Wrinkling of Atomic Planes in Ultrathin Au Nanowires

A detailed understanding of structure and stability of nanowires is critical for applications. Atomic resolution imaging of ultrathin single crystalline Au nanowires using aberration-corrected microscopy reveals an intriguing relaxation whereby the atoms in the close-packed atomic planes normal to the growth direction are displaced in the axial direction leading to wrinkling of the (111) atomic plane normal to the wire axis. First-principles calculations of the structure of such nanowires confirm this wrinkling phenomenon, whereby the close-packed planes relax to form saddle-like surfaces. Molecular dynamics studies of wires with varying diameters and different bounding surfaces point to the key role of surface stress on the relaxation process. Using continuum mechanics arguments, we show that the wrinkling arises due to anisotropy in the surface stresses and in the elastic response, along with the divergence of surface-induced bulk stress near the edges of a faceted structure. The observations provide new understanding on the equilibrium structure of nanoscale systems and could have important implications for applications in sensing and actuation.

New Insights into Electronic and Geometric Effects in the Enhanced Photoelectrooxidation of Ethanol Using ZnO Nanorod/Ultrathin Au Nanowire Hybrids

Oxidation of small organic molecules in a fuel cell is a viable method for energy production. However, the key issue is the development of suitable catalysts that exhibit high efficiencies and remain stable during operation. Here, we demonstrate that amine-modified ZnO nanorods on which ultrathin Au nanowires are grown act as an excellent catalyst for the oxidation of ethanol. We show that the modification of the ZnO nanorods with oleylamine not only modifies the electronic structure favorably but also serves to anchor the Au nanowires on the nanorods. The adsorption of OH- species on the Au nanowires that is essential for ethanol oxidation is facilitated at much lower potentials as compared to bare Au nanowires leading to high activity. While ZnO shows negligible electrocatalytic activity under normal conditions, there is significant enhancement in the activity under light irradiation. We demonstrate a synergistic enhancement in the photoelectrocatalytic activity of the ZnO/Au nanowire hybrid and provide mechanistic explanation for this enhancement based on both electronic as well as geometric effects. The principles developed are applicable for tuning the properties of other metal/semiconductor hybrids with potentially interesting applications beyond the fuel cell application demonstrated here.

Room Temperature Growth of Ultrathin Au Nanowires with High Areal Density over Large Areas by in Situ Functionalization of Substrate

Although ultrathin Au nanowires (similar to 2 nm diameter) are expected to demonstrate several interesting properties, their extreme fragility has hampered their use in potential applications. One way to improve the stability is to grow them on substrates; however, there is no general method to grow these wires over large areas. The existing methods suffer from poor coverage and associated formation of larger nanoparticles on the substrate. Herein, we demonstrate a room temperature method for growth of these nanowires with high coverage over large areas by in situ functionalization of the substrate. Using control experiments, we demonstrate that an in situ functionalization of the substrate is the key step in controlling the areal density of the wires on the substrate. We show that this strategy works for a variety of substrates ranging like graphene, borosil glass, Kapton, and oxide supports. We present initial results on catalysis using the wires grown on alumina and silica beads and also extend the method to lithography-free device fabrication. This method is general and may be extended to grow ultrathin Au nanowires on a variety of substrates for other applications.

Synthesis and Characterization of Au@Pt Nanoparticles with Ultrathin Platinum Overlayers

Gold-core platinum-shell (Au@Pt) nanoparticles with ultrathin platinum overlayers, ranging from submonolayer to two monolayers of platinum atoms, were prepared at room-temperature using a scalable, wet-chemical synthesis route. The synthesis involved the reduction of chloroauric acid with tannic acid to form 5 nm (nominal dia.) gold nanoparticles followed by addition of desired amount of chloroplatinic acid and hydrazine to form platinum overlayers with bulk Pt/Au atomic ratios (Pt surface coverages) corresponding to 0.19 (half monolayer), 0.39 (monolayer), 0.58 (1.5 monolayer) and 0.88 (2 monolayers). The colloidal particles were coated with octadecanethiol and phase-transferred into chlroform-hexane mixture to facilitate sample preparation for structural characterization. The structure of the resultant nanoparticles were determined to be Au@Pt using HRTEM, SAED, XPS, UV-vis and confirmed by cyclic voltammetry (CV) studies. Monolayers of octadecanethiol coated Au@Pt nanoparticles were self-assembled at an air-water interface and transfer printed twice onto a gold substrate to form bilayer films for electrochemical characterization. Electrochemical activity on such films was observed only after the removal of the octadecanethiol ligand coating the nanoparticles, using a RF plasma etching process. The electrochemical activity (HOR, MOR studies) of Au@Pt nanoparticles was found to be highest for particles having a two atom thick platinum overlayer. These nanoparticles can significantly enhance platinum utilization in electrocatalytic applications as their platinum content based activity was three times higher than pure platinum nanoparticles.

