deposit is stratigraphically below an overturned contact between upper and lower pyroclastic units, which overlie the Lincolnton metarhyolite, an intrusive unit. Gold-silver-rich zones in the Main pit are partly coincident with lenses of siliceous barite rock, but not confined to them, and occur more commonly in pyrite-quartz-altered fragmental rock. The Main pit ore is stratigraphically overlain by a zone of base metal and barite enrichment, which is, in turn, overlain by a talc-tremolite alteration zone locally. Siliceous barite zones are absent in the Rainsford pit, and gold-silver minerals are associated with silicified rocks and chert. The Barite Hill deposit is interpreted to be the result of Kuroko-type, volcanogenic, base metal sulfide mineralization, followed by gold-silver mineralization under epithermal conditions with the following stages of evolution: (1) massive sulfides, barite, and fine-grained siliceous exhalites were deposited during Late Proterozoic to Cambrian submarine volcanism, which was related to plate convergence and subduction in a microcontinental or island-arc setting distant from the North American continental plate; (2) Au-Ag-Te and base and precious metal Te-Se-Bi minerals were deposited either during waning stages of

  12. Multicellular density fluctuations in epithelial monolayers

    NASA Astrophysics Data System (ADS)

    Zehnder, Steven M.; Wiatt, Marina K.; Uruena, Juan M.; Dunn, Alison C.; Sawyer, W. Gregory; Angelini, Thomas E.

    2015-09-01

    Changes in cell size often accompany multicellular motion in tissue, and cell number density is known to strongly influence collective migration in monolayers. Density fluctuations in other forms of active matter have been explored extensively, but not the potential role of density fluctuations in collective cell migration. Here we investigate collective motion in cell monolayers, focusing on the divergent component of the migration velocity field to probe density fluctuations. We find spatial patterns of diverging and converging cell groups throughout the monolayers, which oscillate in time with a period of approximately 3-4 h. Simultaneous fluorescence measurements of a cytosol dye within the cells show that fluid passes between groups of cells, facilitating these oscillations in cell density. Our findings reveal that cell-cell interactions in monolayers may be mediated by intercellular fluid flow.

  13. Accurate Molecular Dimensions from Stearic Acid Monolayers.

    ERIC Educational Resources Information Center

    Lane, Charles A.; And Others

    1984-01-01

    Discusses modifications in the fatty acid monolayer experiment to reduce the inaccurate moleculary data students usually obtain. Copies of the experimental procedure used and a Pascal computer program to work up the data are available from the authors. (JN)

  14. Method to synthesize metal chalcogenide monolayer nanomaterials

    SciTech Connect

    Hernandez-Sanchez, Bernadette A.; Boyle, Timothy J.

    2016-12-13

    Metal chalcogenide monolayer nanomaterials can be synthesized from metal alkoxide precursors by solution precipitation or solvothermal processing. The synthesis routes are more scalable, less complex and easier to implement than other synthesis routes.

  15. Electrochemical investigations of 3-(3-thienyl) acrylic acid protected nanoclusters and planar gold surfaces.

    PubMed

    Nirmal, R G; Kavitha, A L; Berchmans, Sheela; Yegnaraman, V

    2007-06-01

    Formation of self assembled monolayers on gold surface by thiols and disulphides is a well known phenomenon and extensive research work has been carried out in this area with envisaged applications in the area of sensors, molecular electronics, lithography, device fabrication using bottom-up approach, etc. Recently, it has been established that thiophene molecules can self assemble on gold surface due to Au-S interactions. 3-(3-thienyl) acrylic acid, a bifunctional ligand is used in this work to form self-assembled monolayers on planar gold surfaces (two dimensional assemblies) and to prepare monolayer protected gold nano clusters (three-dimensional assemblies). The electron transfer blocking properties of the two-dimensional monolayers were evaluated by using standard redox probes like ferrocyanide anions and Ruthenium hexamine cations. The functionalisation of the two-dimensional and three-dimensional assemblies has been carried out with ferrocene carboxylic acid and the functionalised monolayers were characterized by Cyclic voltammetry. The formation of thienyl acrylic acid protected nanoclusters has been verified by TEM and surface plasmon resonance absorption. It has been observed that when thiophene based ligands are used as stabilizers for the formation of metal nanoparticles, they tend to aggregate as a result of pi-pi interactions between adjacent thiophene ligands. In this case it is found that aggregation is prevented. The substituent at the thiophene ring hinders pi-pi interactions. The quantised nature of electrochemical charging of these nanoparticles has been demonstrated by differential pulse voltammetry (DPV), which exhibit peak like features (coulomb's staircase). This work also explores the possibility of using 3-(3-thienyl) acrylic acid as building blocks or spacers on planar and colloidal gold surfaces for potential applications in the field of sensors and devices.

  16. Gold-Silver mineralization in porphyry-epithermal systems of the Baimka trend, western Chukchi Peninsula, Russia

    NASA Astrophysics Data System (ADS)

    Nikolaev, Yu. N.; Baksheev, I. A.; Prokofiev, V. Yu.; Nagornaya, E. V.; Marushchenko, L. I.; Sidorina, Yu. N.; Chitalin, A. F.; Kal'ko, I. A.

    2016-07-01

    Mineralogical, fluid inclusion, and geochemical studies of precious metal mineralization within the Baimka trend in the western Chukchi Peninsula have been preformed. Porphyry copper-molybdenum-gold deposits and prospects of the Baimka trend are spatially related to monzonitic rocks of the Early Cretaceous Egdygkych Complex. Four types of precious metal-bearing assemblages have been identified: (1) chalcopyrite + bornite + quartz with high-fineness native gold enclosed in bornite, (2) low-Mn dolomite + quartz + sulfide (chalcopyrite, sphalerite, galena, tennantite-tetrahedrite) ± tourmaline with low-fineness native gold and hessite, (3) rhodochrosite + high-Mn dolomite + quartz + sulfide (chalcopyrite, sphalerite, galena, tennantite- tetrahedrite) with low-fineness native gold, electrum, acanthite, Ag and Au-Ag tellurides, and Ag sulfosalts, and (4) calcite + quartz + sulfide (chalcopyrite, sphalerite, galena) with low-fineness native gold, Ag sulfides and selenides, and Ag-bearing sulfosalts. Study of fluid inclusions from quartz, sphalerite, and fluorite have revealed that hydrothermal ores within the Baimka trend precipitated from fluids with strongly variable salinity at temperatures and pressures ranging from 594 to 104°C and from 1200 to 170 bar, respectively. An indicator of vertical AgPbZn/CuBiMo geochemical zoning is proposed. The value range of this indicator makes it possible to estimate the erosion level of the porphyry-epithermal system. The erosion level of the Baimka deposits and prospects deepens in the following order: Vesenny deposit → Pryamoi prospect → Nakhodka prospect → Peschanka deposit → III Vesenny prospect.

  17. Alkanetelluroxide-protected gold nanoparticles.

    PubMed

    Li, Ying; Silverton, Latoya C; Haasch, Richard; Tong, Yu Ye

    2008-07-15

    The synthesis and characterization of the first air-stable tellurium-containing ligand-protected gold nanoparticles (NPs) are reported. Although the synthesis largely followed the well-known Brust two-phase approach, the starting ligand was dioctyl ditelluride rather than alkanetellurol, which is an analogue of the widely used alkanethiol. Dioctyl ditelluride was used because alkanetellurol is unstable. The 1H and 13C NMR spectra, as well as infrared spectra (IR) of the formed Au NPs, indicated that the Te-Te bond in the starting ligand was broken but the octyl group was intact. This was further corroborated by the solid-state 125Te NMR spectrum that displayed a very broad and significantly downfield-shifted peak, indicating that tellurium was directly bound to the Au core. Furthermore, the O 1s and Te 3d XPS spectra of the Au NPs indicated that the capping ligands were octanetelluroxide. An average particle size of 2.7 nm diameter as measured by transmission electron microscopy (TEM) corresponded to an Au607 core. A two-step weight loss of approximately 22.2% in total was observed in the thermogravimetric analysis, which indicated about 53% ligand monolayer coverage (i.e., Au607(Te(=O)C8H17)133). Additionally, dioctyl ditelluride demonstrated an intriguing reductive power that led to a more sophisticated chemistry of forming the air-stable octanetelluroxide-protected gold NPs. It has been found that (1) when the ratio of Au to Te was about 1.5 a colorless intermediate state similar to Au(I)-SR (the intermediate state widely accepted in the synthesis of thiolate-protected Au NPs) could be obtained and (2) this kind of intermediate state played a key role in the formation of stable Au NPs.

  18. Sulfidation mechanism for zinc oxide nanoparticles and the effect of sulfidation on their solubility.

    PubMed

    Ma, Rui; Levard, Clément; Michel, F Marc; Brown, Gordon E; Lowry, Gregory V

    2013-03-19

    Environmental transformations of nanoparticles (NPs) affect their properties and toxicity potential. Sulfidation is an important transformation process affecting the fate of NPs containing metal cations with an affinity for sulfide. Here, the extent and mechanism of sulfidation of ZnO NPs were investigated, and the properties of resulting products were carefully characterized. Synchrotron X-ray absorption spectroscopy and X-ray diffraction analysis reveal that transformation of ZnO to ZnS occurs readily at ambient temperature in the presence of inorganic sulfide. The extent of sulfidation depends on sulfide concentration, and close to 100% conversion can be obtained in 5 days given sufficient addition of sulfide. X-ray diffraction and transmission electron microscopy showed formation of primarily ZnS NPs smaller than 5 nm, indicating that sulfidation of ZnO NPs occurs by a dissolution and reprecipitation mechanism. The solubility of partially sulfidized ZnO NPs is controlled by the remaining ZnO core and not quenched by a ZnS shell formed as was observed for partially sulfidized Ag NPs. Sulfidation also led to NP aggregation and a decrease of surface charge. These changes suggest that sulfidation of ZnO NPs alters the behavior, fate, and toxicity of ZnO NPs in the environment. The reactivity and fate of the resulting <5 nm ZnS particles remains to be determined.

  19. C60 fullerene promotes lung monolayer collapse

    PubMed Central

    Barnoud, Jonathan; Urbini, Laura; Monticelli, Luca

    2015-01-01

    Airborne nanometre-sized pollutants are responsible for various respiratory diseases. Such pollutants can reach the gas-exchange surface in the alveoli, which is lined with a monolayer of lung surfactant. The relationship between physiological effects of pollutants and molecular-level interactions is largely unknown. Here, we determine the effects of carbon nanoparticles on the properties of a model of lung monolayer using molecular simulations. We simulate phase-separated lipid monolayers in the presence of a model pollutant nanoparticle, C60 fullerene. In the absence of nanoparticles, the monolayers collapse only at very low surface tensions (around 0 mN m−1). In the presence of nanoparticles, instead, monolayer collapse is observed at significantly higher surface tensions (up to ca 10 mN m−1). Collapse at higher tensions is related to lower mechanical rigidity of the monolayer. It is possible that similar mechanisms operate on lung surfactant in vivo, which suggests that health effects of airborne carbon nanoparticles may be mediated by alterations of the mechanical properties of lung surfactant. PMID:25589571

  20. Ultrafast electron dynamics in gold nanoshells

    NASA Astrophysics Data System (ADS)

    Westcott, Sarah Linda

    2001-10-01

    In metallic nanostructures, the interaction of excited electrons with the nanostructure surface may result in electron relaxation dynamics that are significantly different than those predicted by electron-lattice coupling. These ultrafast electron dynamics were monitored by pump-probe measurements of the time-resolved change in transmission. Using femtosecond pulses from a cavity-dumped titanium-doped sapphire laser, two types of nanoparticles with a core-shell geometry were studied. Nanoshells are nanoparticles with a dielectric core surrounded by a continuous thin metal shell. For nanoshells, the plasmon resonance wavelength is tunable by changing the core and shell dimensions. For nanoshells with a gold sulfide core and a gold shell, two conditions were observed under which electron relaxation was different than predicted by electron-phonon coupling. First, electron relaxation occurred more rapidly for gold-gold sulfide nanoshells embedded in polymer films than for nanoshells dispersed in water, with lifetimes of 1.6 ps and 3 to 5 ps, respectively. Second, for nanoshells dispersed in water, the electron relaxation lifetime decreased with adsorption of p-aminobenzoic acid (to 1.7 ps) or aniline (to 1.9 ps) on the nanoshells. With adsorbed n-propylamine or p-mercaptobenzoic acid, electron relaxation transpired in 2.8 ps or 2.4 ps, respectively. Density functional theory calculations indicated that the molecules leading to the fastest electron relaxation possessed the largest induced dipole moments near a metal surface. Semicontinuous gold films grown around a silica nanoparticle core exhibited spectral and dynamical optical signatures of the percolation threshold. Compared to continuous shells, the electron dynamics in the semicontinuous shell layer were dramatically different as additional induced bleaching was observed in the first 500 fs. The observed dynamics are consistent with a rate equation model in which the electrons are initially excited in localized

  1. Photochemical Reactions in Self-Assembled Organic Monolayers Characterized by using Scanning Tunneling Microscopy.

    PubMed

    Guo, Chao; Li, Min; Kang, ShiZhao

    2016-03-16

    Research on the supramolecular self-assembly behavior at interfaces is of great importance to improving the performance of nanodevices that are based on optical functional materials. In this Minireview, several photoinduced isomerization and polymerization reactions in self-assembled organic monolayers on surfaces are discussed. Typical organic molecules contain azobenzene, alkynyl, or olefins groups. The feature surface base is a highly oriented pyrolytic graphite (HOPG) surface or a gold surface. Scanning tunneling microscopy (STM) is used as a strong tool to characterize new species' structures before and after illumination.

  2. Biocompatible glutathione capped gold clusters as one- and two-photon excitation fluorescence contrast agents for live cells imaging

    NASA Astrophysics Data System (ADS)

    Polavarapu, Lakshminarayana; Manna, Manoj; Xu, Qing-Hua

    2011-02-01

    The one- and two-photon excitation emission properties of water soluble glutathione monolayer protected gold clusters were investigated. Strong two-photon emission was observed from the gold clusters. The two-photon absorption cross section of these gold clusters in water was deduced from the z-scan measurement to be 189 740 GM, which is much higher compared to organic fluorescent dyes and quantum dots. These gold clusters also showed high photo-stability. The MTT assay showed that these gold clusters have low toxicity even at high concentrations. We have successfully demonstrated their applications for both one and two-photon excitation live cell imaging. The exceptional properties of these gold clusters make them a promising alternative for one- and two-photon bio-imaging and other nonlinear optical applications.The one- and two-photon excitation emission properties of water soluble glutathione monolayer protected gold clusters were investigated. Strong two-photon emission was observed from the gold clusters. The two-photon absorption cross section of these gold clusters in water was deduced from the z-scan measurement to be 189 740 GM, which is much higher compared to organic fluorescent dyes and quantum dots. These gold clusters also showed high photo-stability. The MTT assay showed that these gold clusters have low toxicity even at high concentrations. We have successfully demonstrated their applications for both one and two-photon excitation live cell imaging. The exceptional properties of these gold clusters make them a promising alternative for one- and two-photon bio-imaging and other nonlinear optical applications. Electronic supplementary information (ESI) available: Control experiments; blinking studies of gold clusters. See DOI: 10.1039/c0nr00458h

  3. Controlled Scalable Synthesis of Uniform, High-Quality Monolayer and Few-layer MoS2 Films

    PubMed Central

    Yu, Yifei; Li, Chun; Liu, Yi; Su, Liqin; Zhang, Yong; Cao, Linyou

    2013-01-01

    Two dimensional (2D) materials with a monolayer of atoms represent an ultimate control of material dimension in the vertical direction. Molybdenum sulfide (MoS2) monolayers, with a direct bandgap of 1.8 eV, offer an unprecedented prospect of miniaturizing semiconductor science and technology down to a truly atomic scale. Recent studies have indeed demonstrated the promise of 2D MoS2 in fields including field effect transistors, low power switches, optoelectronics, and spintronics. However, device development with 2D MoS2 has been delayed by the lack of capabilities to produce large-area, uniform, and high-quality MoS2 monolayers. Here we present a self-limiting approach that can grow high quality monolayer and few-layer MoS2 films over an area of centimeters with unprecedented uniformity and controllability. This approach is compatible with the standard fabrication process in semiconductor industry. It paves the way for the development of practical devices with 2D MoS2 and opens up new avenues for fundamental research. PMID:23689610

  4. Thiolated cyclodextrin self-assembled monolayer-like characterized with secondary ion mass spectrometry

    NASA Astrophysics Data System (ADS)

    Rabara, L.; Aranyosiova, M.; Velic, D.

    2011-01-01

    In the work the focus is on the preparation of self-assembled monolayer-like films consisting of thiolated cyclodextrin on gold substrate and a characterization by using secondary ion mass spectrometry. The short (1 min) and long (1 h) time preparations of self-assembled monolayer-like films, resulting in submonolayer and monolayer regimes, are investigated, respectively. The observed species of thiolated cyclodextrin (M as molecular ion) self-assembled monolayer-like films are assigned to three groups: Au xH yS z clusters, fragments with origin in cyclodextrin molecule associated with Au, and molecular ions. The group of Au xH yS z ( x = 2-17, y = 0-2, z = 1-5) clusters have higher intensities than other species in the positive and even more in negative mass spectra. Interestingly, the dependence between the number of Au and S atoms shows that with the increasing size of Au xH yS z clusters up to 11 Au atoms, the number of associated S atoms is also increasing and then decreasing. Molecular species as (M-S+H)Na +, (M+H)Na +, AuMNa +, (M 2-S)Na +, and M 2Na + are determined, and also in cationized forms with K +. The intensities of thiolated cyclodextrin fragments at the long time preparation are approximately 10 times higher than the intensities of the same fragments observed at the short time. The largest observed ions in thiolated cyclodextrin self-assembled monolayer-like films are AuM 2 and Au 2M. The thiolated cyclodextrin molecular ions are compared with hexadecanethiol molecular ions in the form of Au xM w where the values of x and w are smaller for thiolated cyclodextrin than for hexadecanethiol. This result is supported with larger, more compact, and more stabile thiolated cyclodextrin molecule.

  5. 40 CFR 425.03 - Sulfide analytical methods and applicability.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... Provisions § 425.03 Sulfide analytical methods and applicability. (a) The potassium ferricyanide titration... the potassium ferricyanide titration method for the determination of sulfide in wastewaters...

  6. Synthesis and Optical Properties of Sulfide Nanoparticles Prepared in Dimethylsulfoxide

    SciTech Connect

    Li, Yuebin; Ma, Lun; Zhang, Xing; Joly, Alan G.; Liu, Zuli; Chen, Wei

    2008-11-01

    Many methods have been reported for the formation of sulfide nanoparticles by the reaction of metallic salts with sulfide chemical sources in aqueous solutions or organic solvents. Here, we report the formation of sulfide nanoparticles in dimethylsulfoxide (DMSO) by boiling metallic salts without sulfide sources. The sulfide sources are generated from the boiling of DMSO and react with metallic salts to form sulfide nanoparticles. In this method DMSO functions as a solvent and a sulfide source as well as a stabilizer for the formation of the nanoparticles. The recipe is simple and economical making sulfide nanoparticles formed in this way readily available for many potential applications.

  7. Medical Functions of Hydrogen Sulfide.

    PubMed

    Olas, Beata

    2016-01-01

    Hydrogen sulfide (H(2)S) is a gasomediator synthesized from L- and D-cysteine in various tissues. It is involved in a number of physiological and pathological processes. H(2)S exhibits antiatherosclerotic, vasodilator, and proangiogenic properties, and protects the kidney and heart from damage following ischemia/reperfusion injury. H(2)S donors may be natural or synthetic, and may be used for the safe treatment of a wide range of diseases. This review article summarizes the current state of knowledge of the therapeutic function of H(2)S.

  8. Preparation of amorphous sulfide sieves

    DOEpatents

    Siadati, Mohammad H.; Alonso, Gabriel; Chianelli, Russell R.

    2006-11-07

    The present invention involves methods and compositions for synthesizing catalysts/porous materials. In some embodiments, the resulting materials are amorphous sulfide sieves that can be mass-produced for a variety of uses. In some embodiments, methods of the invention concern any suitable precursor (such as thiomolybdate salt) that is exposed to a high pressure pre-compaction, if need be. For instance, in some cases the final bulk shape (but highly porous) may be same as the original bulk shape. The compacted/uncompacted precursor is then subjected to an open-flow hot isostatic pressing, which causes the precursor to decompose and convert to a highly porous material/catalyst.

  9. Molybdenum sulfide/carbide catalysts

    DOEpatents

    Alonso, Gabriel; Chianelli, Russell R.; Fuentes, Sergio; Torres, Brenda

    2007-05-29

    The present invention provides methods of synthesizing molybdenum disulfide (MoS.sub.2) and carbon-containing molybdenum disulfide (MoS.sub.2-xC.sub.x) catalysts that exhibit improved catalytic activity for hydrotreating reactions involving hydrodesulfurization, hydrodenitrogenation, and hydrogenation. The present invention also concerns the resulting catalysts. Furthermore, the invention concerns the promotion of these catalysts with Co, Ni, Fe, and/or Ru sulfides to create catalysts with greater activity, for hydrotreating reactions, than conventional catalysts such as cobalt molybdate on alumina support.

