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Understanding electron transport at the organic-inorganic interface is crucial for many research fields including surface physics and chemistry. In this article, we report the nonlocal chemical reactivity of one monolayer copper hexadecafluorophthalocyanine (F(16)CuPc) adsorbed on two different substrates, Ag(111) and Au(111), by injecting hot electrons from a scanning tunneling microscope tip. On the basis of experimental and theoretical results, the nonlocal reactions are proposed to strongly depend on hot-electron transport through molecule-substrate interface states. This observation of nonlocal reactivity increases our understanding of electron transport at organic-metal interfaces.
ACS Nano 2009 Nov 24
PMID:Nonlocal chemical reactivity at organic-metal interfaces. 1992 32

The nematode Caenorhabditis elegans is an excellent model organism for studies of glycan dynamics, a goal that requires tools for imaging glycans in vivo. Here we applied the bioorthogonal chemical reporter technique for the molecular imaging of mucin-type O-glycans in live C. elegans. We treated worms with azidosugar variants of N-acetylglucosamine (GlcNAc), N-acetylgalactosamine (GalNAc), and N-acetylmannosamine (ManNAc), resulting in the metabolic labeling of their cell-surface glycans with azides. Subsequently, the worms were reacted via copper-free click reaction with fluorophore-conjugated difluorinated cyclooctyne (DIFO) reagents. We identified prominent localization of mucins in the pharynx of all four larval stages, in the adult hermaphrodite pharynx, vulva and anus, and in the tail of the adult male. Using a multicolor, time-resolved imaging strategy, we found that the distribution and dynamics of the glycans varied anatomically and with respect to developmental stage.
ACS Chem Biol 2009 Dec 18
PMID:In vivo imaging of Caenorhabditis elegans glycans. 1995 90

The template-directed assembly of two planar molecules (copper phthalocyanine (CuPc) and pentacene) on SiC nanomesh has been studied by scanning tunneling microscopy and photoelectron spectroscopy, respectively. Both molecules are trapped as single molecules in the cells of SiC nanomesh at low coverage. At high coverage, CuPc forms a highly ordered single-molecular array with identical symmetry and periodicity as the substrate, whereas pentacene forms a quasi-amorphous layer due to the random mixture of three different adsorption configurations. This difference in adsorption behavior is attributed to differences in molecular geometries. The measured changes of work functions reveal weak charge transfer between the molecules and substrate. Both molecules are preferentially adsorbed on the SiC nanomesh rather than on graphene. The CuPc single-molecular array possesses good long-range order, large area coverage, and a molecular density of over 3.0 x 10(13) molecules/cm(2).
ACS Nano 2010 Feb 23
PMID:Template-directed molecular assembly on silicon carbide nanomesh: comparison between CuPc and pentacene. 2005 Jun 39

The symmetry-broken geometry and variation of metal composition of semishells induce new plasmonic properties. A system of separated metallic semishells embedded in a poly(dimethylsiloxane) polymer film provides an ideal platform to investigate the localized surface plasmon resonance modes of semishells. We demonstrate experimentally that silver, gold, copper, and aluminum semishells can offer distinct plasmonic responses due to the wide range of their material parameters. Numerical calculations combined with the plasmon hybridization theory render us a clear understanding and assignment of the plasmonic modes of the semishells.
ACS Nano 2010 Mar 23
PMID:Plasmonic modes of metallic semishells in a polymer film. 2013 53

A powerful means of enhancing our understanding of the structures and functions of enzymes that contain nickel-sulfur bonds, such as Ni superoxide dismutase, acetyl-coenzyme A synthase/carbon monoxide dehydrogenase, [NiFe] hydrogenase, and methyl-CoM reductase, involves the investigation of model compounds with similar structural and/or electronic properties. In this study, we have characterized a trans-mu-1,2-disulfido-bridged dinickel(II) species, [{(tmc)Ni}(2)(S(2))](2+) (1, tmc = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) by using electronic absorption, magnetic circular dichroism (MCD), and resonance Raman (rR) spectroscopic techniques, as well as density functional theory (DFT) and time-dependent DFT computational methods. Our computational results, validated on the basis of the experimental MCD data and previously reported (1)H NMR spectra, reveal that 1 is best described as containing two antiferromagnetically coupled high-spin Ni(II) centers. A normal coordinate analysis of the rR vibrational data was performed to quantify the core bond strengths, yielding force constants of k(Ni-S) = 2.69 mdyn/A and k(S-S) = 2.40 mdyn/A. These values provide a useful basis for a comparison of metal-S/O bonding in 1 and related Ni(2)(O(2)), Cu(2)(O(2)), and Cu(2)(S(2)) dimers. In both the disulfido and the peroxo species, the lower effective nuclear charge of Ni(II) as compared to Cu(II) results in a decreased covalency, and thus relatively weaker metal-S/O bonding interactions in the Ni(2) dimers than in the Cu(2) complexes.
 ...
PMID:Spectroscopic and computational studies of a trans-mu-1,2-disulfido-bridged dinickel species, [{(tmc)Ni}(2)(S(2))](OTf)(2): comparison of end-on disulfido and peroxo bonding in (Ni(II))(2) and (Cu(II))(2) species. 2019 95