Reversible Aptamer-Au Plasmon Rulers for Secreted Single Molecules

Plasmon rulers, consisting of pairs of gold nanoparticles, allow single-molecule analysis without photobleaching or blinking; however, current plasmon rulers are irreversible, restricting detection to only single events. Here, we present a reversible plasmon ruler, comprised of coupled gold nanoparticles linked by a single aptamer, capable of binding individual secreted molecules with high specificity. We show that the binding of target secreted molecules to the reversible plasmon ruler is characterized by single-molecule sensitivity, high specificity, and reversibility. Such reversible plasmon rulers should enable dynamic and adaptive live-cell measurement of secreted single molecules in their local microenvironment.

Morphology control synthesis of Au-Cu2S metal-semiconductor hybrid nanostructures by modulating reaction constituents

A facile methodology for synthesizing Au-Cu2S hybrid nanoparticles is presented. Au-Cu2S nanoparticles have application in visible light driven photocatalytic degradation of dyes. Detailed microstructural and compositional characterization illustrated that the hybrid nanoparticles are composed of cube shaped Au-Cu solid solution and hemispherical shaped Cu2S phases. Investigation of nanoparticles extracted at different stages of the synthesis process revealed that the mechanism of formation of hybrid nanoparticles involved initial formation of isolated cube shaped pure Au nanoparticles and Cu-thiolate complex. In the subsequent stages, the Au nanoparticles get adsorbed onto the Cu-thiolate complex which is followed by the decomposition of the Cu-thiolate complex to form Au-Cu2S hybrid nanoparticles. This study also illustrates that an optimum concentration of dodecanethiol is required both for achieving size and morphological uniformity of the participating phases and for their attachment to form a hybrid nanoparticle.

Ultrathin Au nanowires supported on rGO/TiO2 as an efficient photoelectrocatalyst

We report the synthesis of stable rGO/TiO2/Au nanowire hybrids showing excellent electrocatalytic activity for ethanol oxidation. Phase-pure anatase TiO2 nanoparticles (similar to 3 nm) were grown on GO sheets followed by the growth of ultrathin Au nanowires leading to the formation of a multidimensional ternary structure (0-D TiO2 and 1-D Au on 2-D graphene oxide). The oleylamine used for the synthesis of the Au nanowires not only leads to stable Au nanowires anchored on the GO sheets but also leads to the functionalization and room temperature reduction of GO. Using control experiments, we delineate the role of the three components in the hybrid and show that there is a significant synergy. We show that the catalytic activity for ethanol oxidation primarily stems from the Au nanowires. While TiO2 triggers the formation of oxygenated species on the Au nanowire surface at a lower potential and also imparts photoactivity, rGO provides a conducting support to minimize the charge transfer resistance in addition to stabilizing the Au nanowires. Compared with nanoparticle hybrids, the nanowire hybrids display a much better electrocatalytic performance. In addition to high efficiency, the nanowire hybrids also show a remarkable tolerance towards H2O2. While our study has a direct bearing on fuel cell technology, the insights gained are sufficiently general such that they provide guiding principles for the development of multifunctional ternary hybrids.

Graphene-oxide-supported ultrathin Au nanowires: efficient electrocatalysts for borohydride oxidation

We report stable ultrathin Au nanowires supported on reduced graphene oxide with outstanding electrocatalytic activity for borohydride oxidation. Electrochemical impedance spectroscopy measurements showed abnormal inductive behavior, indicative of surface reactivation. DFT calculations indicate that the origin of the high activity stems from the position of the Au d-band center.

Density control of ZnO nanowires grown using Au-PMMA nanoparticles and their growth behavior.