  10. Lithium-cupric sulfide cell

    SciTech Connect

    Cuesta, A.J.; Bump, D.D.

    1980-01-01

    Lithium cells have become the primary power source for cardiac pacemakers due to their reliability and longevity at low current drain rates. A lithium-cupric sulfide cell was developed which makes maximum use of the shape of a pacemaker's battery compartment. The cell has a stable voltage throughout 90% of its lifetime. It then drops to a second stable voltage before depletion. The voltage drop creates a small decrease in pacemaker rate, which alerts the physician to replace the pacemaker. No loss of capacity due to self-discharge as been seen to date, and cells have proven to be safe under extreme conditions. 2 refs.

  11. Brazil's premier gold province. Part II: geology and genesis of gold deposits in the Archean Rio das Velhas greenstone belt, Quadrilátero Ferrífero

    NASA Astrophysics Data System (ADS)

    Lobato, Lydia; Ribeiro-Rodrigues, Luiz; Vieira, Frederico

    2001-07-01

    Orogenic, gold deposits are hosted by rocks of the Archean Rio das Velhas greenstone belt in the Quadrilátero Ferrífero region, Minas Gerais state, Brazil, one of the major gold provinces in the world. The gold deposits occur at the base of the mafic-ultramafic succession, with the most important orebodies controlled by E-W-striking, strike-slip faults. The main mineralization styles are (1) structurally controlled, sulfide replacement zones in banded iron formation (BIF); (2) disseminated sulfide minerals and gold in hydrothermally altered rocks along shear zones; and (3) auriferous quartz-carbonate-sulfide veins and veinlets in mafic, ultramafic, and felsic volcanic rocks, and also in clastic sedimentary rocks. The most common host rocks for ore are metamorphosed oxide- and carbonate-facies banded iron (± iron-rich metachert) formations (e.g., the Cuiabá, São Bento and Raposos deposits) and the lapa seca unit, which is a local term for intensely carbonatized rock (e.g., the giant Morro Velho mine with >450 t of contained gold). Metabasalts host most of the remaining gold deposits. Mineralogical characteristics and fluid inclusion studies suggest variations in the H2O/CO2 ratio of a low-salinity, near-neutral, reducing, sulfur-bearing, ore fluid. The presence of abundant CH4-rich inclusions is related to reduction of the original H2O-CO2 fluid via interaction with carbonaceous matter in the wallrocks. Oxygen fugacity was close to that of graphite saturation, with variations likely to have been influenced by reaction with the carbonaceous matter. Carbon-rich phyllites and schists, which commonly bound ore-bearing horizons, seem to have played both a physical and chemical role in localizing hydrothermal mineral deposition. Microtextural studies indicate that gold deposition was mainly related to desulfidation reactions, and was paragenetically coeval with precipitation of arsenic-rich iron sulfide minerals. Carbon isotope data are compatible with dissolution of

  12. Interaction of bovine serum albumin protein with self assembled monolayer of mercaptoundecanoic acid

    NASA Astrophysics Data System (ADS)

    Poonia, Monika; Agarwal, Hitesh; Manjuladevi, V.; Gupta, R. K.

    2016-05-01

    Detection of proteins and other biomolecules in liquid phase is the essence for the design of a biosensor. The sensitivity of a sensor can be enhanced by the appropriate functionalization of the sensing area so as to establish the molecular specific interaction. In the present work, we have studied the interaction of bovine serum albumin (BSA) protein with a chemically functionalized surface using a quartz crystal microbalance (QCM). The gold-coated quartz crystals (AT-cut/5 MHz) were functionalized by forming self-assembled monolayer (SAM) of 11-Mercaptoundecanoic acid (MUA). The adsorption characteristics of BSA onto SAM of MUA on quartz crystal are reported. BSA showed the highest affinity for SAM of MUA as compared to pure gold surface. The SAM of MUA provides carboxylated surface which enhances not only the adsorption of the BSA protein but also a very stable BSA-MUA complex in the liquid phase.

  13. Variation in sulfide tolerance of photosystem II in phylogenetically diverse cyanobacteria from sulfidic habitats

    NASA Technical Reports Server (NTRS)

    Miller, Scott R.; Bebout, Brad M.

    2004-01-01

    Physiological and molecular phylogenetic approaches were used to investigate variation among 12 cyanobacterial strains in their tolerance of sulfide, an inhibitor of oxygenic photosynthesis. Cyanobacteria from sulfidic habitats were found to be phylogenetically diverse and exhibited an approximately 50-fold variation in photosystem II performance in the presence of sulfide. Whereas the degree of tolerance was positively correlated with sulfide levels in the environment, a strain's phenotype could not be predicted from the tolerance of its closest relatives. These observations suggest that sulfide tolerance is a dynamic trait primarily shaped by environmental variation. Despite differences in absolute tolerance, similarities among strains in the effects of sulfide on chlorophyll fluorescence induction indicated a common mode of toxicity. Based on similarities with treatments known to disrupt the oxygen-evolving complex, it was concluded that sulfide toxicity resulted from inhibition of the donor side of photosystem II.

  14. Emergence of complex chemistry on an organic monolayer.

    PubMed

    Prins, Leonard J

    2015-07-21

    In many origin-of-life scenarios, inorganic materials, such as FeS or mineral clays, play an important role owing to their ability to concentrate and select small organic molecules on their surface and facilitate their chemical transformations into new molecules. However, considering that life is made up of organic matter, at a certain stage during the evolution the role of the inorganic material must have been taken over by organic molecules. How this exactly happened is unclear, and, indeed, a big gap separates the rudimentary level of organization involving inorganic materials and the complex organization of cells, which are the building blocks of life. Over the past years, we have extensively studied the interaction of small molecules with monolayer-protected gold nanoparticles (Au NPs) for the purpose of developing innovative sensing and catalytic systems. During the course of these studies, we realized that the functional role of this system is very similar to that typically attributed to inorganic surfaces in the early stages of life, with the important being difference that the functional properties (molecular recognition, catalysis, signaling, adaptation) originate entirely from the organic monolayer rather than the inorganic support. This led us to the proposition that this system may serve as a model that illustrates how the important role of inorganic surfaces in dictating chemical processes in the early stages of life may have been taken over by organic matter. Here, we reframe our previously obtained results in the context of the origin-of-life question. The following functional roles of Au NPs will be discussed: the ability to concentrate small molecules and create different local populations, the ability to catalyze the chemical transformation of bound molecules, and, finally, the ability to install rudimentary signaling pathways and display primitive adaptive behavior. In particular, we will show that many of the functional properties of the system

  15. The role of hydrogen sulfide in burns.

    PubMed

    Akter, Farhana

    2016-05-01

    Hydrogen sulfide is a novel gasotransmitter that has been shown to play a major role in regulating vascular tone. However, the role of hydrogen sulfide in inflammation, sepsis and burns has only recently been studied. In animal studies, hydrogen sulfide has been shown to play a role in both promoting and inhibiting inflammation. Understanding the role of H2S in sepsis and shock is particularly important due to the high mortality associated with both conditions. In animal sepsis models, hydrogen sulfide appears to increase survival. Severe burns are associated with an inflammatory response that causes increased permeability and edema. Currently, there are few studies that have examined the exact role of hydrogen sulfide in burns. However, the role of hydrogen sulfide in inflammation enables us to hypothesize its role in burns. This review highlights the role of hydrogen sulfide in the mechanisms of action underlying inflammation, wound healing and sepsis as well as examining the potential role of hydrogen sulfide in burns. The authors of this article hope that this review will stimulate research to discover the exact role of this fascinating molecule in burns.

  16. Catalyst and process for oxidizing hydrogen sulfide

    SciTech Connect

    Hass, R.H.; Ward, J.W.

    1984-04-24

    Catalysts comprising bismuth and vanadium components are highly active and stable, especially in the presence of water vapor, for oxidizing hydrogen sulfide to sulfur or SO/sub 2/. Such catalysts have been found to be especially active for the conversion of hydrogen sulfide to sulfur by reaction with oxygen or SO/sub 2/.

  17. Ferrous and Sulfide Treatment of Electroplating Wastewater.

    DTIC Science & Technology

    chromium contaminants and the precipitation of heavy metal contaminants from contaminated electroplating wastewater. The wastewater is first adjusted...to a pH of from about 8 to 10 and then treated with sodium sulfide to provide sulfide ions to effect precipitation of heavy metal contaminants followed

  18. Ammonia and hydrogen sulfide removal using biochar

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Reducing ammonia and hydrogen sulfide emissions from livestock facilities is an important issue for many communities and livestock producers. Ammonia has been regarded as odorous, precursor for particulate matter (PM), and contributed to livestock mortality. Hydrogen sulfide is highly toxic at elev...

  19. Hydrogen sulfide pollution in wastewater treatment facilities

    SciTech Connect

    AlDhowalia, K.H. )

    1987-01-01

    The hydrogen sulfide (H{sub 2}S) found in wastewater collection systems and wastewater treatment facilities results from the bacterial reduction of the sulfate ion (SO{sub 4}). Hydrogen sulfide is a gas that occurs both in the sewer atmosphere and as a dissolved gas in the wastewater. When raw wastewater first enters the wastewater treatment facility by gravity most of the hydrogen sulfide is in the gaseous phase and will escape into the atmosphere at the inlet structures. Also some of the dissolved hydrogen sulfide will be released at points of turbulance such as at drops in flow, flumes, or aeration chambers. Several factors can cause excessive hydrogen sulfide concentrations in a sewerage system. These include septic sewage, long flow times in the sewerage system, high temperatures, flat sewer grades, and poor ventilation. These factors are discussed in this paper.

  20. Biocompatible glutathione capped gold clusters as one- and two-photon excitation fluorescence contrast agents for live cells imaging.

    PubMed

    Polavarapu, Lakshminarayana; Manna, Manoj; Xu, Qing-Hua

    2011-02-01

    The one- and two-photon excitation emission properties of water soluble glutathione monolayer protected gold clusters were investigated. Strong two-photon emission was observed from the gold clusters. The two-photon absorption cross section of these gold clusters in water was deduced from the z-scan measurement to be 189 740 GM, which is much higher compared to organic fluorescent dyes and quantum dots. These gold clusters also showed high photo-stability. The MTT assay showed that these gold clusters have low toxicity even at high concentrations. We have successfully demonstrated their applications for both one and two-photon excitation live cell imaging. The exceptional properties of these gold clusters make them a promising alternative for one- and two-photon bio-imaging and other nonlinear optical applications.

  1. Covalent immobilization of native biomolecules onto Au(111) via N-hydroxysuccinimide ester functionalized self-assembled monolayers for scanning probe microscopy.

    PubMed Central

    Wagner, P; Hegner, M; Kernen, P; Zaugg, F; Semenza, G

    1996-01-01

    We have worked out a procedure for covalent binding of native biomacromolecules on flat gold surfaces for scanning probe microscopy in aqueous buffer solutions and for other nanotechnological applications, such as the direct measurement of interaction forces between immobilized macromolecules, of their elastomechanical properties, etc. It is based on the covalent immobilization of amino group-containing biomolecules (e.g., proteins, phospholipids) onto atomically flat gold surfaces via omega-functionalized self-assembled monolayers. We present the synthesis of the parent compound, dithio-bis(succinimidylundecanoate) (DSU), and a detailed study of the chemical and physical properties of the monolayer it forms spontaneously on Au(111). Scanning tunneling microscopy and atomic force microscopy (AFM) revealed a monolayer arrangement with the well-known depressions that are known to stem from an etch process during the self-assembly. The total density of the omega-N-hydroxysuccinimidyl groups on atomically flat gold was 585 pmol/cm(2), as determined by chemisorption of (14)C-labeled DSU. This corresponded to approximately 75% of the maximum density of the omega-unsubstituted alkanethiol. Measurements of the kinetics of monolayer formation showed a very fast initial phase, with total coverage within 30 S. A subsequent slower rearrangement of the chemisorbed molecules, as indicated by AFM, led to a decrease in the number of monolayer depressions in approximately 60 min. The rate of hydrolysis of the omega-N-hydroxysuccinimide groups at the monolayer/water interface was found to be very slow, even at moderately alkaline pH values. Furthermore, the binding of low-molecular-weight amines and of a model protein was investigated in detail. Images FIGURE 1 FIGURE 2 FIGURE 9 PMID:9172730

  2. Weathering of sulfides on Mars

    NASA Technical Reports Server (NTRS)

    Burns, Roger G.; Fisher, Duncan S.

    1987-01-01

    Pyrrhotite-pentlandite assemblages in mafic and ultramafic igneous rocks may have contributed significantly to the chemical weathering reactions that produce degradation products in the Martian regolith. By analogy and terrestrial processes, a model is proposed whereby supergene alteration of these primary Fe-Ni sulfides on Mars has generated secondary sulfides (e.g., pyrite) below the water table and produced acidic groundwater containing high concentrations of dissolved Fe, Ni, and sulfate ions. The low pH solutions also initiated weathering reactions of igneous feldspars and ferromagnesian silicates to form clay silicate and ferric oxyhydroxide phases. Near-surface oxidation and hydrolysis of ferric sulfato-and hydroxo-complex ions and sols formed gossan above the water table consisting of poorly crystalline hydrated ferric sulfates (e.g., jarosite), oxides (ferrihydrite, goethite), and silica (opal). Underlying groundwater, now permafrost contains hydroxo sulfato complexes of Fe, Al, Mg, Ni, which may be stabilized in frozen acidic solutions beneath the surface of Mars. Sublimation of permafrost may replenish colloidal ferric oxides, sulfates, and phyllosilicates during dust storms on Mars.

  3. Orogenic-type copper-gold-arsenic-(bismuth) mineralization at Flatschach (Eastern Alps), Austria

    NASA Astrophysics Data System (ADS)

    Raith, Johann G.; Leitner, Thomas; Paar, Werner H.

    2015-10-01

    Structurally controlled Cu-Au mineralization in the historic Flatschach mining district (Styria, Austria) occurs in a NE-SW to NNE-WSW oriented vein system as multiple steep-dipping calcite-(dolomite)-quartz veins in amphibolite facies metamorphic rocks (banded gneisses/amphibolites, orthogneisses, metagranitoids) of the poly-metamorphosed Austroalpine Silvretta-Seckau nappe. Vein formation postdated ductile deformation events and Eoalpine (Late Cretaceous) peak metamorphism but predated Early to Middle Miocene sediment deposition in the Fohnsdorf pull-apart basin; coal-bearing sediments cover the metamorphic basement plus the mineralized veins at the northern edge of the basin. Three gold-bearing ore stages consist of a stage 1 primary hydrothermal (mesothermal?) ore assemblage dominated by chalcopyrite, pyrite and arsenopyrite. Associated minor minerals include alloclasite, enargite, bornite, sphalerite, galena, bismuth and matildite. Gold in this stage is spatially associated with chalcopyrite occurring as inclusions, along re-healed micro-fractures or along grain boundaries of chalcopyrite with pyrite or arsenopyrite. Sericite-carbonate alteration is developed around the veins. Stage 2 ore minerals formed by the replacement of stage 1 sulfides and include digenite, anilite, "blue-remaining covellite" (spionkopite, yarrowite), bismuth, and the rare copper arsenides domeykite and koutekite. Gold in stage 2 is angular to rounded in shape and occurs primarily in the carbonate (calcite, Fe-dolomite) gangue and less commonly together with digenite, domeykite/koutekite and bismuth. Stage 3 is a strongly oxidized assemblage that includes hematite, cuprite, and various secondary Cu- and Fe-hydroxides and -carbonates. It formed during supergene weathering. Stage 1 and 2 gold consists mostly of electrum (gold fineness 640-860; mean = 725; n = 46), and rare near pure gold (fineness 930-940; n = 6). Gold in stage 3 is Ag-rich electrum (fineness 350-490, n = 12), and has a

  4. Phase-Specific Diffusivity of DPPG Monolayers

    NASA Astrophysics Data System (ADS)

    Dewitt, Joel; Thapa, Prem; Flanders, Bret

    2004-03-01

    The primary role of lung surfactant is to reduce the alveolar surface tension during exhalation in a reversible manner. Failure to do so results in respiratory distress syndrome. Model lung surfactants provide simplified systems for studying the mechanisms that underlie this essential role of alveolar surfactant. Dipalmitoyl-phosphatidylglycerol (DPPG) monolayers exhibit reversible folding when compressed to a critical surface tension. This process may exemplify how the compression-expansion cycle attains reversibility and, thus, requires penetrating study. The buckling theory for reversible collapse provides a promising though untested description of this process, but poor knowledge of domain boundary widths in DPPG monolayers impedes the evaluation of this theory as a model for the observed behavior. In turn, the measurement of the domain boundary widths requires knowledge of the phase-specific viscosities of the monolayer. In this study, multi-particle tracking has been used to determine the phase-specific diffusion coefficients of polystyrene spheres embedded in DPPG monolayers. By invoking a Stokes-Einstein relationship that is appropriate for spheres diffusing in a viscous surfactant, the phase specific viscosities of the monolayers have been estimated. The rationale for this work is that this knowledge will promote the quantitative evaluation of buckling as a model for reversible folding and, thus, promote growth in understanding of the folding mechanism in model lung surfactants.

  5. Nanoparticle interaction with model lung surfactant monolayers

    PubMed Central

    Harishchandra, Rakesh Kumar; Saleem, Mohammed; Galla, Hans-Joachim

    2010-01-01

    One of the most important functions of the lung surfactant monolayer is to form the first line of defence against inhaled aerosols such as nanoparticles (NPs), which remains largely unexplored. We report here, for the first time, the interaction of polyorganosiloxane NPs (AmorSil20: 22 nm in diameter) with lipid monolayers characteristic of alveolar surfactant. To enable a better understanding, the current knowledge about an established model surface film that mimics the surface properties of the lung is reviewed and major results originating from our group are summarized. The pure lipid components dipalmitoylphosphatidylcholine and dipalmitoylphosphatidylglycerol have been used to study the biophysical behaviour of their monolayer films spread at the air–water interface in the presence of NPs. Film balance measurements combined with video-enhanced fluorescence microscopy have been used to investigate the formation of domain structures and the changes in the surface pattern induced by NPs. We are able to show that NPs are incorporated into lipid monolayers with a clear preference for defect structures at the fluid–crystalline interface leading to a considerable monolayer expansion and fluidization. NPs remain at the air–water interface probably by coating themselves with lipids in a self-assembly process, thereby exhibiting hydrophobic surface properties. We also show that the domain structure in lipid layers containing surfactant protein C, which is potentially responsible for the proper functioning of surfactant material, is considerably affected by NPs. PMID:19846443

  6. GOLD PLATING PROCESS

    DOEpatents

    Seegmiller, R.

    1957-08-01

    An improved bath is reported for plating gold on other metals. The composition of the plating bath is as follows: Gold cyanide from about 15 to about 50 grams, potassium cyanide from about 70 to about 125 grams, and sulfonated castor oil from about 0.1 to about 10 cc. The gold plate produced from this bath is smooth, semi-hard, and nonporous.

  7. Self-assembly of large-scale crack-free gold nanoparticle films using a ‘drain-to-deposit’ strategy

    SciTech Connect

    Yang, Guang; Hallinan, Daniel T.

    2016-04-26

    Gold nanoparticles are widely studied due to the ease of controlled synthesis, facile surface modification, and interesting physical properties. However, a technique for depositing large-area, crack-free monolayers on solid substrates is lacking. Herein is presented a method for accomplishing this. Spherical gold nanoparticles were synthesized as an aqueous dispersion. Assembly into monolayers and ligand exchange occurred simultaneously at an organic/aqueous interface. Then the monolayer film was deposited onto arbitrary solid substrates by slowly pumping out the lower, aqueous phase. This allowed the monolayer film (and liquid–liquid interface) to descend without significant disturbance, eventually reaching substrates contained in the aqueous phase. The resulting macroscopic quality of the films was found to be superior to films transferred by Langmuir techniques. The surface plasmon resonance and Raman enhancement of the films were evaluated and found to be uniform across the surface of each film.

  8. Growth of pentacene on clean and modified gold surfaces

    SciTech Connect

    Kaefer, Daniel; Ruppel, Lars; Witte, Gregor

    2007-02-15

    The growth and evolution of pentacene films on gold substrates have been studied. By combining complementary techniques including scanning tunneling microscopy, atomic force microscopy, scanning electron microscopy, near-edge x-ray-absorption fine structure, and x-ray diffraction, the molecular orientation, crystalline structure, and morphology of the organic films were characterized as a function of film thickness and growth parameters (temperature and rate) for different gold substrates ranging from Au(111) single crystals to polycrystalline gold. Moreover, the influence of precoating the various gold substrates with self-assembled monolayers (SAM's) of organothiols with different chemical terminations has been studied. On bare gold the growth of pentacene films is characterized by a pronounced dewetting while the molecular orientation within the resulting crystalline three-dimensional islands depends distinctly on the roughness and cleanliness of the substrate surface. After completion of the first wetting layer where molecules adopt a planar orientation parallel to the surface the molecules continue to grow in a tilted fashion: on Au(111) the long molecular axis is oriented parallel to the surface while on polycrystalline gold it is upstanding oriented and thus parallels the crystalline orientation of pentacene films grown on SiO{sub 2}. On SAM pretreated gold substrates the formation of a wetting layer is effectively suppressed and pentacene grows in a quasi-layer-by-layer fashion with an upstanding orientation leading to rather smooth films. The latter growth mode is observed independently of the chemical termination of the SAM's and the roughness of the gold substrate. Possible reasons for the different growth mechanism as well as consequences for the assignment of spectroscopic data of thin pentacene film are discussed.