Facile chemical approaches for the controllable synthesis of CuSe, CuInSe2 nanowire, and CuInSe2/CuInS2 core/shell nanocable bundles were developed. Hexagonal CuSe nanowire bundles with lengths up to hundreds of micrometers, consisting of many aligned nanowires with a diameter of about 10-15 nm, were prepared by reacting cubic Cu(2-x)Se nanowire bundles with a sodium citrate solution at room temperature. The CuSe nanowire bundles were then used as self-sacrificial templates for making bundles of tetragonal chalcopyrite CuInSe2 nanowires by reacting with InCl3 via a solvothermal process. Furthermore, bundles of CuInSe2/CuInS2 core/shell nanocables were obtained by adding sulfur to the reaction system, and the shell thickness of the polycrystalline CuInS2 in the nanocables increased with increasing S/Se molar ratios. It was found that the small radius of copper ions allows their fast outward diffusion from the interior to the surface of nanowires to react with sulfur atoms/anions and indium ions to form a CuInS2 shell. Enhanced optical absorption in the vis-NIR region of CuInSe2/CuInS2 core/shell nanocable bundles is demonstrated, which is considered beneficial for applications in optoelectronic devices and solar energy conversion.
ACS Nano 2010 Apr 27
PMID:Large-scale synthesis and phase transformation of CuSe, CuInSe2, and CuInSe2/CuInS2 core/shell nanowire bundles. 2021 Mar 50

For the first time, a conjugated fluorescent polymer was utilized to probe alpha-amino acids, sensitively and selectively, through a new approach. First the strong fluorescence of the prepared polyfluorene (P1) was quenched by trace copper ions, and then the quenched fluorescence was recovered upon the addition of alpha-amino acids, making P1 a new and sensitive biosensor toward alpha-amino acids. The experimental results demonstrated that the alpha-amino acid selective nature of P1 over other analytes was relatively good. Thus, the work reported here might open up a new avenue for developing new biosensors.
ACS Appl Mater Interfaces 2009 Feb
PMID:A new approach to fluorescence "turn-on" sensing of alpha-amino acids. 2035 6

A novel kind of miniature boat that might have many potential applications was fabricated from superhydrophobic copper meshes for the first time. These boats not only floated freely on a water surface but also exhibited striking loading capacities. By selection of the pore size of copper meshes, a loading capacity greater than 11.0 g could be readily achieved for a boat of 8.0 cm(3) in volume. The large loading capacity is believed to arise from the air film surrounding the superhydrophobic surfaces of boats. The results of this study present new applications of artificial superhydrophobic surfaces in areas of miniature aquatic devices.
ACS Appl Mater Interfaces 2009 Feb
PMID:Miniature boats with striking loading capacity fabricated from superhydrophobic copper meshes. 2035 32

The aim of this research was to explore the use of amine-containing polymeric and low-molar-mass organic protecting agents in the preparation of copper nanoparticles. Particles were synthesized using poly(ethylene imine) (PEI) or tetraethylenepentamine (TEPA) as protecting agents. The resulting particles were studied with UV-vis spectrometry, thermogravimetry, scanning electron microscopy, and transmission electron microscopy, wide-angle X-ray scattering with heating, X-ray photoelectron spectroscopy, and Auger electron spectroscopy. The average crystal sizes for the particles were at room temperature 8.5 and 19.4 nm for PEI and TEPA, respectively, and some surface oxidation was observed. The particles were sintered on paper, and the resistance and resistivity were measured. For Cu/PEI samples, the protecting agent was removed upon sintering at relatively low temperatures (between 150 and 200 degrees C). At this temperature range, particles exhibited a rapid increase in the crystal size. Sintered particles exhibited high conductivity, indicating that these kinds of materials might find use in paper-based printing.
ACS Appl Mater Interfaces 2009 Feb
PMID:Poly(ethylene imine) and tetraethylenepentamine as protecting agents for metallic copper nanoparticles. 2035 45

Adding conductive fillers to nonconductive polymers is a common way to make soft conductive materials such as conductive adhesives. An important issue is how to achieve high volume conductivity with acceptable mechanical performance. Two questions pertaining to this issue were studied in this paper. One question was whether the maximum conductivity benefits from larger or smaller particle sizes. The second was what is the maximum achievable conductivity. One incentive for this work is the recent availability of nanomaterials that provide opportunities to make conductive composites using much smaller particles than in the past. We found that the conductivity of platinum, carbon black, and silver particles in their polyurethane composites did not vary greatly with particle size (from micrometer to nanometer range). What was unexpected was that in all the composite examples, the highest conductivity achieved was only on the order of 1% of that of the pure bulk conductive materials. Further experiments to emulate these conductive composites with platinum, carbon black, copper, and nickel particles without polymer matrix showed similar results, indicating the issue is not simply dispersion homogeneity, nano versus macro particles, particle connectivity/percolation, or the presence of the matrix materials. We interpret this to mean that the composite systems are intrinsically limited by the contact between filler particles.
ACS Appl Mater Interfaces 2009 Jan
PMID:Maximum conductivity of packed nanoparticles and their polymer composites. 2035 60


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