Au nanoparticles stabilized by poly(methyl methacrylate) (PMMA) were used as a catalyst to grow vertically aligned ZnO nanowires (NWs). The density of ZnO NWs with very uniform diameter was controlled by changing the concentration of Au-PMMA nanoparticles (NPs). The density was in direct proportion to the concentration of Au-PMMA NPs. Furthermore, the growth process of ZnO NWs using Au-PMMA NPs was systematically investigated through comparison with that using Au thin film as a catalyst. Au-PMMA NPs induced polyhedral-shaped bases of ZnO NWs separated from each other, while Au thin film formed a continuous network of bases of ZnO NWs. This approach provides a facile and cost-effective catalyst density control method, allowing us to grow high-quality vertically aligned ZnO NWs suitable for many viable applications.

Adlayer Structures of DL-Homocysteine and L-Homocysteine Thiolactone on Au(111) Surface: an in situ STM Study

The adsorption Of DL-homocysteine (Hcy) and L-homocysteine thiolactone (HTL) on Au(1 1 1) electrode was investigated in 0.1 M HClO4 by cyclic voltammetry and in situ scanning tunneling microscopy (STM). Hcy and HTL molecules formed highly ordered adlayers on Au(1 1 1) surface. High-resolution STM images revealed the orientation and packing arrangement in the ordered adlayers. Hcy molecules formed (2root3 x 3root3)R30degrees adlayer structure and H-bonds between carboxyl groups were assumed to be responsible for the origin of tail-to-tail or head-to-head molecular arrangement, while HTL molecules formed (4 x 6) adlayer structure, and two different orientations and appearances in the ordered adlayer were found. Structural models were proposed for the two adlayers.

"Aplicación de un sistema multimétrico para evaluar la calidad del agua superficial en la microcuenca El Coyote del Rio Estelí, Nicaragua"

En la microcuenca El Coyote localizada en el municipio de Condega, Estelí, se evaluó la calidad del agua superficial de sde febrero del 2010 a febrero del 2011. El propósito fue la identificación de indicadores que faciliten la vigilancia y monitoreo de la calidad del agua . Se integró un sistema multimétrico utilizando las características físicoquímicas y bacteriológicas, macro invertebrados acuáticos, la caracterización morfométrica de la microcuenca y la información resultante a nivel de comunidad (cambios en el uso del suelo). En la determinación de la relación de la calidad del agua con la estructura de la macrofauna acuática (macroinvertebrados) se usó el método Biological Monitoring Working Party (BMWP/Col ) . La microcuenca tiene 144 afluentes con una forma oval - oblonga - alargada, y su curva hipsométrica refleja un estado de equilibrio relativo de juvenil a madurez. El uso del suelo es inadecuado y su entorno natural fue valorado como subóptimo. Aunque los parámetros fisico químicos indicaron que las aguas son alcalinas, con un nivel aceptable de oxigeno disuelto, categorizadas según el Diagrama de Riverside como aguas aptas par a riego (C2 - S1), y aceptables según valores determinados para DBO 5 y DQO; sin embargo, requieren de un tratamiento de descontaminación previo a su uso doméstico y agropecuario. Además, debido a la presencia de coliformes fecales estas aguas no están aptas para consumo humano . Los macroinvertebrados varían, según la estacionalidad, en riqueza, abundancia y distribución, presentando una disminución en el número de individuos en la época lluviosa (t= 5.21, p<2.18E - 07). E l 6 8 . 91 % de los macroinvertebrados bioin dicadores se distribuyeron en cinco familias : Leptohyphidae , Baetidae , Hydropsychidae , Chironomidae y Physidae , siendo el cariotipo piedra el que present ó mayor diversidad y abundancia . El promedio del BMWP /Col fue de 60.06, indicando una calidad del agua entre dudosa y aceptable , y el índice ASPT de 6.71 señala una contaminación moderada ; estos resultados coincide n con los obtenidos utilizando la batería de indicadores fisicoquímicos y bacteriológicos .

Estado actual del bosque de galería de la parte alta del rio Santa Elena, sector norte de la Universidad Nacional Agraria, Managua