  9. Optical "Turn off" based selective detection and concomitant degradation of 2-chloroethyl ethyl sulfide (CEES) via Mg-porphyrazine complex immobilized on glass.

    PubMed

    Neelam; Singh, Vikram; Gupta, Tarkeshwar

    2014-02-17

    Covalently assembled monolayers (CAMs) of Mg-porphyrazine complex on glass and silicon substrates were fabricated and employed as "Turn off" sensor for ppm level detection and degradation of a sulfur mustard analogue: 2-chloroethyl ethyl sulfide (CEES). The detection process was read-out optically via an off-the-shelf UV/Vis spectrophotometer in transmission mode. Monolayer based sensor system was shown to be quite robust and stable, sufficiently accurate and reversible under given experimental conditions. Notably, the sensor system exhibited marked selectivity for CEES when exposed exclusively or in mix to different potent analytes. Moreover, action of KMnO4 on monolayer-CEES complex lead to CEES degradation and resetting of the sensor to its native state for reuse.

  10. Self-assembled supramolecular array of polymeric phthalocyanine on gold for the determination of hydrogen peroxide.

    PubMed

    Lokesh, Koodlur S; De Wael, Karolien; Adriaens, Annemie

    2010-11-16

    This Article describes for the first time the formation of a supramolecular self-assembled monolayer of polymeric phthalocyanine (poly(CuPc)) onto a gold substrate. The latter is established through the interaction of the cyano group, belonging to the poly(CuPc), with the metal substrate. The functionalized gold substrate was characterized using Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and electrochemical methods. Results clearly demonstrated the interaction between gold and the nitrogen atom of cyano group and showed at the same time the formation of a completely covered polymeric monolayer on the gold surface. In addition, the modified gold surface seems to exhibit a reversible redox behavior and is found to act as an electronic conductor, which allows rapid electron transfer. Electrochemical impedance spectroscopy (EIS) analyses in the presence of [Fe(CN)(6)](3-/4-) as a redox couple revealed that the modified electrode showed a much lower electron transfer resistance compared with bare gold. In addition, the modified electrode is found to catalyze the H(2)O(2) reduction very effectively, showing a catalytic current that varies linearly with the peroxide concentration in the range of 0.35 to 70 μM with a detection limit of 0.25 μM.

  11. Self-assembled monolayers as a base for immunofunctionalisation: unequal performance for protein and bacteria detection.

    PubMed

    Baldrich, Eva; Laczka, Olivier; del Campo, F Javier; Muñoz, Francesc Xavier

    2008-03-01

    Biosensor development strongly depends on the optimisation of surface functionalisation strategies. When gold surfaces are considered, immunofunctionalisation by modification of self-assembled monolayers (SAMs) is one of the preferred approaches. In this respect, SAM-based antibody (Ab) incorporation has shown better performance than Ab physisorption for the detection of proteins and small targets. Reports on bacteria detection are less frequent. In this work, we assess the performance of various SAM-based gold immunofunctionalisation strategies, currently applied to protein detection, in the field of bacteria determination. We present the results for Ab chemical conjugation on mercaptopropanoic acid and mercaptoundecanoic acid SAMs, as well as on a dextranized cysteamine SAM. All the modified surfaces studied were shown to be appropriate for the direct detection of an enzyme-labelled protein, but none succeeded in detecting a bacterial target in a sandwich assay format. Conversely, gold functionalised by Ab physisorption allowed E. coli detection when a sandwich enzyme-linked assay was carried out. The implications of bacteria size and wall complexity are discussed. These results indicate that immunofunctionalisation strategies appropriate for protein detection are not necessarily transferable to work with more complex targets such as bacteria. In this respect, Ab physisorption appears to be a suitable alternative to SAM-based gold functionalisation for bacteria detection.

  12. Giant piezoelectricity of monolayer group IV monochalcogenides

    NASA Astrophysics Data System (ADS)

    Fei, Ruixiang; Li, Wenbin; Li, Ju; Yang, Li

    We predict enormous, anisotropic piezoelectric effects in intrinsic monolayer group IV monochalcogenides (MX, M =Sn or Ge, X =Se or S), including SnSe, SnS, GeSe, and GeS. Using first-principle simulations based on the modern theory of polarization, we find that their piezoelectric coefficients are about one to two orders of magnitude larger than those of other 2D materials, such as MoS2 and GaSe, and bulk quartz and AlN which are widely used in industry. This enhancement is a result of the unique ``puckered'' C2v symmetry and electronic structure of monolayer group IV monochalcogenides. Given the achieved experimental advances in the fabrication of monolayers, their flexible character, and ability to withstand enormous strain, these 2D structures with giant piezoelectric effects may be promising for a broad range of applications such as nano-sized sensors, piezotronics, and energy harvesting in portable electronic devices.

  13. Edge plasmons in monolayer black phosphorus

    NASA Astrophysics Data System (ADS)

    Bao, Zhi-Wei; Wu, Hong-Wei; Zhou, Yu

    2016-12-01

    In this paper, we numerically investigate the edge plasmons in monolayer black phosphorus. It is found that the complex effective indexes of these modes depend on the molecular configuration of the edge. We have calculated the ratio of the real over the imaginary part of the mode effective index, and the results indicate that such edge modes indeed possess outstanding propagation performances in the mid-infrared. In the case of black phosphorus nanoribbon, it seems that only the anti-symmetric modes have low losses, and may be of use in applications. Compared with those at the edge of monolayer black phosphorus, the propagation performances can be further enhanced due to the mode coupling between the two edges. In the end, the effects of substrates are discussed. Our study shows that monolayer black phosphorus may be regarded as a promising candidate for plasmonic applications in the mid-infrared.

  14. Magneto photoluminescence measurements of tungsten disulphide monolayers

    NASA Astrophysics Data System (ADS)

    Kuhnert, Jan; Rahimi-Iman, Arash; Heimbrodt, Wolfram

    2017-03-01

    Layered transition-metal dichalcogenides have attracted great interest in the last few years. Thinned down to the monolayer limit they change from an indirect band structure to a direct band gap in the visible region. Due to the monolayer thickness the inversion symmetry of the crystal is broken and spin and valley are coupled to each other. The degeneracy between the two equivalent valleys, K and K‧, respectively, can be lifted by applying an external magnetic field. Here, we present photoluminescence measurements of CVD-grown tungsten disulphide (WS2) monolayers at temperatures of 2 K. By applying magnetic fields up to 7 T in Faraday geometry, a splitting of the photoluminescence peaks can be observed. The magnetic field dependence of the A-exciton, the trion and three bound exciton states is discussed and the corresponding g-factors are determined.

  15. Transient Kinetic Analysis of Hydrogen Sulfide Oxidation Catalyzed by Human Sulfide Quinone Oxidoreductase.

    PubMed

    Mishanina, Tatiana V; Yadav, Pramod K; Ballou, David P; Banerjee, Ruma

    2015-10-09

    The first step in the mitochondrial sulfide oxidation pathway is catalyzed by sulfide quinone oxidoreductase (SQR), which belongs to the family of flavoprotein disulfide oxidoreductases. During the catalytic cycle, the flavin cofactor is intermittently reduced by sulfide and oxidized by ubiquinone, linking H2S oxidation to the electron transfer chain and to energy metabolism. Human SQR can use multiple thiophilic acceptors, including sulfide, sulfite, and glutathione, to form as products, hydrodisulfide, thiosulfate, and glutathione persulfide, respectively. In this study, we have used transient kinetics to examine the mechanism of the flavin reductive half-reaction and have determined the redox potential of the bound flavin to be -123 ± 7 mV. We observe formation of an unusually intense charge-transfer (CT) complex when the enzyme is exposed to sulfide and unexpectedly, when it is exposed to sulfite. In the canonical reaction, sulfide serves as the sulfur donor and sulfite serves as the acceptor, forming thiosulfate. We show that thiosulfate is also formed when sulfide is added to the sulfite-induced CT intermediate, representing a new mechanism for thiosulfate formation. The CT complex is formed at a kinetically competent rate by reaction with sulfide but not with sulfite. Our study indicates that sulfide addition to the active site disulfide is preferred under normal turnover conditions. However, under pathological conditions when sulfite concentrations are high, sulfite could compete with sulfide for addition to the active site disulfide, leading to attenuation of SQR activity and to an alternate route for thiosulfate formation.

  16. Robust nanogap electrodes by self-terminating electroless gold plating.

    PubMed

    Serdio V, Victor M; Azuma, Yasuo; Takeshita, Shuhei; Muraki, Taro; Teranishi, Toshiharu; Majima, Yutaka

    2012-11-21

    Robust nanogap electrodes for nanodevices with a separation of 3.0 ± 1.7 nm were simultaneously mass-produced at a yield of 90% by a combination of electron beam lithography (EBL) and electroless gold plating (EGP). Nanogap electrodes demonstrated their robustness as they maintained their structure unchanged up to temperatures of 170 °C, during the isotropic oxygen plasma ashing removal of the amorphous carbon overlayer resulting from scanning electron microscopy observations, therefore maintaining their surface reactivity for EGP and formation of a self-assembled monolayer. A gold layer grows over the electrode surface during EGP, narrowing the separation between the electrodes; growth stops around 3 nm due to a self-termination phenomenon. This is the main factor in the high yield and reproducibility of the EGP process because it prevents contact between the electrodes. A 90% yield is achieved by also controlling the etching and physisorption of gold clusters, which is accomplished by reduction of triiodide ions and heat treatment of the EGP solution, respectively. A mixed self-assembled monolayer of octanethiol and decanedithiol can be formed at the surface of the nanogap electrodes after the oxygen plasma treatment, and decanethiol-protected Au nanoparticles were chemisorbed between the self-terminated nanogap electrodes via decanedithiol. Chemically assembled single-electron transistors based on the nanogap electrodes exhibit ideal, stable, and reproducible Coulomb diamonds.

  17. Electrical Detection of Protein Using Gold Nanoparticles and Nanogap Electrodes

    NASA Astrophysics Data System (ADS)

    Tsai, Chien-Ying; Chang, Tien-Li; Uppala, Ramesh; Chen, Chun-Chi; Ko, Fu-Hsiang; Chen, Ping-Hei

    2005-07-01

    A method of electrically detecting of protein described is developed using self-assembled multilayer gold nanoparticles (AuNPs) on a SiO2/Si substrate between gold electrodes. Electrical measurements are performed at room temperature using a probe station. A monoclonal antibody is immobilized on the top surface of the first layer of AuNPs (14 nm). The second layer of AuNPs is formed through specific binding among a target antigen [hepatitis C virus, (HCV)], the monoclonal antibody, and the conjugate of a AuNP-polyclonal antibody. Once the specific binding among the monoclonal antibody, target antigen, and polyclonal antibody occurs, a significant electric current is detected through multilayer self-assembled gold nanoparticles between nanogap electrodes. No significant current (<1 pA) can be measured through a monolayer of AuNPs. A significant difference between the IV curves of the monolayer and the multilayer of AuNPs is used to identify whether the target antigen exists in the tested sample.

  18. Sulfide oxidation as a process for the formation of copper-rich magmatic sulfides

    NASA Astrophysics Data System (ADS)

    Wohlgemuth-Ueberwasser, Cora C.; Fonseca, Raúl O. C.; Ballhaus, Chris; Berndt, Jasper

    2013-01-01

    Typical magmatic sulfides are dominated by pyrrhotite and pentlandite with minor chalcopyrite, and the bulk atomic Cu/Fe ratio of these sulfides is typically less than unity. However, there are rare magmatic sulfide occurrences that are dominated by Cu-rich sulfides (e.g., bornite, digenite, and chalcopyrite, sometimes coexisting with metallic Cu) with atomic Cu/Fe as high as 5. Typically, these types of sulfide assemblages occur in the upper parts of moderately to highly fractionated layered mafic-ultramafic intrusions, a well-known example being the Pd/Au reef in the Upper Middle Zone of the Skaergaard intrusion. Processes proposed to explain why these sulfides are so unusually rich in Cu include fractional crystallization of Fe/(Ni) monosulfide and infiltration of postmagmatic Cu-rich fluids. In this contribution, we explore and experimentally evaluate a third possibility: that Cu-rich magmatic sulfides may be the result of magmatic oxidation. FeS-dominated Ni/Cu-bearing sulfides were equilibrated at variable oxygen fugacities in both open and closed system. Our results show that the Cu/Fe ratio of the sulfide melt increases as a function of oxygen fugacity due to the preferential conversion of FeS into FeO and FeO1.5, and the resistance of Cu2S to being converted into an oxide component even at oxygen fugacities characteristic of the sulfide/sulfate transition (above FMQ + 1). This phenomenon will lead to an increase in the metal/S ratio of a sulfide liquid and will also depress its liquidus temperature. As such, any modeling of the sulfide liquid line of descent in magmatic sulfide complexes needs to address this issue.

  19. Stiffness of lipid monolayers with phase coexistence.

    PubMed

    Caruso, Benjamín; Mangiarotti, Agustín; Wilke, Natalia

    2013-08-27

    The surface dilational modulus--or compressibility modulus--has been previously studied for monolayers composed of pure materials, where a jump in this modulus was related with the onset of percolation as a result of the establishment of a connected structure at the molecular level. In this work, we focused on monolayers composed of two components of low lateral miscibility. Our aim was to investigate the compressibility of mixed monolayers at pressures and compositions in the two-phase region of the phase diagram, in order to analyze the effect of the mechanical properties of each phase on the stiffness of the composite. In nine different systems with distinct molecular dipoles and charges, the stiffness of each phase and the texture at the plane of the monolayer were studied. In this way, we were able to analyze the general compressibility of two-phase lipid monolayers, regardless of the properties of their constituent parts. The results are discussed in the light of the following two hypotheses: first, the stiffness of the composite could be dominated by the stiffness of each phase as a weighted sum according to the percentage of each phase area, regardless of the distribution of the phases in the plane of the monolayer. Alternatively, the stiffness of the composite could be dominated by the mechanical properties of the continuous phase. Our results were better explained by this latter proposal, as in all the analyzed mixtures it was found that the mechanical properties of the percolating phase were the determining factors. The value of the compression modulus was closer to the value of the connected phase than to that of the dispersed phase, indicating that the bidimensional composites displayed mechanical properties that were related to the properties of each phases in a rather complex manner.

  20. Compact autonomous voltammetric sensor for sulfide monitoring in deep sea vent habitats

    NASA Astrophysics Data System (ADS)

    Contreira-Pereira, Leonardo; Yücel, Mustafa; Omanovic, Dario; Brulport, Jean-Pierre; Le Bris, Nadine

    2013-10-01

    methods, but has the advantage of selectivity to free sulfide (compared to colorimetry), low pH sensitivity (compared to amperometry) and lower reconditioning requirement for electrode surface (with respect to gold-amalgam voltammetry). This sensor is therefore a valuable complementary tool for discrete and continuous measurements within the moderate temperature environment of fauna at deep-sea vents.

  1. Microbial Sulfide Filter along a Benthic Redox Gradient in the Eastern Gotland Basin, Baltic Sea

    PubMed Central

    Yücel, Mustafa; Sommer, Stefan; Dale, Andrew W.; Pfannkuche, Olaf

    2017-01-01

    The sediment-water interface is an important site for material exchange in marine systems and harbor unique microbial habitats. The flux of nutrients, metals, and greenhouse gases at this interface may be severely dampened by the activity of microorganisms and abiotic redox processes, leading to the “benthic filter” concept. In this study, we investigate the spatial variability, mechanisms and quantitative importance of a microbially-dominated benthic filter for dissolved sulfide in the Eastern Gotland Basin (Baltic Sea) that is located along a dynamic redox gradient between 65 and 173 m water depth. In August-September 2013, high resolution (0.25 mm minimum) vertical microprofiles of redox-sensitive species were measured in surface sediments with solid-state gold-amalgam voltammetric microelectrodes. The highest sulfide consumption (2.73–3.38 mmol m−2 day−1) occurred within the top 5 mm in sediments beneath a pelagic hypoxic transition zone (HTZ, 80–120 m water depth) covered by conspicuous white bacterial mats of genus Beggiatoa. A distinct voltammetric signal for polysulfides, a transient sulfur oxidation intermediate, was consistently observed within the mats. In sediments under anoxic waters (>140 m depth), signals for Fe(II) and aqueous FeS appeared below a subsurface maximum in dissolved sulfide, indicating a Fe(II) flux originating from older sediments presumably deposited during the freshwater Ancylus Lake that preceded the modern Baltic Sea. Our results point to a dynamic benthic sulfur cycling in Gotland Basin where benthic sulfide accumulation is moderated by microbial sulfide oxidation at the sediment surface and FeS precipitation in deeper sediment layers. Upscaling our fluxes to the Baltic Proper; we find that up to 70% of the sulfide flux (2281 kton yr−1) toward the sediment-seawater interface in the entire basin can be consumed at the microbial mats under the HTZ (80–120 m water depth) while only about 30% the sulfide flux effuses

  2. Mixed DNA/Oligo(ethylene glycol) Functionalized Gold Surface Improve DNA Hybridization in Complex Media

    SciTech Connect

    Lee,C.; Gamble, L.; Grainger, D.; Castner, D.

    2006-01-01

    Reliable, direct 'sample-to-answer' capture of nucleic acid targets from complex media would greatly improve existing capabilities of DNA microarrays and biosensors. This goal has proven elusive for many current nucleic acid detection technologies attempting to produce assay results directly from complex real-world samples, including food, tissue, and environmental materials. In this study, we have investigated mixed self-assembled thiolated single-strand DNA (ssDNA) monolayers containing a short thiolated oligo(ethylene glycol) (OEG) surface diluent on gold surfaces to improve the specific capture of DNA targets from complex media. Both surface composition and orientation of these mixed DNA monolayers were characterized with x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS). XPS results from sequentially adsorbed ssDNA/OEG monolayers on gold indicate that thiolated OEG diluent molecules first incorporate into the thiolated ssDNA monolayer and, upon longer OEG exposures, competitively displace adsorbed ssDNA molecules from the gold surface. NEXAFS polarization dependence results (followed by monitoring the N 1s{yields}{pi}* transition) indicate that adsorbed thiolated ssDNA nucleotide base-ring structures in the mixed ssDNA monolayers are oriented more parallel to the gold surface compared to DNA bases in pure ssDNA monolayers. This supports ssDNA oligomer reorientation towards a more upright position upon OEG mixed adlayer incorporation. DNA target hybridization on mixed ssDNA probe/OEG monolayers was monitored by surface plasmon resonance (SPR). Improvements in specific target capture for these ssDNA probe surfaces due to incorporation of the OEG diluent were demonstrated using two model biosensing assays, DNA target capture from complete bovine serum and from salmon genomic DNA mixtures. SPR results demonstrate that OEG incorporation into the ssDNA adlayer improves surface resistance to both nonspecific DNA and protein

  3. Active Tensile Modulus of an Epithelial Monolayer

    NASA Astrophysics Data System (ADS)

    Vincent, Romaric; Bazellières, Elsa; Pérez-González, Carlos; Uroz, Marina; Serra-Picamal, Xavier; Trepat, Xavier

    2015-12-01

    A general trait of cell monolayers is their ability to exert contractile stresses on their surroundings. The scaling laws that link such contractile stresses with the size and geometry of constituent cells remain largely unknown. In this Letter, we show that the active tension of an epithelial monolayer scales linearly with the size of the constituent cells, a surprisingly simple relationship. The slope of this relationship defines an active tensile modulus, which depends on the concentration of myosin and spans more than 2 orders of magnitude across cell types and molecular perturbations.

  4. Monochromatic electron photoemission from diamondoid monolayers

    SciTech Connect

    Yang, Wanli; Yang, Wanli L.; Fabbri, J.D.; Willey, T.M.; Lee, J.R.I.; Dahl, J.E.; Carlson, R.M.K.; Schreiner, P.R.; Fokin, A.A.; Tkachenko, B.A.; Fokina, N.A.; Meevasana, W.; Mannella, N.; Tanaka, K.; Zhou, X.J.; van Buuren, T.; Kelly, M.A.; Hussain, Z.; Melosh, N.A.; Shen, Z.-X.

    2007-02-27

    We found monochromatic electron photoemission from large-area self-assembled monolayers of a functionalized diamondoid, [121]tetramantane-6-thiol. Photoelectron spectra of the diamondoid monolayers exhibited a peak at the low-kinetic energy threshold; up to 68percent of all emitted electrons were emitted within this single energy peak. The intensity of the emission peak is indicative of diamondoids being negative electron affinity materials. With an energy distribution width of less than 0.5 electron volts, this source of monochromatic electrons may find application in technologies such as electron microscopy, electron beam lithography, and field-emission flatpanel displays.

  5. Monochromatic Electron Photoemission from DiamondoidMonolayers

    SciTech Connect

    Yang, W.L.

    2010-04-15

    We found monochromatic electron photoemission from large-area self-assembled monolayers of a functionalized diamondoid, [121]tetramantane-6-thiol. Photoelectron spectra of the diamondoid monolayers exhibited a peak at the low-kinetic energy threshold; up to 68% of all emitted electrons were emitted within this single energy peak. The intensity of the emission peak is indicative of diamondoids being negative electron affinity materials. With an energy distribution width of less than 0.5 electron volts, this source of monochromatic electrons may find application in technologies such as electron microscopy, electron beam lithography, and field-emission flat-panel displays.

  6. Low temperature photoresponse of monolayer tungsten disulphide

    SciTech Connect

    Cao, Bingchen; Shen, Xiaonan; Shang, Jingzhi; Cong, Chunxiao; Yang, Weihuang; Eginligil, Mustafa E-mail: meginligil@ntu.edu.sg; Yu, Ting E-mail: meginligil@ntu.edu.sg

    2014-11-01

    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.

  7. Self-organization of gold nanoparticles on silanated surfaces

    PubMed Central

    Kyaw, Htet H; Sellai, Azzouz; Dutta, Joydeep

    2015-01-01

    Summary The self-organization of monolayer gold nanoparticles (AuNPs) on 3-aminopropyltriethoxysilane (APTES)-functionalized glass substrate is reported. The orientation of APTES molecules on glass substrates plays an important role in the interaction between AuNPs and APTES molecules on the glass substrates. Different orientations of APTES affect the self-organization of AuNps on APTES-functionalized glass substrates. The as grown monolayers and films annealed in ultrahigh vacuum and air (600 °C) were studied by water contact angle measurements, atomic force microscopy, X-ray photoelectron spectroscopy, UV–visible spectroscopy and ultraviolet photoelectron spectroscopy. Results of this study are fundamentally important and also can be applied for designing and modelling of surface plasmon resonance based sensor applications. PMID:26734526

  8. Metal and fluid sources in a potential world-class gold deposit: El-Sid mine, Egypt

    NASA Astrophysics Data System (ADS)

    Helmy, Hassan; Zoheir, Basem

    2015-04-01

    Lode gold mineralization at the El-Sid mine area is associated with the ca. 600 Ma Fawakhir granite intrusion, which cuts the ~737 Ma ophiolite nappes in the Central Eastern Desert of Egypt. The mineralized quartz veins are hosted by ~E- and NE-trending fault/fracture sets cutting the western boundary of the intrusion and sheared ophiolites. The results of electron microprobe analyses of gold-associated hydrothermal sulfide and silicate minerals suggest that Au was mobilized alongside Ni, Co, Cr and As from the adjacent ophiolitic serpentinite. After granite emplacement, hydrothermal fluids interacted with the sheared serpentinite, leaching metals and re-depositing them in the faults/fractures and adjacent wall rock in a cyclic process. Low-salinity aqueous-carbonic fluids with significant quantities of volatile species (CO2, CH4, and N2 ± H2S) leached and transported Au from deep to shallow crustal levels. Carbon dioxide had a buffering effect on the Au-bearing hydrothermal solution, maintaining its pH within a narrow near-neutral range, where elevated gold concentration was transported by complexation with reduced magmatic sulfur in a reducing environment. Gold deposition along fault/fracture conduits in the Fawakhir granite and adjacent serpentinite resulted from interplay of pressure drop, fluctuations in oxygen and sulfur fugacities, and exsolution of the volatile phases. Infiltration of meteoric water may have contributed to the formation of the late stage gold-sulfide mineralization that formed at shallower levels during terrane uplift. Sulfidation of the Fe-rich magmatic minerals was, on the other hand, the overriding process in the wall rock as evidenced by abundant disseminated sulfides with gold inclusions. Considering the structural control by regional shear zones (fluid conduits) and the voluminous granitic and ophiolitic rocks (metal sources), a high tonnage gold deposit amenable to open pit mining at the El-Sid mine area is very likely.

  9. 40 CFR 425.04 - Applicability of sulfide pretreatment standards.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... hydrogen sulfide gas. (3) The characteristics of the receiving POTWs headworks, preliminary and primary... opportunities for release of hydrogen sulfide gas. (4) The occurrence of any prior sulfide related interference... 40 Protection of Environment 31 2012-07-01 2012-07-01 false Applicability of sulfide...

  10. 40 CFR 425.04 - Applicability of sulfide pretreatment standards.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... hydrogen sulfide gas. (3) The characteristics of the receiving POTWs headworks, preliminary and primary... opportunities for release of hydrogen sulfide gas. (4) The occurrence of any prior sulfide related interference... 40 Protection of Environment 30 2014-07-01 2014-07-01 false Applicability of sulfide...

  11. 40 CFR 425.04 - Applicability of sulfide pretreatment standards.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... hydrogen sulfide gas. (3) The characteristics of the receiving POTWs headworks, preliminary and primary... opportunities for release of hydrogen sulfide gas. (4) The occurrence of any prior sulfide related interference... 40 Protection of Environment 30 2011-07-01 2011-07-01 false Applicability of sulfide...

  12. 40 CFR 425.04 - Applicability of sulfide pretreatment standards.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... hydrogen sulfide gas. (3) The characteristics of the receiving POTWs headworks, preliminary and primary... opportunities for release of hydrogen sulfide gas. (4) The occurrence of any prior sulfide related interference... 40 Protection of Environment 29 2010-07-01 2010-07-01 false Applicability of sulfide...

  13. 40 CFR 425.04 - Applicability of sulfide pretreatment standards.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... hydrogen sulfide gas. (3) The characteristics of the receiving POTWs headworks, preliminary and primary... opportunities for release of hydrogen sulfide gas. (4) The occurrence of any prior sulfide related interference... 40 Protection of Environment 31 2013-07-01 2013-07-01 false Applicability of sulfide...

  14. 21 CFR 73.2995 - Luminescent zinc sulfide.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 1 2014-04-01 2014-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity. The color additive luminescent zinc sulfide is zinc sulfide containing a copper activator....

  15. 21 CFR 73.2995 - Luminescent zinc sulfide.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity. The color additive luminescent zinc sulfide is zinc sulfide containing a copper activator....

  16. 21 CFR 73.2995 - Luminescent zinc sulfide.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 1 2011-04-01 2011-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity. The color additive luminescent zinc sulfide is zinc sulfide containing a copper activator....

  17. 21 CFR 73.2995 - Luminescent zinc sulfide.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 1 2012-04-01 2012-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity. The color additive luminescent zinc sulfide is zinc sulfide containing a copper activator....

  18. 21 CFR 73.2995 - Luminescent zinc sulfide.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 1 2013-04-01 2013-04-01 false Luminescent zinc sulfide. 73.2995 Section 73.2995... COLOR ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2995 Luminescent zinc sulfide. (a) Identity. The color additive luminescent zinc sulfide is zinc sulfide containing a copper activator....

  19. Transmission Measurement of the Third-Order Susceptibility of Gold

    NASA Technical Reports Server (NTRS)

    Smith, David D.; Yoon, Youngkwon; Boyd, Robert W.; Crooks, Richard M.; George, Michael

    1999-01-01

    Gold nanoparticle composites are known to display large optical nonlinearities. In order to assess the validity of generalized effective medium theories (EMT's) for describing the linear and nonlinear optical properties of metal nanoparticle composites, knowledge of the linear and nonlinear susceptibilities of the constituent materials is a prerequisite. In this study the inherent nonlinearity of the metal is measured directly (rather than deduced from a suitable EMT) using a very thin gold film. Specifically, we have used the z-scan technique at a wavelength near the transmission window of bulk gold to measure the third-order susceptibility of a continuous thin gold film deposited on a quartz substrate surface-modified with a self-assembled monolayer to promote adhesion and uniformity without affecting the optical properties. We compare our results with predictions which ascribe the nonlinear response to a Fermi-smearing mechanism. Further, we note that the sign of the nonlinear susceptibility is reversed from that of gold nanoparticle composites.

  20. Patterned Array of Poly(ethylene glycol) Silane Monolayer for Label-Free Detection of Dengue

    PubMed Central

    Rosly, Nor Zida; Ahmad, Shahrul Ainliah Alang; Abdullah, Jaafar; Yusof, Nor Azah

    2016-01-01

    In the present study, the construction of arrays on silicon for naked-eye detection of DNA dengue was demonstrated. The array was created by exposing a polyethylene glycol (PEG) silane monolayer to 254 nm ultraviolet (UV) light through a photomask. Formation of the PEG silane monolayer and photomodifed surface properties was thoroughly characterized by using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. The results of XPS confirmed that irradiation of ultraviolet (UV) light generates an aldehyde functional group that offers conjugation sites of amino DNA probe for detection of a specific dengue virus target DNA. Employing a gold enhancement process after inducing the electrostatic interaction between positively charged gold nanoparticles and the negatively charged target DNA hybridized to the DNA capture probe allowed to visualize the array with naked eye. The developed arrays demonstrated excellent performance in diagnosis of dengue with a detection limit as low as 10 pM. The selectivity of DNA arrays was also examined using a single base mismatch and noncomplementary target DNA. PMID:27571080

  1. Synthesis of nanoparticle-cored dendrimers by convergent dendritic functionalization of monolayer-protected nanoparticles.

    PubMed

    Shon, Young-Seok; Choi, Daeock; Dare, Jonathan; Dinh, Tuong

    2008-06-01

    This article presents a synthesis method for nanoparticle-cored dendrimers (NCDs), which have dendritic architectures around a monolayer-protected gold nanoparticle. The synthesis method is based on a strategy in which the synthesis of monolayer-protected nanoparticles is followed by adding dendrons on functionalized nanoparticles by a single coupling reaction. NMR spectroscopy, IR spectroscopy, and thermogravimetric analysis (TGA) characterizations confirmed the successful coupling reaction between dendrons with different generations ([G1], [G2], and [G3]) and COOH-functionalized nanoparticles ( approximately Au201L71). The dendrimer wedge density also could be controlled by reacting nanoparticles having different loading of COOH groups ( approximately 60 and approximately 10% COOH of the 71 ligands per gold nanoparticle) with functionalized dendrons. Transmission electron microscope results showed that this synthesis strategy maintains the average size of the nanoparticle core during dendron coupling reactions. This control over the composition and core size makes the systematic study of NCDs with different generations possible. The chemical stability of NCDs was found to be affected by dendron generation around the nanoparticle core. The current-potential response of NCD films on microelectrode arrays exhibited better electrical conductivity for NCDs with lower dendron generation.

  2. Organic surfaces exposed by self-assembled organothiol monolayers: Preparation, characterization, and application

    NASA Astrophysics Data System (ADS)

    Kind, Martin; Wöll, Christof

    2009-07-01

    Organic surfaces play a major role in materials science. Most surfaces that we touch in our daily lives are made from organic materials, e.g., vegetables, fruit, skin, wood, and textiles made from natural fibers. In the context of biology, organic surfaces play a prominent role too, proteins docking onto cell surfaces are a good example. To better understand the characteristics of organic surfaces, including physico-chemical properties like wettability or chemical reactivities and physical properties like friction and lubrication, a structurally well-defined model system that can be investigated with numerous analytical techniques is desirable. In the last two decades, one particular system, self-assembled monolayers or SAMs, have demonstrated their suitability for this purpose. In particular, organothiols consisting of an organic molecule with an attached SH-group are well suited to fabricating structurally well-defined adlayers of monolayer thickness on gold substrates using a simple preparation procedure. These ultrathin monolayers expose an organic surface with properties that can be tailored by varying the type of organothiol employed. After a short introduction into the preparation of SAMs, this article provides an overview of the possibilities and limitations of organic surfaces exposed by Au-thiolate SAMs. Applications are as diverse as the metallization of organic surfaces, a fundamental problem in materials science, and the fabrication of surfaces that resist the adsorption of proteins. In addition to a number of different case studies, we will also discuss the most powerful analytical techniques needed to characterize these important model systems.

  3. Self-assembled matrix monolayer for UV-MALDI mass spectrometry

    SciTech Connect

    Mouradian, S.; Nelson, C.M.; Smith, L.M.

    1996-09-11

    Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry has in recent years significantly advanced the field of polymer analysis. However. the mechanisms of the desorption and ionization processes, and in particular the critical role played by the matrix, remain unclear. In the present work, the usual matrix is replaced with a self-assembled monolayer consisting of a UV absorbing matrix-like compound covalently linked to a gold surface. Analytes such as proteins or oligonucleotides are directly deposited on the covalently modified probe tips and mass analyzed by laser desorption time of flight (TOF) mass spectrometry. Several types of monolayers were investigated and tested for their ability to produce positive and negative analyte ions. Molecular ion signals were obtained for dT{sub 10} oligonucleotides and proteins as large as cytochrome C on monolayers of methyl N-(4-mercaptophenyl)carbamate (MMPC). The amenability of this model system to characterization with established physical and chemical methods should help investigate the processes involved in MALDI. 85 refs., 5 figs., 2 tabs.

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

    NASA Astrophysics Data System (ADS)

    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.

  5. Metal hydrogen sulfide superconducting temperature

    NASA Astrophysics Data System (ADS)

    Kudryashov, N. A.; Kutukov, A. A.; Mazur, E. A.

    2017-01-01

    Éliashberg theory is generalized to the electronphonon (EP) systems with the not constant density of electronic states. The phonon contribution to the anomalous electron Green's function (GF) is considered. The generalized Éliashberg equations with the variable density of electronic states are resolved for the hydrogen sulphide SH3 phase under pressure. The dependence of both the real and the imaginary part of the order parameter on the frequency in the SH3 phase is obtained. The Tc = 177 K value in the hydrogen sulfide SH3 phase at the pressure P = 225 GPa has been defined. The results of the solution of the Eliashberg equations for the Im-3m (170 GPa), Im-3m (200 GPa) and R3m (120 GPa) phases are presented. A peak value Tc = 241 K of the superconducting transition temperature has been predicted.

  6. Redox biochemistry of hydrogen sulfide.

    PubMed

    Kabil, Omer; Banerjee, Ruma

    2010-07-16

    H(2)S, the most recently discovered gasotransmitter, might in fact be the evolutionary matriarch of this family, being both ancient and highly reduced. Disruption of gamma-cystathionase in mice leads to cardiovascular dysfunction and marked hypertension, suggesting a key role for this enzyme in H(2)S production in the vasculature. However, patients with inherited deficiency in gamma-cystathionase apparently do not present vascular pathology. A mitochondrial pathway disposes sulfide and couples it to oxidative phosphorylation while also exposing cytochrome c oxidase to this metabolic poison. This report focuses on the biochemistry of H(2)S biogenesis and clearance, on the molecular mechanisms of its action, and on its varied biological effects.

  7. Structural studies in limestone sulfidation

    SciTech Connect

    Fenouil, Laurent A.

    1993-05-01

    This study investigates the sulfidation of limestone at high temperatures (700--900°C) as the first step in the design of a High-Temperature Coal-Gas Clean-Up system using millimeter-size limestone particles. Several workers have found that the rate of this reaction significantly decreases after an initial 10 to 15% conversion of CaCO3 to CaS. The present work attempts to explain this feature. It is first established that millimeter-size limestone particles do not sinter at temperatures up to the CaCO3 calcination point (899°C at 1.03 bar CO2} partial pressure). It is then shown that CaS sinters rapidly at 750 to 900°C if CO2 is present in the gas phase. Scanning Electron Microscope (SEM) photographs and Electron Dispersive Spectroscopy (EDS) data reveal that the CaS product layer sinters and forms a quasi-impermeable coating around the CaCO3 grains that greatly hinders more H2S from reaching the still unreacted parts of the stone. Moreover, most of the pores initially present within the limestone structure begin to disappear or, at least, are significantly reduced in size. From then on, subsequent conversion is limited by diffusion of H2S through the CaS layer, possibly by S2- ionic diffusion. The kinetics is then adequately described by a shrinking-core model, in which a sharp front of completely converted limestone is assumed to progress toward the center of the pellet. Finally, experimental evidence and computer simulations using simple sintering models suggest that the CaS sintering, responsible for the sharp decrease in the sulfidation rate, is surface-diffusion controlled.

  8. Copper-catalyzed asymmetric oxidation of sulfides.

    PubMed

    O'Mahony, Graham E; Ford, Alan; Maguire, Anita R

    2012-04-06

    Copper-catalyzed asymmetric sulfoxidation of aryl benzyl and aryl alkyl sulfides, using aqueous hydrogen peroxide as the oxidant, has been investigated. A relationship between the steric effects of the sulfide substituents and the enantioselectivity of the oxidation has been observed, with up to 93% ee for 2-naphthylmethyl phenyl sulfoxide, in modest yield in this instance (up to 30%). The influence of variation of solvent and ligand structure was examined, and the optimized conditions were then used to oxidize a number of aryl alkyl and aryl benzyl sulfides, producing sulfoxides in excellent yields in most cases (up to 92%), and good enantiopurities in certain cases (up to 84% ee).

  9. Microbial control of hydrogen sulfide production

    SciTech Connect

    Montgomery, A.D.; Bhupathiraju, V.K.; Wofford, N.; McInerney, M.J.

    1995-12-31

    A sulfide-resistant strain of Thiobacillus denitrificans, strain F, prevented the accumulation of sulfide by Desulfovibrio desulfuricans when both organisms were grown in liquid medium. The wild-type strain of T. denitrificans did not prevent the accumulation of sulfide produced by D. desulfuricans. Strain F also prevented the accumulation of sulfide by a mixed population of sulfate-reducing bacteria enriched from an oil field brine. Fermentation balances showed that strain F stoichiometrically oxidized the sulfide produced by D. desulfuricans and the oil field brine enrichment to sulfate. The ability of a strain F to control sulfide production in an experimental system of cores and formation water from the Redfield, Iowa, natural gas storage facility was also investigated. A stable, sulfide-producing biofilm was established in two separate core systems, one of which was inoculated with strain F while the other core system (control) was treated in an identical manner, but was not inoculated with strain F. When formation water with 10 mM acetate and 5 mM nitrate was injected into both core systems, the effluent sulfide concentrations in the control core system ranged from 200 to 460 {mu}M. In the test core system inoculated with strain F, the effluent sulfide concentrations were lower, ranging from 70 to 110 {mu}M. In order to determine whether strain F could control sulfide production under optimal conditions for sulfate-reducing bacteria, the electron donor was changed to lactate and inorganic nutrients (nitrogen and phosphate sources) were added to the formation water. When nutrient-supplemented formation water with 3.1 mM lactate and 10 mM nitrate was used, the effluent sulfide concentrations of the control core system initially increased to about 3,800 {mu}M, and then decreased to about 1,100 {mu}M after 5 weeks. However, in the test core system inoculated with strain F, the effluent sulfide concentrations were much lower, 160 to 330 {mu}M.

  10. Nanostructured lead sulfide: synthesis, structure and properties

    NASA Astrophysics Data System (ADS)

    Sadovnikov, S. I.; Gusev, A. I.; Rempel, A. A.

    2016-07-01

    The theoretical and experimental results of recent studies dealing with nanostructured lead sulfide are summarized and analyzed. The key methods for the synthesis of nanostructured lead sulfide are described. The crystal structure of PbS in nanopowders and nanofilms is discussed. The influence of the size of nanostructure elements on the optical and thermal properties of lead sulfide is considered. The dependence of the band gap of PbS on the nanoparticle (crystallite) size for powders and films is illustrated. The bibliography includes 222 references.

  11. Removal of methanethiol, dimethyl sulfide, dimethyl disulfide, and hydrogen sulfide from contaminated air by Thiobacillus thioparus TK-m

    SciTech Connect

    Kanagawa, T.; Mikami, E.

    1989-03-01

    Methanethiol, dimethyl sulfide, dimethyl disulfide, and hydrogen sulfide were efficiently removed from contaminated air by Thiobacillus thioparus TK-m and oxidized to sulfate stoichiometrically. More than 99.99% of dimethyl sulfide was removed when the load was less than 4.0 g of dimethyl sulfide per g (dry cell weight) per day.