~vii~ RESUMEN La presente investigación se realizó en el bosque de galería de la parte alta del río Santa Elena, de la Universidad Nacional Agraria, donde se identificó el estado actual y la estructura horizontal y vertical, la composición florística en el estrato arbóreo del río, además, se determinó la diversidad a través del índice ecológico de Shannon-Weiner, por lo cual se realizó un inventario al cien por ciento (100 %). En cuanto a la estructura horizontal, se encontró el mayor número de individuos correspondiendo a la categoría 10 a 19.9 cm, la que presento menores cantidades de árboles fue la categoría mayor de 90cm, la dominancia más alta fue para Ficus trigonata (Chilamate). En cuanto al índice de valor de importancia (IVI), los valores más altos, le corresponden a las especies, Ficus trigonata (Chilamate), seguido por Guazuma ulmifolia (Guácimo de ternero) y Pithecellobium dulce (Espino de playa), con respecto a la abundancia específica, Ficus trigonata (Chilamate) y Guazuma ulmifolia (Guácimo de ternero), son las más abundantes, obteniéndose el mayor valor en la ribera 4, similares resultados para la ribera 2, ribera 3, y los que presentaron menor diversidad fueron ribera 1 e Isla, existiendo las mayores abundancias para la ribera 4 y la ribera 2, sobresaliendo las especies de: Ficus trigonata (Chilamate), Inga vera (Guavillo) y Terminalia catappa (Almendra), las cuales se encuentran en todas las riberas, y otras presentes en tres y dos riberas, no obstante, las actividades que se realizan en el área y los en sayos de agricultura han permitido que disminuya la cobertura vegetal y dando espacio a nuevas especies arvense que se desarrollen llegando incluso a las orillas del río, por esta razón se proponen soluciones para conservar el recurso bosque de galería.

Induccion del celo en vacas en anestro post parto mediante la administracion de sales minerales, vitaminas y masajes ovaricos. Realizada en el municipio de Rio Blanco, departamento de Matagalpa

El presente estudio se realizó con el objetivo de establecer la efectividad del tratamiento de Inducción al celo de vacas en anestro post parto por medio de la administración de sales minerales, vitaminas y masajes ovarios; dicho tratamiento fue llevado a cabo en el municipio de Río Blanco departamento de Matagalpa. Caracterizándose por una buena distribución de las lluvias la mayor parte del año. El dicho municipio se da una predominancia de una cultura de gran alta productividad ganadera, el tamaño requerido de la muestra de este trabajo de 20 hembras en periodo de anestro post parto mayor de 50 días, las cuales fueron seleccionadas al azar y evalua das clínicamente por palpación rectal por un profesional de la medicina veterinaria. Los datos fueron analizados mediante la prueba de chi –cuadrado habiendo obtenido un resultado significativo a un nivel de confianza del 95% entre los tratamientos. Con base en los resultados obtenidos posterior al tratamiento de la administración de sales minerales, vitamina y masaje ovárico se alcan zó una respuesta positiva del 80 % al celo, el 80% en tasa de preñez y en relación a la aparición del celo posteri or al tratamiento se alcanzo una media de 6.13 días que al comparar la efectividad del tratamiento de solo la aplicación de masaje ovárico se observo un buen resultado positivo, superando las expectativas. En comparación con las hembras tratadas con solo masaje ovárico se obtuvo una respuesta positiva al celo de un 60%, con un 30% de tasa de preñez y 7.33 días promedio en anestro posterior al tratamiento, por lo tanto elaboramos la hipótesis basándonos en el estadígrafo de Chi-cuadrado obteniendo un resultado significativo empleando un nivel de significancia del 0.05% por lo que atribuimos las diferencias de ambos tratamientos.

Electrochemical, spectroscopic and SPM evidence for the controlled formation of self-assembled monolayers and organised multilayers of ferrocenyl alkyl thiols on Au(111)

Organised multilayers were formed from the controlled self-assembly of ferrocene alkyl thiols on Au(111) surfaces. The control was accomplished by increasing the concentration of the thiol solutions used for the assembly. Cyclic voltammetry, ellipsometry, scanning probe microscopy (STM and AFM) and in situ FTIR spectroscopy were used to probe the differences between mono- and multilayers of the same compounds. Electrochemical desorption studies confirmed that the multilayer structure is attached to the surface via one monolayer. The electrochemical behaviour of the multilayers indicated the presence of more than one controlling factor during the oxidation step, whereas the reduction was kinetically controlled which contrasts with the behaviour of monolayers, which exhibit kinetic control for the oxidation and reduction steps. Conventional and imaging ellipsometry confirmed that multilayers with well-defined increments in thickness could be produced. However, STM indicated that at the monolayer stage, the thiols used promote the mobility of Au atoms on the surface. It is very likely that the multilayer structure is held together through hydrogen bonding. To the best of out knowledge, this is the first example of a controlled one-step growth of multilayers of ferrocenyl alkyl thiols using self-assembly techniques.