  12. Investigation on laboratory and pilot-scale airlift sulfide oxidation reactor under varying sulfide loading rate.

    PubMed

    Pokasoowan, Chanya; Kanitchaidecha, Wilawan; K C, Bal Krishna; Annachhatre, Ajit P

    2009-01-01

    Airlift bioreactor was established for recovering sulfur from synthetic sulfide wastewater under controlled dissolved oxygen condition. The maximum recovered sulfur was 14.49 g/day when sulfide loading rate, dissolved oxygen (DO) and pH values were 2.97 kgHS(-)/m(3)-day, 0.2-1.0 mg/L and 7.2-7.8, respectively. On the other hand, the increase in recovered sulfur reduced the contact surface of sulfide oxidizing bacteria which affects the recovery process. This effect caused to reduce the conversion of sulfide to sulfur. More recovered sulfur was produced at high sulfide loading rate due to the change of metabolic pathway of sulfide-oxidizing bacteria which prevented the toxicity of sulfide in the culture. The maximum activity in this system was recorded to be about 3.28 kgS/kgVSS-day. The recovered sulfur contained organic compounds which were confirmed by the results from XRD and CHN analyzer. Afterwards, by annealing the recovered sulfur at 120 degrees C for 24 hrs under ambient Argon, the percentage of carbon reduced from 4.44% to 0.30%. Furthermore, the percentage of nitrogen and hydrogen decreased from 0.79% and 0.48% to 0.00% and 0.14%, respectively. This result showed the success in increasing the purity of recovered sulfur by using the annealing technique. The pilot-scale biological sulfide oxidation process was carried out using real wastewater from Thai Rayon Industry in Thailand. The airlift reactor successfully removed sulfide more than 90% of the influent sulfide at DO concentration of less than 0.1 mg/L, whereas the elementary sulfur production was 2.37 kgS/m(3)-day at sulfide loading rate of 2.14 kgHS(-)/m(3)-day. The sulfur production was still increasing as the reactor had not yet reached its maximum sulfide loading rate.

  13. UV/vis and NIR light-responsive spiropyran self-assembled monolayers.

    PubMed

    Ivashenko, Oleksii; van Herpt, Jochem T; Feringa, Ben L; Rudolf, Petra; Browne, Wesley R

    2013-04-02

    Self-assembled monolayers of a 6-nitro BIPS spiropyran (SP) modified with a disulfide-terminated aliphatic chain were prepared on polycrystalline gold surfaces and characterized by UV/vis absorption, surface-enhanced Raman scattering (SERS), and X-ray photoelectron spectroscopies (XPS). The SAMs obtained are composed of the ring-closed form (i.e., spiropyran) only. Irradiation with UV light results in conversion of the monolayer to the merocyanine form (MC), manifested in the appearance of an N(+) contribution in the N 1s region of the XPS spectrum of the SAMs, the characteristic absorption band of the MC form in the visible region at 555 nm, and the C-O stretching band in the SERS spectrum. Recovery of the initial state of the monolayer was observed both thermally and after irradiation with visible light. Several switching cycles were performed and monitored by SERS spectroscopy, demonstrating the stability of the SAMs during repeated switching between SP and MC states. A key finding in the present study is that ring-opening of the surface-immobilized spiropyrans can be induced by irradiation with continuous wave NIR (785 nm) light as well as by irradiation with UV light. We demonstrate that ring-opening by irradiation at 785 nm proceeds by a two-photon absorption pathway both in the SAMs and in the solid state. Hence, spiropyran SAMs on gold can undergo reversible photochemical switching from the SP to the MC form with both UV and NIR and the reverse reaction induced by irradiation with visible light or heating. Furthermore, the observation of NIR-induced switching with a continuous wave source holds important consequences in the study of photochromic switches on surfaces using SERS and emphasizes the importance of the use of multiple complementary techniques in characterizing photoresponsive SAMs.

  14. Compressibility study of quaternary phospholipid blend monolayers.

    PubMed

    Cavalcanti, Leide P; Tho, Ingunn; Konovalov, Oleg; Fossheim, Sigrid; Brandl, Martin

    2011-07-01

    The mechanical properties of liposome membranes are strongly dependent on type and ratio of lipid compounds, which can have important role in drug targeting and release processes when liposome is used as drug carrier. In this work we have used Brewster's angle microscopy to monitor the lateral compression process of lipid monolayers containing as helper lipids either distearoyl phosphatidylethanolamine (DSPE) or dioleoyl phophatidylethanolamine (DOPE) molecules on the Langmuir trough. The compressibility coefficient was determined for lipid blend monolayers containing the helper lipids above, cholesterol, distearoyl phosphatidylcholine (DSPC) and pegylated-DSPE at room temperature. Two variables, the cholesterol fraction and the ratio ρ between the helper lipid (either DSPE or DOPE) and the reference lipid DSPC, were studied by multivariate analysis to evaluate their impact on the compressibility coefficient of the monolayers. The cholesterol level was found to be the most significant variable for DSPE blends while the ratio ρ was the most significant one for DOPE blend monolayers. It was also found that these two variables can exhibit positive interaction and the same compressibility value can be obtained with different blend compositions.

  15. Adsorption of Ions at Uncharged Insoluble Monolayers.

    PubMed

    Peshkova, Tatyana V; Minkov, Ivan L; Tsekov, Roumen; Slavchov, Radomir I

    2016-09-06

    A method is proposed for the experimental determination of the adsorption of inorganic electrolytes at a surface covered with insoluble surfactant monolayer. This task is complicated by the fact that the change of the salt concentration alters both chemical potentials of the electrolyte and the surfactant. Our method resolves the question by combining data for the surface pressure versus area of the monolayer at several salt concentrations with data for the equilibrium spreading pressure of crystals of the surfactant (used to fix a standard state). We applied the method to alcohols spread at the surface of concentrated halide solutions. The measured salt adsorption is positive and has nonmonotonic dependence on the area per surfactant molecule. For the liquid expanded film, depending on the concentration, there is one couple of ions adsorbed per each 3-30 surfactant molecules. We analyzed which ion, the positive or the negative, stands closer to the surface, by measuring the effect of NaCl on the Volta potential of the monolayer. The potentiometric data suggest that Na(+) is specifically adsorbed, while Cl(-) remains in the diffuse layer, i.e., the surface is positively charged. The observed reverse Hofmeister series of the adsorptions of NaF, NaCl, and NaBr suggests the same conclusion holds for all these salts. The force that causes the adsorption of Na(+) seems to be the interaction of the ion with the dipole moment of the monolayer.

  16. Hydrolytic kinetics of biodegradable polyester monolayers

    SciTech Connect

    Lee, W.K.; Gardella, J.A. Jr.

    2000-04-04

    The rate of hydrolysis of Langmuir monolayer films of a series of biodegradable polyesters was investigated at the air/water interface. The present study investigated parameters such as degradation medium, pH, and time. The hydrolysis of polyester monolayers strongly depended on both the degradation medium used to control subphase pH and the concentration of active ions. Under the conditions studied here, polymer monolayers showed faster hydrolysis when they were exposed to a basic subphase rather than that of acidic or neutral subphase. The basic (pH = 10) hydrolysis of [poly(l-lactide)/polycaprolactone](l-PLA/PCL 1/1 by mole) blend was faster than that of each homopolymer at the initial stage. This result is explained by increasing numbers of base attack sites per unit area owing to the very slow hydrolysis of PCL, a dilution effect on the concentration of l-PLA monolayers. Conversely the hydrolytic behavior of l-lactide-co-caprolactone (1/1 by mole) was similar to that of PCL even though the chemical compositions of the blend and the copolymer are very similar to each other. The resistance of the copolymer to hydrolysis might be attributed to the hydrophobicity and the steric hindrance of caprolactone unit in the copolymer.

  17. Adsorption of Ions at Uncharged Insoluble Monolayers

    NASA Astrophysics Data System (ADS)

    Peshkova, T. V.; Minkov, I. L.; Tsekov, R.; Slavchov, R. I.

    2016-08-01

    A method is proposed for the experimental determination of the adsorption of inorganic electrolytes at a surface covered with insoluble surfactant monolayer. This task is complicated by the fact that the change of the salt concentration alters both chemical potentials of the electrolyte and the surfactant. Our method resolves the question by combining data for the surface pressure versus area of the monolayer at several salt concentrations with data for the equilibrium spreading pressure of crystals of the surfactant (used to fix a standard state). We applied the method to alcohols spread at the surface of concentrated halide solutions. The measured salt adsorption is positive and has nonmonotonic dependence on the area per surfactant molecule. For the liquid expanded film, depending on the concentration, there is one couple of ions adsorbed per each 3–30 surfactant molecules. We analyzed which ion, the positive or the negative, stands closer to the surface, by measuring the effect of NaCl on the Volta potential of the monolayer. The potentiometric data suggest that Na+ is specifically adsorbed, while Cl– remains in the diffuse layer, i.e., the surface is positively charged. The observed reverse Hofmeister series of the adsorptions of NaF, NaCl, and NaBr suggests the same conclusion holds for all these salts. The force that causes the adsorption of Na+ seems to be the interaction of the ion with the dipole moment of the monolayer.

  18. Modulation of dipalmitoylphosphatidylcholine monolayers by dimethyl sulfoxide.

    PubMed

    Dabkowska, Aleksandra P; Collins, Louise E; Barlow, David J; Barker, Robert; McLain, Sylvia E; Lawrence, M Jayne; Lorenz, Christian D

    2014-07-29

    The action of the penetration-enhancing agent, dimethyl sulfoxide (DMSO), on phospholipid monolayers was investigated at the air-water interface using a combination of experimental techniques and molecular dynamics simulations. Brewster angle microscopy revealed that DPPC monolayers remained laterally homogeneous at subphase concentrations up to a mole fraction of 0.1 DMSO. Neutron reflectometry of the monolayers in combination with isotopic substitution enabled the determination of solvent profiles as a function of distance perpendicular to the interface for the different DMSO subphase concentrations. These experimental results were compared to those obtained from molecular dynamic (MD) simulations of the corresponding monolayer systems. There was excellent agreement found between the MD-derived reflectivity curves and the measured data for all of the H/D contrast variations investigated. The MD provide a detailed description of the distribution of water and DMSO molecules around the phosphatidylcholine headgroup, and how this distribution changes with increasing DMSO concentrations. Significantly, the measurements and simulations that are reported here support the hypothesis that DMSO acts by dehydrating the phosphatidylcholine headgroup, and as such provide the first direct evidence that it does so primarily by displacing water molecules bound to the choline group.

  19. Nitrate-reducing, sulfide-oxidizing bacteria as microbial oxidants for rapid biological sulfide removal.

    PubMed

    De Gusseme, Bart; De Schryver, Peter; De Cooman, Michaël; Verbeken, Kim; Boeckx, Pascal; Verstraete, Willy; Boon, Nico

    2009-01-01

    The emission of hydrogen sulfide into the atmosphere of sewer systems induces the biological production of sulfuric acid, causing severe concrete corrosion. As a possible preventive solution, a microbial consortium of nitrate-reducing, sulfide-oxidizing bacteria (NR-SOB) was enriched in a continuously stirred tank reactor in order to develop a biological technique for the removal of dissolved sulfide. The consortium, dominated by Arcobacter sp., was capable of removing 99% of sulfide. Stable isotope fractioning of the sulfide indicated that the oxidation was a biological process. The capacity of the NR-SOB consortium for rapid removal of sulfide was demonstrated by using it as an inoculum in synthetic and real sewage. Removal rates up to 52 mg sulfide-S g VSS(-1) h(-1) were achieved, to our knowledge the highest removal rate reported so far for freshwater species in the absence of molecular oxygen. Further long-term incubation experiments revealed the capacity of the bacteria to oxidize sulfide without the presence of nitrate, suggesting that an oxidized redox reserve is present in the culture.

  20. The role of decarbonization and structure in the Callie gold deposit, Tanami Region of northern Australia

    NASA Astrophysics Data System (ADS)

    Williams, Nicholas C.

    2007-01-01

    The Callie deposit is the largest (6.0 Moz Au) of several gold deposits in the Dead Bullock Soak goldfield of the Northern Territory’s Tanami Region, 550 km northwest of Alice Springs. The Callie ore lies within corridors, up to 180 m wide, of sheeted en echelon quartz veins where they intersect the 500-m-wide hinge of an ESE-plunging F1 anticlinorium. The host rocks are the Blake beds, of the Paleoproterozoic Dead Bullock Formation, which consist of a > 350-m-thick sequence of lower greenschist facies graphitic turbidites and mudstones overlying in excess of 100 m of thickly bedded siltstones and fine sandstones. The rocks are Fe-rich and dominated by assemblages of chlorite and biotite, both of which are of hydrothermal and metamorphic origin. A fundamental characteristic of the hydrothermal alteration is the removal of graphite, a process which is associated with bleaching and the development of bedding-parallel bands of coarse biotite augen. Gold is found only in quartz veins and only where they cut decarbonized chloritic rock with abundant biotite augen and no sulfide minerals. Auriferous quartz veins differ from barren quartz veins by the presence of ilmenite, apatite, xenotime, and gold and the absence of sulfide minerals. The assemblage of gold-ilmenite-apatite-xenotime indicates a linked genesis and mobility of Ti, P, and Y in the mineralizing fluids. Geochemical analysis of samples throughout the deposit shows that gold only occurs in sedimentary rocks with high FeO/(FeO+Fe2O3) and low C/(C+CO2) ratios (> 0.8 and < 0.2, respectively). This association can be explained by reactions that convert C from reduced graphitic host rocks into CO2 and reduce ferric iron in the host rocks to ferrous iron in biotite and chlorite. These reactions would increase the CO2 content of the fluid, facilitating the transport of Ti, P, and Y from the host rocks into the veins. Both CO2 and CH4 produced by reaction of H2O with graphite, effervesced under the lower confining

  1. Bald Mountain gold mining district, Nevada: A Jurassic reduced intrusion-related gold system

    USGS Publications Warehouse

    Nutt, C.J.; Hofstra, A.H.

    2007-01-01

    The Bald Mountain mining district has produced about 2 million ounces (Moz) of An. Geologic mapping, field relationships, geochemical data, petrographic observations, fluid inclusion characteristics, and Pb, S, O, and H isotope data indicate that An mineralization was associated with a reduced Jurassic intrusion. Gold deposits are localized within and surrounding a Jurassic (159 Ma) quartz monzonite porphyry pluton and dike complex that intrudes Cambrian to Mississippian carbonate and clastic rocks. The pluton, associated dikes, and An mineralization were controlled by a crustal-scale northwest-trending structure named the Bida trend. Gold deposits are localized by fracture networks in the pluton and the contact metamorphic aureole, dike margins, high-angle faults, and certain strata or shale-limestone contacts in sedimentary rocks. Gold mineralization was accompanied by silicification and phyllic alteration, ??argillic alteration at shallow levels. Although An is typically present throughout, the system exhibits a classic concentric geochemical zonation pattern with Mo, W, Bi, and Cu near the center, Ag, Pb, and Zn at intermediate distances, and As and Sb peripheral to the intrusion. Near the center of the system, micron-sized native An occurs with base metal sulfides and sulfosalts. In peripheral deposits and in later stages of mineralization, Au is typically submicron in size and resides in pyrite or arsenopyrite. Electron microprobe and laser ablation ICP-MS analyses show that arsenopyrite, pyrite, and Bi sulfide minerals contain 10s to 1,000s of ppm Au. Ore-forming fluids were aqueous and carbonic at deep levels and episodically hypersaline at shallow levels due to boiling. The isotopic compositions of H and O in quartz and sericite and S and Pb in sulfides are indicative of magmatic ore fluids with sedimentary sulfur. Together, the evidence suggests that Au was introduced by reduced S-bearing magmatic fluids derived from a reduced intrusion. The reduced

  2. Shape control of gold nanoparticles by silver underpotential deposition.

    PubMed

    Personick, Michelle L; Langille, Mark R; Zhang, Jian; Mirkin, Chad A

    2011-08-10

    Four different gold nanostructures: octahedra, rhombic dodecahedra, truncated ditetragonal prisms, and concave cubes, have been synthesized using a seed-mediated growth method by strategically varying the Ag(+) concentration in the reaction solution. Using X-ray photoelectron spectroscopy and inductively coupled plasma atomic emission spectroscopy, we provide quantitative evidence that Ag underpotential deposition is responsible for stabilizing the various surface facets that enclose the above nanoparticles. Increasing concentrations of Ag(+) in the growth solution stabilize more open surface facets, and experimental values for Ag coverage on the surface of the particles fit well with a calculated monolayer coverage of Ag, as expected via underpotential deposition.

  3. Ridding Groundwater of Hydrogen Sulfide. Part 1.

    ERIC Educational Resources Information Center

    Lochrane, Thomas G.

    1979-01-01

    This article is the first in a series reviewing the problems associated with hydrogen sulfide in drinking water sources. Discussion centers on identification of a cost-effective balance between aeration and chlorination treatment operations. (AS)

  4. Hydrogen sulfide in hemostasis: friend or foe?

    PubMed

    Olas, Beata

    2014-06-25

    Hydrogen sulfide (H2S) is a well known toxic gas that is synthesized from the amino acids: cysteine (Cys) and homocysteine (Hcy) by three enzymes: cystathionine-β-synthase (CBS), cystathionine-γ-lyase (CSE) and mercaptopyruvate sulfurtransferase (3-MST). Hydrogen sulfide, like carbon monoxide (CO) or nitric oxide (NO) is a signaling molecule in different biological systems, including the cardiovascular system. Moreover, hydrogen sulfide plays a role in the pathogenesis of various cardiovascular diseases. It modulates different elements of hemostasis (activation of blood platelet, and coagulation process) as well as proliferation and apoptosis of vascular smooth muscle cells. However, the biological role and the therapeutic potential of H2S is not clear. This review summarizes the different functions of hydrogen sulfide in hemostasis.

  5. [Fatal outcome of an hydrogen sulfide poisoning].

    PubMed

    Querellou, E; Jaffrelot, M; Savary, D; Savry, C; Perfus, J-P

    2005-10-01

    We report a case of fatal outcome poisoning by massive exposure to hydrogen sulfide of a sewer worker. This rare event was associated with a moderate intoxication of two members of the rescue team. The death was due to asystole and massive lung oedema. Autopsy analysis showed diffuse necrotic lesions in lungs. Hydrogen sulfide is a direct and systemic poison, produced by organic matter decomposition. The direct toxicity mechanism is still unclear. The systemic toxicity is due to an acute toxicity by oxygen depletion at cellular level. It is highly diffusable and potentially very dangerous. At low concentration, rotten egg smell must trigger hydrogen sulfide suspicion since at higher concentration it is undetectable, making intoxication possible. In case of acute intoxication, there is an almost instantaneous cardiovascular failure and a rapid death. Hydrogen sulfide exposure requires prevention measures and more specifically the use of respiratory equipment for members of the rescue team.

  6. Oxygen in activator centers of zinc sulfide

    SciTech Connect

    Golobeva, N.P.; Fok, M.V.

    1986-05-01

    The authors observed the sensitized luminescence of Tm and Dy without addition of Cu and Ag in samples which had been obtained by the sulfonation of zinc sulfide in hydrogen sulfide; the zinc sulfide has a copper concentration below 5.10/sup -6/ mass %. In this case the excitation can be transmitted from the ZnS lattice to the rare-earth activators mainly through defects including oxygen. The following conclusions were made. In the case of activated ZnS, oxygen is present in formations accounting for the excitation and luminescence of a number of luminophors. When an activator is introduced in the region of ZnS layer faults, where also the oxygen must be located, the positioning of the faults in close vicinity is facilitated even when the oxygen concentration of the ZnS is low. All this must be considered when models of luminescence centers of zinc sulfide are developed.

  7. Bimetallic gold-silver nanoplate array as a highly active SERS substrate for detection of streptavidin/biotin assemblies.

    PubMed

    Bi, Liyan; Dong, Jian; Xie, Wei; Lu, Wenbo; Tong, Wei; Tao, Lin; Qian, Weiping

    2013-12-17

    The silver-modified gold nanoplate arrays as bimetallic surface-enhanced Raman scattering (SERS) substrates were optimized for the surface-enhanced Raman detection of streptavidin/biotin monolayer assemblies. The bimetallic gold-silver nanoplate arrays were fabricated by coating silver nanoparticles uniformly on the gold nanoplate arrays. Depending on silver nanoparticle coating, the localized surface plasmon resonance (LSPR) peak of the bimetallic gold-silver nanoplate arrays blue-shifted and broadened significantly. The common probe molecule, Niel Blue A sulfate (NBA) was used for testing the SERS activity of the bimetallic gold-silver nanoplate arrays. The SERS intensity increased with the silver nanoparticle coating, due to a large number of hot spots and nanoparticle interfaces. The platforms were tested against a monolayer of streptavidin functionalized over the bimetallic gold-silver nanoplate arrays showing that good quality spectra could be acquired with a short acquisition time. The supramolecular interaction between streptavidin (strep) and biotin showed subsequent modification of Raman spectra that implied a change of the secondary structure of the host biomolecule. And the detection concentration for biotin by this method was as low as 1.0 nM. The enhanced SERS performance of such bimetallic gold-silver nanoplate arrays could spur further interest in the integration of highly sensitive biosensors for rapid, nondestructive, and quantitative bioanalysis, particularly in microfluidics.

  8. Ore petrology and geochemistry of Tertiary gold telluride deposits of the Colorado mineral belt

    SciTech Connect

    Saunders, J.A.; Romberger, S.B.

    1985-01-01

    Epithermal gold telluride deposits from the Colorado mineral belt share a number of similarities: relationship to alkalic stocks; high fluorine and CO/sub 2/ content; and similar paragenesis. Petrography of deposits in the Jamestown, Cripple Creek, and La Plata districts has resulted in a composite paragenesis: early Fe-Cu-Pb-Zn sulfides + hematite; tetrahedrite; high Te tellurides; low Te tellurides; late native gold. Fluid inclusion studies suggest telluride deposition occurred below 200/sup 0/C from low salinity. Gangue and alteration mineralogy indicates the ore fluids were near neutral pH during telluride deposition. The presence of hematite and locally barite suggest relatively oxidizing conditions. Evaluation of thermodynamic stabilities of tellurides and aqueous tellurium species indicates that progressive oxidation is consistent with the observed ore mineral paragenesis. Available data on gold bisulfide and chloride complexes suggest neither were important in the transport of gold in these systems. Thermodynamic data suggest the ditelluride ion (Te/sub 2//sup 2 -/) predominates in the range of inferred physiochemical conditions for the transport and deposition of gold in these systems. Inferred complexes such as AuTe/sub 2//sup -/ could account for the gold transport, and oxidation would be the most effective mechanism of precipitation of gold telluride or native gold. Published data suggest the associated alkalic stocks may be the ultimate source of the metals, since they are enriched in Au, Ag, Te, As, and Bi.

  9. Upper critical field of copper molybdenum sulfide

    NASA Technical Reports Server (NTRS)

    Alterovitz, S. A.; Woollam, J. A.

    1978-01-01

    The upper critical field of sintered and sputtered copper molybdenum sulfide Cu(x)Mo6S8 was measured and found to exceed the Werthamer, Helfand, and Hohenberg (1966) value for a type II superconductor characterized by dirty limit, weak isotropic electron phonon coupling, and no paramagnetic limiting. It is suggested that the enhancement results from anisotropy or clean limit or both. Other ternary molybdenum sulfides appear to show similar anomalies.

  10. The subchronic oral toxicity of polyphenylene sulfide.

    PubMed

    Thomas, W C; Kirwin, C J; Wazeter, F X; Jessup, D C

    1984-02-01

    Polyphenylene sulfide was offered to Charles River CD rats for 6 months in the diet at concentrations of 0.00, 0.50, 2.75 and 5.00% (w/w). In this study, animals of both sexes consumed polyphenylene sulfide for 6 months without exhibiting compound-related effects. Parameters studied were: body weight, hematology, clinical chemistry, urinalysis, organ weights, gross pathology and histopathology.

  11. Development of Zinc Sulfide Seeker Window Material

    DTIC Science & Technology

    2007-11-02

    currently valid OMB control number. 1. REPORT DATE 15 JAN 2005 2. REPORT TYPE N/A 3. DATES COVERED - 4. TITLE AND SUBTITLE Development of...contrasting to the currently used THAAD sapphire window and validate the predictions for an alternate seeker window material, multispectral zinc...and validate the capability of multispectral zinc sulfide seeker window material. The use of zinc sulfide as a replacement window for the current

  12. Effect of Nitrate on Biogenic Sulfide Production

    PubMed Central

    Jenneman, Gary E.; McInerney, M. J.; Knapp, Roy M.

    1986-01-01

    The addition of 59 mM nitrate inhibited biogenic sulfide production in dilute sewage sludge (10% [vol/vol]) amended with 20 mM sulfate and either acetate, glucose, or hydrogen as electron donors. Similar results were found when pond sediment or oil field brines served as the inoculum. Sulfide production was inhibited for periods of at least 6 months and was accompanied by the oxidation of resazurin from its colorless reduced state to its pink oxidized state. Lower amounts of nitrate (6 or 20 mM) and increased amounts of sewage sludge resulted in only transient inhibition of sulfide production. The addition of 156 mM sulfate to bottles with 59 mM nitrate and 10% (vol/vol) sewage sludge or pond sediment resulted in sulfide production. Nitrate, nitrite, and nitrous oxide were detected during periods where sulfide production was inhibited, whereas nitrate, nitrite, and nitrous oxide were below detectable levels at the time sulfide production began. The oxidation of resazurin was attributed to an increase in nitrous oxide which persisted in concentration of about 1.0 mM for up to 5 months. The numbers of sulfate-reducing organisms decreased from 106 CFU ml−1 sludge to less than detectable levels after prolonged incubation of oxidized bottles. The addition of 10 mM glucose to oxidized bottles after 14.5 weeks of incubation resulted in rereduction of the resazurin and subsequent sulfide production. The prolonged inhibition of sulfide production was attributed to an increase in oxidation-reduction potential due to biogenic production of nitrous oxide, which appeared to have a cytotoxic effect on sulfate-reducing populations. PMID:16347078

  13. Photooxidation of methyl sulfide, ethyl sulfide, and methanethiol

    SciTech Connect

    Grosjean, D.

    1984-06-01

    Products of sunlight-irradiated mixtures of oxides of nitrogen and alkyl sulfides (RSR, R = CH/sub 3/, C/sub 2/H/sub 5/) and methanethiol (CH/sub 3/SH) in air include formaldehyde (R = CH/sub 3/), acetaldehyde and PAN (R = C/sub 2/H/sub 5/), sulfur dioxide, and alkyl nitrates (RONO/sub 2/) as well as particulate alkanesulfonic acids (RSO/sub 2/OH) and inorganic sulfate. The nature and yields of gaseous and particulate products are discussed in terms of OH-initiated reaction pathways, including C-S bond scission, and subsequent reactions of alkythiyl radicals (RS), including those leading to photolabile RSNO and stable RSNO/sub 2/ products for which indirect evidence is presented. SO/sub 2/ yields are found to vary according to the relative importance of the competing pathways RS + O/sub 2/ (a) and RS + NO/sub 2/ (b), for which a ratio k/sub b/ / k/sub a/ approx. 2 x 10/sup 6/ is derived from data for irradiated RSR-NO/sub x/, RSH-Cl/sub 2/, and RSH-Cl/sub 2/-NO/sub 2/ mixtures.

  14. Remnant colloform pyrite at the haile gold deposit, South Carolina: A textural key to genesis

    USGS Publications Warehouse

    Foley, N.; Ayuso, R.A.; Seal, R.R.

    2001-01-01

    Auriferous iron sulfide-bearing deposits of the Carolina slate belt have distinctive mineralogical and textural features-traits that provide a basis to construct models of ore deposition. Our identification of paragenetically early types of pyrite, especially remnant colloform, crustiform, and layered growth textures of pyrite containing electrum and pyrrhotite, establishes unequivocally that gold mineralization was coeval with deposition of host rocks and not solely related to Paleozoic tectonic events. Ore horizons at the Haile deposit, South Carolina, contain many remnants of early pyrite: (1) fine-grained cubic pyrite disseminated along bedding; (2) fine- grained spongy, rounded masses of pyrite that may envelop or drape over pyrite cubes; (3) fragments of botryoidally and crustiform layered pyrite, and (4) pyritic infilling of vesicles and pumice. Detailed mineral chemistry by petrography, microprobe, SEM, and EDS analysis of replaced pumice and colloform structures containing both arsenic compositional banding and electrum points to coeval deposition of gold and the volcanic host rocks and, thus, confirms a syngenetic origin for the gold deposits. Early pyrite textures are present in other major deposits of the Carolina slate belt, such as Ridgeway and Barite Hill, and these provide strong evidence for models whereby the sulfide ores formed prior to tectonism. The role of Paleozoic metamorphism was to remobilize and concentrate gold and other minerals in structurally prepared sites. Recognizing the significance of paragenetically early pyrite and gold textures can play an important role in distinguishing sulfide ores that form in volcanic and sedimentary environments from those formed solely by metamorphic processes. Exploration strategies applied to the Carolina slate belt and correlative rocks in the eastern United States in the Avalonian basement will benefit from using syngenetic models for gold mineralization.

  15. Adhesion of human leukocytes to biomaterials: an in vitro study using alkanethiolate monolayers with different chemically functionalized surfaces.

    PubMed

    Barbosa, Judite N; Barbosa, Mário A; Aguas, Artur P

    2003-06-15

    The adhesion of human leukocytes to self-assembled monolayers of well-defined surface chemistry was investigated in vitro. Polymorphonuclear (PMN) and mononuclear leukocytes were isolated from human blood by centrifugation techniques. The effect on adhesion of cell activation produced by pre-incubation of leukocytes with phytohemagglutinin (PHA) and phorbol 12-myristate 13-acetate (PMA) was also studied. Gold substrates were modified by treatment with alkanethiols with three different terminal chemical groups: COOH, OH, and CH(3). After incubation with the two subpopulations of leukocytes, the monolayers were washed, treated with fixative, stained with a Giemsa method, and observed by light microscopy to quantify the number of attached leukocytes. Comparative quantification of the density of leukocyte adhesion to the three types of self-assembled monolayers was determined. The hydrophobic surface expressing CH(3) was found to be the one that induced the highest adhesion density of leukocytes, both of PMN and mononuclear cells. In vitro activation of both mononuclear and PMN leukocytes further increased cell adhesion to the chemically defined monolayers that were used. This enhancement was higher for PHA-activated than for PMA-stimulated mononuclear cells, whereas PMA treatment of neutrophils resulted in a higher rate of adhesion of these cells than PHA stimulation.

  16. Chalcogenide centred gold complexes.

    PubMed

    Gimeno, M Concepción; Laguna, Antonio

    2008-09-01

    Chalcogenide-centred gold complexes are an important class of compounds in which a central chalcogen is surrounded by several gold atoms or gold and other metals. They have special characteristics such as unusual geometries, electron deficiency and properties such as luminescence or non-linear optical properties. The best known species are the trinuclear [E(AuPR3)3]+, 'oxonium' type species, that have high synthetic applicability, not only in other chalcogen-centred species, but in many other organometallic derivatives. The aurophilic interactions play an important role in the stability, preference for a particular geometry and luminescence properties in this type of derivatives (critical review, 117 references).

  17. Analytical performance of molecular beacons on surface immobilized gold nanoparticles of varying size and density.

    PubMed

    Uddayasankar, Uvaraj; Krull, Ulrich J

    2013-11-25

    The high quenching efficiency of metal nanoparticles has facilitated its use as quenchers in molecular beacons. To optimize this system, a good understanding of the many factors that influence molecular beacon performance is required. In this study, molecular beacon performance was evaluated as a function of gold nanoparticle size and its immobilization characteristics. Gold nanoparticles of 4 nm, 15 nm and 87 nm diameter, were immobilized onto glass slides. Each size regime offered distinctive optical properties for fluorescence quenching of molecular dyes that were conjugated to oligonucleotides that were immobilized to the gold nanoparticles. Rigid double stranded DNA was used as a model to place fluorophores at different distances from the gold nanoparticles. The effect of particle size and also the immobilization density of nanoparticles was evaluated. The 4 nm and 87 nm gold nanoparticles offered the highest sensitivity in terms of the change in fluorescence intensity as a function of distance (3-fold improvement for Cy5). The optical properties of the molecular fluorophore was of significance, with Cy5 offering higher contrast ratios than Cy3 due to the red-shifted emission spectrum relative to the plasmon peak. A high density of gold nanoparticles reduced contrast ratios, indicating preference for a monolayer of immobilized nanoparticles when considering analytical performance. Molecular beacon probes were then used in place of the double stranded oligonucleotides. There was a strong dependence of molecular beacon performance on the length of a linker used for attachment to the nanoparticle surface. The optimal optical performance was obtained with 4 nm gold nanoparticles that were immobilized as monolayers of low density (5.7×10(11)particles cm(-2)) on glass surfaces. These nanoparticle surfaces offered a 2-fold improvement in analytical performance of the molecular beacons when compared to other nanoparticle sizes investigated. The principles developed

  18. Gold deposits in the late Archaean Nzega-Igunga greenstone belt, central plateau of tanzania

    SciTech Connect

    Feiss, P.G.; Siyomana, S.

    1985-01-01

    2.2 m oz of gold have been produced, since 1935, from late Archaean (2480-2740 Ma) greenstone belts of the Central Plateau, Tanzania. North and east of Nzega (4/sup 0/12'S, 3/sup 0/11'E), 18% of the exposed basement, mainly Dodoman schists and granites, consists of metavolcanics and metasediments of the Nyanzian and Kavirondian Series. Four styles of mineralization are observed. 1. Stratabound quartz-gold veins with minor sulfides. Host rocks are quartz porphyry, banded iron formation (BIF), magnetite quartzite, and dense, cherty jasperite at the Sekenke and Canuck mines. The Canuck veins are on strike from BIF's in quartz-eye porphyry of the Igusule Hills. 2. Stratabound, disseminated gold in coarse-grained, crowded feldspar porphyry with lithic fragments and minor pyrite. At Bulangamilwa, the porphyry is conformable with Nyanzian-aged submarine (.) greenstone, volcanic sediment, felsic volcanics, and sericite phyllite. The deposits are on strike with BIF of the Wella Hills, which contains massive sulfide with up to 15% Pb+Zn. 3. Disseminated gold in quartz-albite metasomes in Nyanzian greenstones. At Kirondatal, alteration is associated with alaskites and feldspar porphyry dikes traceable several hundred meters into post-Dodoman diorite porphyry. Gold is with pyrite, arsenopyrite, pyrrhotite, minor chalcopyrite, and sphalerite as well as tourmalinite and silica-cemented breccias. 4. Basal Kavirondian placers in metaconglomerates containing cobbles and boulders of Dodoman and Nyanzian rocks several hundred meters up-section from the stratabound, disseminated mineralization at Bulangamilwa.

  19. Comparison of the native antimony-bearing Paiting gold deposit, Guizhou Province, China, with Carlin-type gold deposits, Nevada, USA

    NASA Astrophysics Data System (ADS)

    Xie, Zhuo-Jun; Xia, Yong; Cline, Jean S.; Yan, Bao-Wen; Wang, Ze-Peng; Tan, Qin-Ping; Wei, Dong-Tian

    2017-01-01

    The Paiting gold deposit, Guizhou Province, China, has been regarded as a Carlin-type gold deposit by several researchers. Alteration and ore-related minerals from the Paiting deposit were examined, and results were compared with the Cortez Hills Carlin-type gold deposit, Nevada, USA. Similarities include the structural and stratigraphic controls on the orebodies in both deposits and the occurrence of invisible gold ionically bound in arsenian pyrite. Significant differences include the following: (1) The gold-bearing mineral in Nevada is arsenian pyrite. However, gold-bearing minerals in the Paiting deposit include arsenopyrite, arsenian pyrite, and trace pyrrhotite. Also, euhedral or subhedral gold-bearing arsenian pyrite at Paiting contains significantly less As, Cu, and Hg than gold-bearing pyrite from Nevada. (2) Alteration in the Paiting deposit displays significantly less decarbonatization. Instead, dolomite precipitation, which has not been described in Nevada deposits, is associated with deposition of gold-bearing sulfide minerals. (3) Stibnite and minor native antimony typify Paiting late-ore-stage minerals, whereas in Nevada, realgar, orpiment, and calcite are common late-ore-stage minerals. Precipitation of native antimony in the Paiting deposit reflects the evolution of a late-ore fluid with unusually low sulfur and oxygen fugacities. Some characteristics of the Paiting gold deposit, including formation of ore-stage dolomite and precipitation from CO2-rich ore fluids at temperatures in excess of 250 °C, are more typical of orogenic deposits than Nevada Carlin deposits. The presence of similarities in the Paiting deposit to both Carlin type and orogenic deposits is consistent with formation conditions intermediate to those typical of Carlin type and orogenic systems.

  20. Facile fabrication of large-area and uniform silica nanospheres monolayer for efficient surface-enhanced Raman scattering

    NASA Astrophysics Data System (ADS)

    Tang, Junqi; Zhao, Qianrun; Zhang, Ning; Man, Shi-Qing

    2014-07-01

    A large-area efficient surface enhanced Raman scattering (SERS) substrate was deposited by Langmuir-Blodgett (LB) assembly and followed by sputter coating process. The interparticle distance of silica nanospheres was convenient and readily regulated by controlling the surface pressure. After sputter coating with a small amount of gold, the nanocomposite film was formed. The surfaces of nanostructures were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The applicability of the nanostructures as SERS substrates was investigated by adsorption of crystal violet (CV) molecules. Different SERS effects were observed on deposited gold nanostructure upon large-area silica nanospheres monolayer with diameter of 250, 570 and 800 nm. It was also discussed the nanospheres with diameter of 250 nm for the fabrication of ordered arrangement of monolayers at surface pressures of 10-30 mN/m. These substrates with the close-packed nanospheres and sputtering of gold were found to exhibit high and uniform enhancement of the Raman signal across the entire surface. The averaged surface enhancement factor (ASEF) was calculated and discussed. The fabricated nanocomposite structures could be utilized as low-cost SERS-active substrates for biomedical and analytical chemistry field.

  1. Molecular and dissociative adsorption of water and hydrogen sulfide at perfect and defective Cu(110) surfaces.

    PubMed

    Lousada, Cláudio M; Johansson, Adam Johannes; Korzhavyi, Pavel A

    2017-03-07

    We performed a density functional theory (DFT) investigation of the molecular and dissociative adsorption of H2O and H2S at perfect and defective Cu(110) surfaces described using supercells with c(6 × 6) periodicity. The defective surface consists of a terrace surrounded by pits. We found considerable differences in adsorption modes and energies for H2O and H2S. At the defective Cu(110) surface, monomers of H2O and H2S preferentially adsorb at the terrace site and molecular adsorption of H2O is significantly more favorable than that of H2S. For dissociative adsorption however, the sulfur species are considerably more stable than the oxygen species. For monolayer (ML) coverages, there are small differences in the molecular adsorption energies for H2O and H2S. However, for the formation of 1 ML of HO and 1 ML of HS from 1 ML of H2O and 1 ML of H2S, respectively, with the release of H2(g), the differences are very large. The formation of 1 ML HO at the perfect Cu(110) surface is endoergic, while at the defective Cu(110) surface it is exoergic by -0.6 eV. For high coverages, H2S forms stacked half-monolayers that interact with each other via a complex hydrogen bond network with a strength per H2S molecule of -0.140 eV per H2S and -0.120 eV per H2S for H2S located in the underlayer and overlayer, respectively. The large distances between hydrogen bonded H2S molecules explain the preference for the formation of the two stacked half-monolayers of H2S instead of a single monolayer as it happens with H2O. Additionally, the formation of 1 ML of HS does not occur because of the spontaneous splitting of some H-S bonds resulting in surface bound HS and S and H2S molecules. Extensive surface reconstruction and relaxation accompanies adsorption of the sulfur adsorbates. Such reconstructions with outwards pull of Cu atoms can be at the origin of the weak adhesion of sulfide films that explains the release of CuS particles from copper sulfide films at copper surfaces. Overall, the

  2. Multichannel biosensing platform of surface-immobilized gold nanospheres for linear and nonlinear optical imaging.

    PubMed

    Tsuboi, Kazuma; Fukuba, Shinya; Naraoka, Ryo; Fujita, Katsuhiko; Kajikawa, Kotaro

    2007-07-10

    What we believe to be a new label-free multichannel biosensing platform is proposed. It is composed of surface-immobilized gold nanospheres (SIGNs) above a gold surface with a nanogap supported by a merocyanine self-assembled monolayer. The circular SIGN spots with a diameter of 120 microm were arrayed for multichannel biosensing on a glass slide. Two kinds of sensing methods were examined: One is a reflectivity measurement of a blue ray and the other is a second-harmonic generation measurement. It was found that the SIGN system can be used as a promising platform for multichannel biosensing in both sensing methods.

  3. Normal incidence X-ray standing wave analysis of thin gold films

    NASA Astrophysics Data System (ADS)

    Satterley, Christopher J.; Lovelock, Kevin R. J.; Thom, Ian; Dhanak, Vinod R.; Buck, Manfred; Jones, Robert G.

    2006-11-01

    Normal incidence X-ray standing wave (NIXSW) analysis has been successfully performed on epitaxial gold films on mica substrates using reflection from the (1 1 1) planes parallel to the surface. We show that NIXSW can be used to monitor the decrease in order within the gold film caused by annealing, and the position of sulfur within a monolayer of methyl thiolate (CH 3S-) on the surface. The Au-S layer spacing was found to be 2.54 ± 0.05 Å, in close agreement with previous work on a single crystal system.

  4. Improved mechanical stability of acetoxypropyl cellulose upon blending with ultranarrow PbS nanowires in Langmuir monolayer matrix.

    PubMed

    Maji, Subrata; Kundu, Sudarshan; Pinto, L F V; Godinho, M H; Khan, Ali Hossain; Acharya, Somobrata

    2013-12-10

    Cellulose and cellulose derivatives have long been used as membrane fabrication. Langmuir monolayer behavior, which naturally mimics membranes, of acetoxypropyl cellulose (APC) and lead sulfide (PbS) nanowire mixtures at different volume ratios is reported. Surface pressure (π)-area (A) isotherms of APC and PbS nanowires mixtures at different volume ratios show a gradual decrease in the monolayer area with increasing volume fraction of PbS nanowires. Change of surface potential with monolayer area at different volume ratios also reveals a gradual increase in the surface potential indicating incorporation of PbS nanowires within APC matrix. The compressibility and elastic constants measurements reveal an enhancement of the elasticity upon incorporation of PbS nanowires up to certain volume fractions. An enhancement in stability of the blend is observed upon PbS nanowire incorporation to the APC matrix. Rheological measurements also support the robustness of the mixture of APC and PbS nanowires in 3D bulk phase. Such robust ultrathin films of cellulose based-nanowire blend obtained by means of the Langmuir technique may lead to novel routes for designing cellulosic-based thin films and membranes.

  5. The Hatu gold anomaly, Xinjiang-Uygur Autonomous Region, China - testing the hypothesis of aeolian transport of gold

    USGS Publications Warehouse

    Smith, D.B.; Theobald, P.K.; Shiquan, S.; Tianxiang, R.; Zhihui, H.

    1993-01-01

    increase continued to approximately 5.5 km from Qiqu 1. The mean intermediate diameter of gold particles increased from 0.1 mm to approximately 0.25 mm and the gold particle content increased from approximately 0.3 particles per kg of sample to almost 8 particles per kg of sample. The morphology of the gold changed from a delicate filigree texture near Qiqu 1 to coarse, blocky particles in the southern part of the anomaly. The Hatu anomaly is caused primarily by alluvial dispersion of free gold from local point sources along the anomaly. Aeolian dispersion is restricted to very fine-grained (??2 ??m) gold included in sulfide minerals or quartz grains and is significant only within 1-2 km of the known deposits. ?? 1993.

  6. Hydrogen sulfide and translational medicine

    PubMed Central

    Guo, Wei; Cheng, Ze-yu; Zhu, Yi-zhun

    2013-01-01

    Hydrogen sulfide (H2S) along with carbon monoxide and nitric oxide is an important signaling molecule that has undergone large numbers of fundamental investigations. H2S is involved in various physiological activities associated with the regulation of homeostasis, vascular contractility, pro- and anti-inflammatory activities, as well as pro- and anti-apoptotic activities etc. However, the actions of H2S are influenced by its concentration, reaction time, and cell/disease types. Therefore, H2S is a signaling molecule without definite effect. The use of existing H2S donors is limited because of the instant release and short lifetime of H2S. Thus, translational medicine involving the sustained and controlled release of H2S is of great value for both scientific and clinical uses. H2S donation can be manipulated by different ways, including where H2S is given, how H2S is donated, or the specific structures of H2S-releasing drugs and H2S donor molecules. This review briefly summarizes recent progress in research on the physiological and pathological functions of H2S and H2S-releasing drugs, and suggests hope for future investigations. PMID:24096643

  7. Hydrogen Sulfide as a Gasotransmitter

    PubMed Central

    Gadalla, Moataz M.; Snyder, Solomon H.

    2010-01-01

    Nitric oxide (NO) and carbon monoxide (CO) are well established as messenger molecules throughout the body, gasotransmitters, based on striking alterations in mice lacking the appropriate biosynthetic enzymes. Hydrogen sulfide (H2S) is even more chemically reactive, but till recently there was little definitive evidence for its physiologic formation. Cystathionine β-synthase (CBS, EC 4.2.1.22), and Cystathionine γ-lyase (CSE; EC 4.4.1.1), also known as cytathionase, can generate H2S from cyst(e)ine. Very recent studies with mice lacking these enzymes have established that CSE is responsible for H2S formation in the periphery, while in the brain CBS is the biosynthetic enzyme. Endothelial-derived relaxing factor (EDRF) activity is reduced 80% in the mesenteric artery of mice with deletion of CSE, establishing H2S as a major physiologic EDRF. H2S appears to signal predominantly by S-sulfhydrating cysteines in its target proteins, analogous to S-nitrosylation by NO. Whereas S-nitrosylation typically inhibits enzymes, S-sulfhydration activates them. S-nitrosylation basally affects 1–2% of its target proteins, while 10–25% of H2S target proteins are S-sulfhydrated. In summary, H2S appears to be a physiologic gasotransmitter of comparable importance to NO and CO. PMID:20067586

  8. NEAR-CONTINUOUS MEASUREMENT OF HYDROGEN SULFIDE AND CARBONYL SULFIDE BY AN AUTOMATIC GAS CHROMATOGRAPH

    EPA Science Inventory

    An automatic gas chromatograph with a flame photometric detector that samples and analyzes hydrogen sulfide and carbonyl sulfide at 30-s intervals is described. Temperature programming was used to elute trace amounts of carbon disulfide present in each injection from a Supelpak-S...

  9. Hydrogen sulfide induces oxidative damage to RNA and DNA in a sulfide-tolerant marine invertebrate.

    PubMed

    Joyner-Matos, Joanna; Predmore, Benjamin L; Stein, Jenny R; Leeuwenburgh, Christiaan; Julian, David

    2010-01-01

    Hydrogen sulfide acts as an environmental toxin across a range of concentrations and as a cellular signaling molecule at very low concentrations. Despite its toxicity, many animals, including the mudflat polychaete Glycera dibranchiata, are periodically or continuously exposed to sulfide in their environment. We tested the hypothesis that a broad range of ecologically relevant sulfide concentrations induces oxidative stress and oxidative damage to RNA and DNA in G. dibranchiata. Coelomocytes exposed in vitro to sulfide (0-3 mmol L(-1) for 1 h) showed dose-dependent increases in oxidative stress (as 2',7'-dichlorofluorescein fluorescence) and superoxide production (as dihydroethidine fluorescence). Coelomocytes exposed in vitro to sulfide (up to 0.73 mmol L(-1) for 2 h) also acquired increased oxidative damage to RNA (detected as 8-oxo-7,8-dihydroguanosine) and DNA (detected as 8-oxo-7,8-dihydro-2'-deoxyguanosine). Worms exposed in vivo to sulfide (0-10 mmol L(-1) for 24 h) acquired elevated oxidative damage to RNA and DNA in both coelomocytes and body wall tissue. While the consequences of RNA and DNA oxidative damage are poorly understood, oxidatively damaged deoxyguanosine bases preferentially bind thymine, causing G-T transversions and potentially causing heritable point mutations. This suggests that sulfide can be an environmental mutagen in sulfide-tolerant invertebrates.

  10. Electrochemical and surface plasmon resonance characterization of β-cyclodextrin-based self-assembled monolayers and evaluation of their inclusion complexes with glucocorticoids

    NASA Astrophysics Data System (ADS)

    Frasconi, Marco; Mazzei, Franco

    2009-07-01

    This paper describes the characterization of a self-assembled β-cyclodextrin (β-CD)-derivative monolayer (β-CD-SAM) on a gold surface and the study of their inclusion complexes with glucocorticoids. To this aim the arrangement of a self-assembled β-cyclodextrin-derivative monolayer on a gold surface was monitored in situ by means of surface plasmon resonance (SPR) spectroscopy and double-layer capacitance measurements. Film thickness and dielectric constant were evaluated for a monolayer of β-CD using one-color-approach SPR. The selectivity of the β-CD host surface was verified by using electroactive species permeable and impermeable in the β-CD cavity. The redox probe was selected according to its capacity to permeate the β-CD monolayer and its electrochemical behavior. In order to evaluate the feasibility of an inclusion complex between β-CD-SAM with some steroids such as cortisol and cortisone, voltammetric experiments in the presence of the redox probes as molecules competitive with the steroids have been performed. The formation constant of the surface host-guest by β-CD-SAM and the steroids under study was calculated.

  11. Gold nanoprobes for theranostics

    PubMed Central

    Panchapakesan, Balaji; Book-Newell, Brittany; Sethu, Palaniappan; Rao, Madhusudhana; Irudayaraj, Joseph

    2011-01-01

    Gold nanoprobes have become attractive diagnostic and therapeutic agents in medicine and life sciences research owing to their reproducible synthesis with atomic level precision, unique physical and chemical properties, versatility of their morphologies, flexibility in functionalization, ease of targeting, efficiency in drug delivery and opportunities for multimodal therapy. This review highlights some of the recent advances and the potential for gold nanoprobes in theranostics. PMID:22122586

  12. Gold-bearing skarns

    USGS Publications Warehouse

    Theodore, Ted G.; Orris, Greta J.; Hammerstrom, Jane M.; Bliss, James D.

    1991-01-01

    In recent years, a significant proportion of the mining industry's interest has been centered on discovery of gold deposits; this includes discovery of additional deposits where gold occurs in skarn, such as at Fortitude, Nevada, and at Red Dome, Australia. Under the classification of Au-bearing skarns, we have modeled these and similar gold-rich deposits that have a gold grade of at least 1 g/t and exhibit distinctive skarn mineralogy. Two subtypes, Au-skarns and byproduct Au-skarns, can be recognized on the basis of gold, silver, and base-metal grades, although many other geological factors apparently are still undistinguishable largely because of a lack of detailed studies of the Au-skarns. Median grades and tonnage for 40 Au-skarn deposits are 8.6 g/t Au, 5.0 g/t Ag, and 213,000 t. Median grades and tonnage for 50 byproduct and Au-skarn deposits are 3.7 g/t Au, 37 g/t Ag, and 330,000 t. Gold-bearing skarns are generally calcic exoskarns associated with intense retrograde hydrosilicate alteration. These skarns may contain economic amounts of numerous other commodities (Cu, Fe, Pb, Zn, As, Bi, W, Sb, Co, Cd, and S) as well as gold and silver. Most Au-bearing skarns are found in Paleozoic and Cenozoic orogenic-belt and island-arc settings and are associated with felsic to intermediate intrusive rocks of Paleozoic to Tertiary age. Native gold, electru, pyrite, pyrrhotite, chalcopyrite, arsenopyrite, sphalerite, galena, bismuth minerals, and magnetite or hematite are the most common opaque minerals. Gangue minerals typically include garnet (andradite-grossular), pyroxene (diopside-hedenbergite), wollastonite, chlorite, epidote, quartz, actinolite-tremolite, and (or) calcite.

  13. ARSENIC MINERALS AS INDICATORS OF CONDITIONS OF GOLD DEPOSITION IN CARLIN-TYPE GOLD DEPOSITS.

    USGS Publications Warehouse

    Rytuba, James J.

    1984-01-01

    Arsenic minerals commonly occurring in Carlin-type gold deposits include orpiment and realgar and, more rarely, native arsenic and arsenopyrite. Other arsenic-bearing phases present include arsenian pyrite and stibnite and a number of thallium and mercury sulfides. Under conditions of constant temperature and pressure, the relative stability of arsenic minerals is a function of sulfur activity. At high sulfur activity, orpiment is the stable phase. As sulfur activity is decreased, more sulfur-deficient arsenic phases become stable with the progressive formation of realgar, native arsenic, arsenopyrite, and finally, loellingite at very low sulfur activity. Three univariant equilibrium assemblages: orpiment plus realgar, realgar plus native arsenic and native arsenic plus arsenopyrite are useful indicators of sulfur activity and commonly occur in the epithermal environment.

  14. Tectonic setting and metallogenesis of volcanogenic massive sulfide deposits in the Bonnifield Mining District, Northern Alaska Range: Chapter B in Recent U.S. Geological Survey studies in the Tintina Gold Province, Alaska, United States, and Yukon, Canada--results of a 5-year project

    USGS Publications Warehouse

    Dusel-Bacon, Cynthia; Aleinikoff, John N.; Premo, Wayne R.; Paradis, Suzanne; Lohr-Schmidt, Ilana; Gough, Larry P.; Day, Warren C.

    2007-01-01

    This paper summarizes the results of field and laboratory investigations, including whole-rock geochemistry and radiogenic isotopes, of outcrop and drill core samples from volcanogenic massive sulfide (VMS) deposits and associated metaigneous rocks in the Wood River area of the Bonnifield mining district, northern Alaska Range (see fig. 1 of Editors’ Preface and Overview). U-Pb zircon igneous crystallization ages from felsic rocks indicate a prolonged period of Late Devonian to Early Mississippian (373±3 to 357±4 million years before present, or Ma) magmatism. This magmatism occurred in a basinal setting along the ancient Pacific margin of North America. The siliceous and carbonaceous compositions of metasedimentary rocks, Precambrian model ages based on U-Pb dating of zircon and neodymium ages, and for some units, radiogenic neodymium isotopic compositions and whole-rock trace-element ratios similar to those of continental crust are evidence for this setting. Red Mountain (also known as Dry Creek) and WTF, two of the largest VMS deposits, are hosted in peralkaline metarhyolite of the Mystic Creek Member of the Totatlanika Schist. The Mystic Creek Member is distinctive in having high concentrations of high-field-strength elements (HFSE) and rare-earth elements (REE), indicative of formation in a within-plate (extensional) setting. Mystic Creek metarhyolite is associated with alkalic, within-plate basalt of the Chute Creek Member; neodymium isotopic data indicate an enriched mantle component for both members of this bimodal (rhyolite-basalt) suite. Anderson Mountain, the other significant VMS deposit, is hosted by the Wood River assemblage. Metaigneous rocks in the Wood River assemblage span a wide compositional range, including andesitic rocks, which are characteristic of arc volcanism. Our data suggest that the Mystic Creek Member likely formed in an extensional, back-arc basin that was associated with an outboard continental-margin volcanic arc that included

  15. Getting the Gold Treatment

    NASA Technical Reports Server (NTRS)

    2002-01-01

    Epner Technology, Inc., worked with Goddard Space Center to apply gold coating to the Vegetation Canopy Lidar (VCL) mirror. This partnership resulted in new commercial applications for Epner's LaserGold(R) process in the automotive industry. Previously, the company did not have equipment large enough to handle the plating of the stainless steel panels cost effectively. Seeing a chance to renew this effort, Epner Technology and Goddard entered into an agreement by which NASA would fund the facility needed to do the gold-plating, and Epner Technology would cover all other costs as part of their internal research and development. The VCL mirror project proceeded successfully, fulfilling Goddard's needs and leaving Epner Technology with a new facility to provide LaserGold for the automotive industry. The new capability means increased power savings and improvements in both quality and production time for BMW Manufacturing Corporation of Spartanburg, South Carolina, and Cadillac of Detroit, Michigan, as well as other manufacturers who have implemented Epner Technology's LaserGold process. LaserGold(R) is a registered trademark of Epner Technology, Inc.

  16. Experimental simulations of sulfide formation in the solar nebula.

    PubMed

    Lauretta, D S; Lodders, K; Fegley, B

    1997-07-18

    Sulfurization of meteoritic metal in H2S-H2 gas produced three different sulfides: monosulfide solid solution [(Fe,Ni)1-xS], pentlandite [(Fe,Ni)9-xS8], and a phosphorus-rich sulfide. The composition of the remnant metal was unchanged. These results are contrary to theoretical predictions that sulfide formation in the solar nebula produced troilite (FeS) and enriched the remaining metal in nickel. The experimental sulfides are chemically and morphologically similar to sulfide grains in the matrix of the Alais (class CI) carbonaceous chondrite, suggesting that these meteoritic sulfides may be condensates from the solar nebula.

  17. Realization of continuous Zachariasen carbon monolayer.

    PubMed

    Joo, Won-Jae; Lee, Jae-Hyun; Jang, Yamujin; Kang, Seog-Gyun; Kwon, Young-Nam; Chung, Jaegwan; Lee, Sangyeob; Kim, Changhyun; Kim, Tae-Hoon; Yang, Cheol-Woong; Kim, Un Jeong; Choi, Byoung Lyong; Whang, Dongmok; Hwang, Sung-Woo

    2017-02-01

    Rapid progress in two-dimensional (2D) crystalline materials has recently enabled a range of device possibilities. These possibilities may be further expanded through the development of advanced 2D glass materials. Zachariasen carbon monolayer, a novel amorphous 2D carbon allotrope, was successfully synthesized on germanium surface. The one-atom-thick continuous amorphous layer, in which the in-plane carbon network was fully sp(2)-hybridized, was achieved at high temperatures (>900°C) and a controlled growth rate. We verified that the charge carriers within the Zachariasen carbon monolayer are strongly localized to display Anderson insulating behavior and a large negative magnetoresistance. This new 2D glass also exhibited a unique ability as an atom-thick interface layer, allowing the deposition of an atomically flat dielectric film. It can be adopted in conventional semiconductor and display processing or used in the fabrication of flexible devices consisting of thin inorganic layers.

  18. Ground state structures in ferrofluid monolayers.

    PubMed

    Prokopieva, Taisia A; Danilov, Victor A; Kantorovich, Sofia S; Holm, Christian

    2009-09-01

    A combination of analytical calculations and Monte Carlo simulations is used to find the ground state structures in monodisperse ferrofluid monolayers. Taking into account the magnetic dipole-dipole interaction between all particles in the system we observe different topological structures that are likely to exist at low temperatures. The most energetically favored structures we find are rings, embedded rings, and rings side by side, and we are able to derive analytical expressions for the total energy of these structures. A detailed analysis of embedded rings and rings side by side shows that the interring interactions are negligible. We furthermore find that a single ideal ring is the ground state structure for a ferrofluid monolayer. We compared our theoretical predictions to the results of simulated annealing data and found them to be in excellent agreement.

  19. Piezoelectric monolayers as nonlinear energy harvesters.

    PubMed

    López-Suárez, Miquel; Pruneda, Miguel; Abadal, Gabriel; Rurali, Riccardo

    2014-05-02

    We study the dynamics of h-BN monolayers by first performing ab-initio calculations of the deformation potential energy and then solving numerically a Langevine-type equation to explore their use in nonlinear vibration energy harvesting devices. An applied compressive strain is used to drive the system into a nonlinear bistable regime, where quasi-harmonic vibrations are combined with low-frequency swings between the minima of a double-well potential. Due to its intrinsic piezoelectric response, the nonlinear mechanical harvester naturally provides an electrical power that is readily available or can be stored by simply contacting the monolayer at its ends. Engineering the induced nonlinearity, a 20 nm2 device is predicted to harvest an electrical power of up to 0.18 pW for a noisy vibration of 5 pN.

  20. Collective cell motion in endothelial monolayers

    PubMed Central

    Szabó, A.; Ünnep, R.; Méhes, E.; Twal, W. O.; Argraves, S. W.; Cao, Y.; Czirók, A.

    2011-01-01

    Collective cell motility is an important aspect of several developmental and pathophysiological processes. Despite its importance, the mechanisms that allow cells to be both motile and adhere to one another are poorly understood. In this study we establish statistical properties of the random streaming behavior of endothelial monolayer cultures. To understand the reported empirical findings, we expand the widely used cellular Potts model to include active cell motility. For spontaneous directed motility we assume a positive feedback between cell displacements and cell polarity. The resulting model is studied with computer simulations, and is shown to exhibit behavior compatible with experimental findings. In particular, in monolayer cultures both the speed and persistence of cell motion decreases, transient cell chains move together as groups, and velocity correlations extend over several cell diameters. As active cell motility is ubiquitous both in vitro and in vivo, our model is expected to be a generally applicable representation of cellular behavior. PMID:21076204

  1. Visualizing Individual Nitrogen Dopants in Monolayer Graphene

    SciTech Connect

    L Zhao; R He; K Rim; T Schiros; K Kim; H Zhou; C Gutierrez; S Chockalingam; C Arguello; et al.

    2011-12-31

    In monolayer graphene, substitutional doping during growth can be used to alter its electronic properties. We used scanning tunneling microscopy, Raman spectroscopy, x-ray spectroscopy, and first principles calculations to characterize individual nitrogen dopants in monolayer graphene grown on a copper substrate. Individual nitrogen atoms were incorporated as graphitic dopants, and a fraction of the extra electron on each nitrogen atom was delocalized into the graphene lattice. The electronic structure of nitrogen-doped graphene was strongly modified only within a few lattice spacings of the site of the nitrogen dopant. These findings show that chemical doping is a promising route to achieving high-quality graphene films with a large carrier concentration.

  2. Fracture characteristics of monolayer CVD-graphene.

    PubMed

    Hwangbo, Yun; Lee, Choong-Kwang; Kim, Sang-Min; Kim, Jae-Hyun; Kim, Kwang-Seop; Jang, Bongkyun; Lee, Hak-Joo; Lee, Seoung-Ki; Kim, Seong-Su; Ahn, Jong-Hyun; Lee, Seung-Mo

    2014-03-24

    We have observed and analyzed the fracture characteristics of the monolayer CVD-graphene using pressure bulge testing setup. The monolayer CVD-graphene has appeared to undergo environmentally assisted subcritical crack growth in room condition, i.e. stress corrosion cracking arising from the adsorption of water vapor on the graphene and the subsequent chemical reactions. The crack propagation in graphene has appeared to be able to be reasonably tamed by adjusting applied humidity and stress. The fracture toughness, describing the ability of a material containing inherent flaws to resist catastrophic failure, of the CVD-graphene has turned out to be exceptionally high, as compared to other carbon based 3D materials. These results imply that the CVD-graphene could be an ideal candidate as a structural material notwithstanding environmental susceptibility. In addition, the measurements reported here suggest that specific non-continuum fracture behaviors occurring in 2D monoatomic structures can be macroscopically well visualized and characterized.

  3. Fracture Characteristics of Monolayer CVD-Graphene

    NASA Astrophysics Data System (ADS)

    Hwangbo, Yun; Lee, Choong-Kwang; Kim, Sang-Min; Kim, Jae-Hyun; Kim, Kwang-Seop; Jang, Bongkyun; Lee, Hak-Joo; Lee, Seoung-Ki; Kim, Seong-Su; Ahn, Jong-Hyun; Lee, Seung-Mo

    2014-03-01

    We have observed and analyzed the fracture characteristics of the monolayer CVD-graphene using pressure bulge testing setup. The monolayer CVD-graphene has appeared to undergo environmentally assisted subcritical crack growth in room condition, i.e. stress corrosion cracking arising from the adsorption of water vapor on the graphene and the subsequent chemical reactions. The crack propagation in graphene has appeared to be able to be reasonably tamed by adjusting applied humidity and stress. The fracture toughness, describing the ability of a material containing inherent flaws to resist catastrophic failure, of the CVD-graphene has turned out to be exceptionally high, as compared to other carbon based 3D materials. These results imply that the CVD-graphene could be an ideal candidate as a structural material notwithstanding environmental susceptibility. In addition, the measurements reported here suggest that specific non-continuum fracture behaviors occurring in 2D monoatomic structures can be macroscopically well visualized and characterized.

  4. Realization of continuous Zachariasen carbon monolayer

    PubMed Central

    Joo, Won-Jae; Lee, Jae-Hyun; Jang, Yamujin; Kang, Seog-Gyun; Kwon, Young-Nam; Chung, Jaegwan; Lee, Sangyeob; Kim, Changhyun; Kim, Tae-Hoon; Yang, Cheol-Woong; Kim, Un Jeong; Choi, Byoung Lyong; Whang, Dongmok; Hwang, Sung-Woo

    2017-01-01

    Rapid progress in two-dimensional (2D) crystalline materials has recently enabled a range of device possibilities. These possibilities may be further expanded through the development of advanced 2D glass materials. Zachariasen carbon monolayer, a novel amorphous 2D carbon allotrope, was successfully synthesized on germanium surface. The one-atom-thick continuous amorphous layer, in which the in-plane carbon network was fully sp2-hybridized, was achieved at high temperatures (>900°C) and a controlled growth rate. We verified that the charge carriers within the Zachariasen carbon monolayer are strongly localized to display Anderson insulating behavior and a large negative magnetoresistance. This new 2D glass also exhibited a unique ability as an atom-thick interface layer, allowing the deposition of an atomically flat dielectric film. It can be adopted in conventional semiconductor and display processing or used in the fabrication of flexible devices consisting of thin inorganic layers. PMID:28246635

  5. Fracture Characteristics of Monolayer CVD-Graphene

    PubMed Central

    Hwangbo, Yun; Lee, Choong-Kwang; Kim, Sang-Min; Kim, Jae-Hyun; Kim, Kwang-Seop; Jang, Bongkyun; Lee, Hak-Joo; Lee, Seoung-Ki; Kim, Seong-Su; Ahn, Jong-Hyun; Lee, Seung-Mo

    2014-01-01

    We have observed and analyzed the fracture characteristics of the monolayer CVD-graphene using pressure bulge testing setup. The monolayer CVD-graphene has appeared to undergo environmentally assisted subcritical crack growth in room condition, i.e. stress corrosion cracking arising from the adsorption of water vapor on the graphene and the subsequent chemical reactions. The crack propagation in graphene has appeared to be able to be reasonably tamed by adjusting applied humidity and stress. The fracture toughness, describing the ability of a material containing inherent flaws to resist catastrophic failure, of the CVD-graphene has turned out to be exceptionally high, as compared to other carbon based 3D materials. These results imply that the CVD-graphene could be an ideal candidate as a structural material notwithstanding environmental susceptibility. In addition, the measurements reported here suggest that specific non-continuum fracture behaviors occurring in 2D monoatomic structures can be macroscopically well visualized and characterized. PMID:24657996

  6. Monitoring Morphological Changes in 2D Monolayer Semiconductors Using Atom-Thick Plasmonic Nanocavities

    PubMed Central

    2015-01-01

    Nanometer-sized gaps between plasmonically coupled adjacent metal nanoparticles enclose extremely localized optical fields, which are strongly enhanced. This enables the dynamic investigation of nanoscopic amounts of material in the gap using optical interrogation. Here we use impinging light to directly tune the optical resonances inside the plasmonic nanocavity formed between single gold nanoparticles and a gold surface, filled with only yoctograms of semiconductor. The gold faces are separated by either monolayers of molybdenum disulfide (MoS2) or two-unit-cell thick cadmium selenide (CdSe) nanoplatelets. This extreme confinement produces modes with 100-fold compressed wavelength, which are exquisitely sensitive to morphology. Infrared scattering spectroscopy reveals how such nanoparticle-on-mirror modes directly trace atomic-scale changes in real time. Instabilities observed in the facets are crucial for applications such as heat-assisted magnetic recording that demand long-lifetime nanoscale plasmonic structures, but the spectral sensitivity also allows directly tracking photochemical reactions in these 2-dimensional solids. PMID:25495220

  7. Electrically Modulated Localized Surface Plasmon around Self-Assembled-Monolayer-Covered Nanoparticles.

    PubMed

    Ma, Liyuan; Xu, Shandong; Wang, Chaoming; Wang, Haining; Zou, Shengli; Su, Ming

    2017-02-14

    This article reports the observation of electrical modulation of localized surface plasmon around self-assembled monolayer (SAM)-modified gold nanoparticles and the establishment of a new spectroscopy technique, that is, dynamic electro-optical spectroscopy (DEOS). The gold nanoparticles are deposited onto a transparent conductive substrate, and an electrical bias applied on the conductive substrate can cause shift of resonance plasmon response, where the direction of peak shift is related to the polarity of applied bias. The peak shift observed at 2.4 V is approximately ten times larger than those reported in previous work. It is postulated that significant peak shift is the result of reorientation of adsorbed water on electrode, which can change local dielectric environment of nanoparticles. An energy barrier is identified when adsorbed water molecules are turned from oxygen-down to oxygen-up. Frequency-dependent peak shifts on surface-modified gold nanoparticles show that reorientation is a fast reversible process with rich dynamics.

  8. Reduction of acid rock drainage using steel slag in cover systems over sulfide rock waste piles.

    PubMed

    de Almeida, Rodrigo Pereira; Leite, Adilson do Lago; Borghetti Soares, Anderson

    2015-04-01

    The extraction of gold, coal, nickel, uranium, copper and other earth-moving activities almost always leads to environmental damage. In metal and coal extraction, exposure of sulfide minerals to the atmosphere leads to generation of acid rock drainage (ARD) and in underground mining to acid mine drainage (AMD) due to contamination of infiltrating groundwater. This study proposes to develop a reactive cover system that inhibits infiltration of oxygen and also releases alkalinity to increase the pH of generated ARD and attenuate metal contaminants at the same time. The reactive cover system is constructed using steel slag, a waste product generated from steel industries. This study shows that this type of cover system has the potential to reduce some of the adverse effects of sulfide mine waste disposal on land. Geochemical and geotechnical characterization tests were carried out. Different proportions of sulfide mine waste and steel slag were studied in leachate extraction tests. The best proportion was 33% of steel slag in dry weight. Other tests were conducted as follows: soil consolidation, saturated permeability and soil water characteristic curve. The cover system was numerically modeled through unsaturated flux analysis using Vadose/w. The solution proposed is an oxygen transport barrier that allows rain water percolation to treat the ARD in the waste rock pile. The results showed that the waste pile slope is an important factor and the cover system must have 5 m thickness to achieve an acceptable effectiveness.

  9. Grafted silane monolayers: reconsideration of growth mechanisms

    NASA Astrophysics Data System (ADS)

    Ivanov, D. A.; Nysten, B.; Jonas, A. M.; Legras, R.

    1998-03-01

    Chemical force microscopy is a new technique devised to image chemical heterogeneities on surfaces. It requires the chemical modification of Atomic Force Microscopy (AFM) tips in order to create chemical probes. In this respect, self-assembled monolayers (SAM) of alkylchlorosilanes are particularly interesting as modifying agents for AFM tips. We report here our results on the kinetics of silanization and on the structure of such SAM's grafted on model surfaces (hydroxylated Si(100) wafers). AFM, contact angle measurements, X-ray reflectivity and X-ray photoelectron spectroscopy were used to characterize SAM's of octadecyltrichlorosilane (OTS) and octadecyldimethylchlorosilane (ODMS) grown from hexadecane and toluene solutions. The mechanism of grafting of OTS follows two stages. The first rapid stage corresponds to the nucleation and growth of island-like monolayer domains. The second slower stage is related to the densification of the monolayer. SAM's of ODMS were found to form thinner layers as compared to OTS, due to their lower grafting density probably resulting in a more disordered state of grafted alkyl chains. We also address the problems concerning the relationships between the quality of final SAM structures and the water content as well as the nature of the solvent used for silanization.

  10. Exploring atomic defects in molybdenum disulphide monolayers

    PubMed Central

    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 × 1013 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. PMID:25695374

  11. Investigation on gallium ions impacting monolayer graphene

    SciTech Connect

    Wu, Xin; Zhao, Haiyan Yan, Dong; Pei, Jiayun

    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.

  12. Phase transitions of monolayers on graphene

    NASA Astrophysics Data System (ADS)

    Kahn, Joshua; Dzyubenko, Boris; Vilches, Oscar; Cobden, David

    We have studied physisorbed layers of monatomic and diatomic gases on graphene. We used devices in which few-layer graphene, ranging from monolayer to trilayer, is suspended across a trench between two platinum contacts and are cleaned by thermal and current annealing. We found that the density of adsorbates is revealed by the conductance, similar to the case with nanotubes. The conductance change for a monolayer can be large. On trilayer graphene the adsorbed gases can be seen to exhibit transitions between two-dimensional phases identical to those on bulk graphite, including incommensurate and commensurate solid, fluid and vapor and multiple layers. New features appear in the conductance at the boundaries of the commensurate phase of Kr. We are able to measure single-particle binding energies very accurately and see how it depends on thickness; investigate the effects of changing disorder by gradually current annealing; and search for new phases in the case of monolayer graphene where atoms adsorbed on both sides can interact. We can map out the 2d phase diagrams very quickly by ohmic heating, which gives nearly instantaneous control of the temperature.

  13. Biocompatible Ferromagnetic Cr-Trihalide Monolayers

    NASA Astrophysics Data System (ADS)

    Sun, Qiang

    Cr with an electronic configuration of 3d54s1 possesses the largest atomic magnetic moment (6µB) of all elements in the 3d transition metal series. Furthermore, the trivalent chromium (Cr3+) is biocompatible and is widely found in food and supplements. Here using first principles calculations combined with Monte Carlo simulations based on Ising model, we systematically study a class of 2D ferromagnetic monolayers CrX3 (X = Cl, Br, I). The feasibility of exfoliation from their layered bulk phase is confirmed by the small cleavage energy and high in-plane stiffness. Spin-polarized calculations, combined with self consistently determined Hubbard U that accounts for strong correlation energy, demonstrate that CrX3 (X =Cl, Br, I) monolayers are ferromagnetic and Cr is trivalent and carries a magnetic moment of 3µB, the resulting Cr3+ ions are biocompatible. The corresponding Curie temperatures for CrCl3 CrBr3 CrI3 are are found to 66, 86, and 107 K, respectively, which can be increased to 323, 314, 293 K by hole doping. The biocompatibility and ferromagnetism render these Cr-containing trichalcogenide monolayers unique for applications.

  14. Synthesized “IN SITU” in Reverse Micelles of Silver-Sulfide Semiconductors

    NASA Astrophysics Data System (ADS)

    Pileni, M. P.; Motte, L.; Billoudet, F.; Petit, C.

    Functionalized reverse micelles are used to control the size of silver sulfide, Ag2S, nanosize particles. The size of the crystallites varies linearly with the water content from 2 to 10 nm. The particles have been coated with dodecanethiol and extracted from micelles. The size of the particles dispersed in heptane has been determined by small-angles x-ray scattering (SAXS) experiments and compared to those obtained by transmission electron microscopy (TEM). A good agreement between results is obtained by these two techniques. A drop of particles previously dispersed in heptane is dried on a carbon grill. A network of the particles forming monolayers of crystallites in a hexagonal distribution appears.

  15. Geochemical and mineralogical characterization of the abandoned Valzinco (lead-zinc) and Mitchell (gold) mine sites prior to reclamation, Spotsylvania County, Virginia

    USGS Publications Warehouse

    Hammarstrom, Jane M.; Johnson, Adam N.; Seal, Robert R., II; Meier, Allen L.; Briggs, Paul L.; Piatak, Nadine M.

    2006-01-01

    The Virginia gold-pyrite belt, part of the central Virginia volcanic-plutonic belt, hosts numerous abandoned metal mines. The belt extends from about 50 km south of Washington, D.C., for approximately 175 km to the southwest into central Virginia. The rocks that comprise the belt include metamorphosed volcanic and clastic (noncarbonate) sedimentary rocks that were originally deposited during the Ordovician). Deposits that were mined can be classified into three broad categories: 1. volcanic-associated massive sulfide deposits, 2. low-sulfide quartz-gold vein deposits, 3. gold placer deposits, which result from weathering of the vein deposits The massive sulfide deposits were historically mined for iron and pyrite (sulfur), zinc, lead, and copper but also yielded byproduct gold and silver. The most intensely mineralized and mined section of the belt is southwest of Fredericksburg, in the Mineral district of Louisa and Spotsylvania counties. The Valzinco Piatak lead-zinc mine and the Mitchell gold prospect are abandoned sites in Spotsylvania County. As a result of environmental impacts associated with historic mining, both sites were prioritized for reclamation under the Virginia Orphaned Land Program administered by the Virginia Department of Mines, Minerals, and Energy (VDMME). This report summarizes geochemical data for all solid sample media, along with mineralogical data, and results of weathering experiments on Valzinco tailings and field experiments on sediment accumulation in Knights Branch. These data provide a framework for evaluating water-rock interactionsand geoenvironmental signatures of long-abandoned mines developed in massive sulfide deposits and low-sulfide gold-quartz vein deposits in the humid temperate ecosystem domain in the eastern United States.

  16. Highly active engineered-enzyme oriented monolayers: formation, characterization and sensing applications

    PubMed Central

    2011-01-01

    Background The interest in introducing ecologically-clean, and efficient enzymes into modern industry has been growing steadily. However, difficulties associated with controlling their orientation, and maintaining their selectivity and reactivity is still a significant obstacle. We have developed precise immobilization of biomolecules, while retaining their native functionality, and report a new, fast, easy, and reliable procedure of protein immobilization, with the use of Adenylate kinase as a model system. Methods Self-assembled monolayers of hexane-1,6-dithiol were formed on gold surfaces. The monolayers were characterized by contact-angle measurements, Elman-reagent reaction, QCM, and XPS. A specifically designed, mutated Adenylate kinase, where cysteine was inserted at the 75 residue, and the cysteine at residue 77 was replaced by serine, was used for attachment to the SAM surface via spontaneously formed disulfide (S-S) bonds. QCM, and XPS were used for characterization of the immobilized protein layer. Curve fitting in XPS measurements used a Gaussian-Lorentzian function. Results and Discussion Water contact angle (65-70°), as well as all characterization techniques used, confirmed the formation of self-assembled monolayer with surface SH groups. X-ray photoelectron spectroscopy showed clearly the two types of sulfur atom, one attached to the gold (triolate) and the other (SH/S-S) at the ω-position for the hexane-1,6-dithiol SAMs. The formation of a protein monolayer was confirmed using XPS, and QCM, where the QCM-determined amount of protein on the surface was in agreement with a model that considered the surface area of a single protein molecule. Enzymatic activity tests of the immobilized protein confirmed that there is no change in enzymatic functionality, and reveal activity ~100 times that expected for the same amount of protein in solution. Conclusions To the best of our knowledge, immobilization of a protein by the method presented here, with the

  17. Lebediny gold deposit, Central Aldan: Mineral parageneses, stages, and formation conditions

    NASA Astrophysics Data System (ADS)

    Dobrovol'skaya, M. G.; Razin, M. V.; Prokof'ev, V. Yu.

    2016-07-01

    The mineral parageneses and succession of their formation are considered for the first time for the Zverevsky, Orekhovy, and Vodonosny ore lodes of the Lebediny gold deposit and the Radostny prospect in the Central Aldan ore district, which are genetically related to the epoch of Mesozoic tectonomagmatic reactivation. The orebodies, represented by two morphological varieties—ribbonlike lodes and steeply dipping veins—are hosted in lower part of the Vendian-Cambrian dolomitic sequence, which is cut through by Mesozoic subalkaline intrusive bodies. The chemistry of fahlore and rare minerals, including native gold and bismuth, altaite, aikinite, tetradymite, and sulfosalts of lillianite series, has been studied. Native gold is related to the late hydrothermal process and occurs in skarn and in quartz-tremolite-sulfide and quartz-carbonate-sulfide veins. The data on stable sulfur (δ34S) isotopes of sulfides, oxygen (δ18O) and carbon (δ13C) isotopes of carbonates, as well as on fluid inclusions in various generations of tremolite and quartz, provide evidence for the heterogeneity of ore-bearing solutions, their relationships to magmatism, the depth of the source feeding each specific lode, and different sources of ore-forming hydrothermal solutions.

  18. A study of the stability of cadmium sulfide/copper sulfide and cadmium sulfide copper-indium-diselenide solar cells

    NASA Astrophysics Data System (ADS)

    Noel, G.; Richard, N.; Gaines, G.

    1984-08-01

    Groups of high efficiency cadmium sulfide/copper sulfide solar cells were exposed to combinations of stresses designed to isolate and accelerate intrinsic degradation mechanisms. Stresses included elevated temperature, illumination intensity, and cell loading conditions. All stress exposures and tests were conducted in a benign (high purity argon) atmosphere. Two primary intrinsic modes of degradation were identified: degradation of the open circuit voltage under continuous illumination and nonzero loading was found to be self recovering upon interruption of illumination or upon shorting or reverse biasing the cells. It was attributed to traps in the depletion region. Recovery from decay of light generated current was not spontaneous but could be partially accomplished by annealing in a reducing (hydrogen) environment. It was attributed to changes in the stoichiometry of the copper sulfide under the influence of electric fields and currents.

  19. Hydrogen Sulfide Inhibits Amyloid Formation

    PubMed Central

    2015-01-01

    Amyloid fibrils are large aggregates of misfolded proteins, which are often associated with various neurodegenerative diseases such as Alzheimer’s, Parkinson’s, Huntington’s, and vascular dementia. The amount of hydrogen sulfide (H2S) is known to be significantly reduced in the brain tissue of people diagnosed with Alzheimer’s disease relative to that of healthy individuals. These findings prompted us to investigate the effects of H2S on the formation of amyloids in vitro using a model fibrillogenic protein hen egg white lysozyme (HEWL). HEWL forms typical β-sheet rich fibrils during the course of 70 min at low pH and high temperatures. The addition of H2S completely inhibits the formation of β-sheet and amyloid fibrils, as revealed by deep UV resonance Raman (DUVRR) spectroscopy and ThT fluorescence. Nonresonance Raman spectroscopy shows that disulfide bonds undergo significant rearrangements in the presence of H2S. Raman bands corresponding to disulfide (RSSR) vibrational modes in the 550–500 cm–1 spectral range decrease in intensity and are accompanied by the appearance of a new 490 cm–1 band assigned to the trisulfide group (RSSSR) based on the comparison with model compounds. The formation of RSSSR was proven further using a reaction with TCEP reduction agent and LC-MS analysis of the products. Intrinsic tryptophan fluorescence study shows a strong denaturation of HEWL containing trisulfide bonds. The presented evidence indicates that H2S causes the formation of trisulfide bridges, which destabilizes HEWL structure, preventing protein fibrillation. As a result, small spherical aggregates of unordered protein form, which exhibit no cytotoxicity by contrast with HEWL fibrils. PMID:25545790

  20. [Sulfide removal from wastewater by nanoscale iron].

    PubMed

    Xi, Hong-bo; Yang, Qi; Shang, Hai-tao; Hao, Chun-bo; Li, Zhi-ling

    2008-09-01

    Influencing factors, adsorption isotherm, adsorption kinetics and preliminary discussion on the mechanism of sulfide adsorption by nanoscale iron prepared in laboratory were studied using manual simulation sulfide wastewater. Experimental results indicate that the removal efficiency of S2- increases with increasing iron dosage and decreases with increasing initial S2- concentration and pH values. The removal efficiency of S2- is 100% when initial concentration is less than 100 mg x L(-1) and are 87.34%, 65.80% and 44.61% at pH 2, 7 and 13. The temperature at 25 degrees C favors the maximum adsorption of S2- with 19.17 mg x g(-1) of equilibrium adsorption quantity and the adsorption capacity decreas at higher or lower temperature. The adsorption data fit well to the Langmuir equation and the Freundlich equation. The sulfide adsorption follows the pseudo second order equation with the maximum initial sorption rate(h) is 1.575 3 mg x (g x mg)(-1) at 25 degrees C and the adsorption rate constant increases with the increasing of temperature. The activation energy(Ea) is 8.22 kJ x mol(-1). The mechanism of sulfide removal is being sorbed onto the iron nanoparticles via formation of surface compleses, FeOSH and iron sulfides (FeS, FeS2, FeSn).