Kinetic energy sum spectra in nonmesonic weak decay of hypernuclei

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Outlining precision boundaries among areas with different variability standards using magnetic susceptibility and geomorphic surfaces

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

TOPOLOGY OF SINPLE SINGULARITIES OF RULED SURFACES IN R-p

In this work we compare the simple singularities of germs from R-2 to R-p with multiplicity 2 or 3 with the singularities appearing in the set of 2-ruled surfaces. We also study the topological type of all finitely determined singularities by studying generic projections of these singularities in R-3. (C) 2011 Elsevier B.V. All rights reserved.

Triboelectricity: Macroscopic Charge Patterns Formed by Self-Arraying Ions on Polymer Surfaces

Tribocharged polymers display macroscopically patterned positive and negative domains, verifying the fractal geometry of electrostatic mosaics previously detected by electric probe microscopy. Excess charge on contacting polyethylene (PE) and polytetrafluoroethylene (PTFE) follows the triboelectric series but with one caveat: net charge is the arithmetic sum of patterned positive and negative charges, as opposed to the usual assumption of uniform but opposite signal charging on each surface. Extraction with n-hexane preferentially removes positive charges from PTFE, while 1,1-difluoroethane and ethanol largely remove both positive and negative charges. Using suitable analytical techniques (electron energy-loss spectral imaging, infrared microspectrophotometry and carbonization/colorimetry) and theoretical calculations, the positive species were identified as hydrocarbocations and the negative species were identified as fluorocarbanions. A comprehensive model is presented for PTFE tribocharging with PE: mechanochemical chain homolytic rupture is followed by electron transfer from hydrocarbon free radicals to the more electronegative fluorocarbon radicals. Polymer ions self-assemble according to Flory-Huggins theory, thus forming the experimentally observed macroscopic patterns. These results show that tribocharging can only be understood by considering the complex chemical events triggered by mechanical action, coupled to well-established physicochemical concepts. Patterned polymers can be cut and mounted to make macroscopic electrets and multipoles.

Synthesis and characterisation of photoreactive silanes for the self-assembly on functionalised silica surfaces

The aim of this thesis was to investigate novel techniques to create complex hierarchical chemical patterns on silica surfaces with micro to nanometer sized features. These surfaces were used for a site-selective assembly of colloidal particles and oligonucleotides. To do so, functionalised alkoxysilanes (commercial and synthesised ones) were deposited onto planar silica surfaces. The functional groups can form reversible attractive interactions with the complementary surface layers of the opposing objects that need to be assembled. These interactions determine the final location and density of the objects onto the surface. Photolithographically patterned silica surfaces were modified with commercial silanes, in order to create hydrophilic and hydrophobic regions on the surface. Assembly of hydrophobic silica particles onto these surfaces was investigated and finally, pH and charge effects on the colloidal assembly were analysed. In the second part of this thesis the concept of novel, "smart" alkoxysilanes is introduced that allows parallel surface activation and patterning in a one-step irradiation process. These novel species bear a photoreactive head-group in a protected form. Surface layers made from these molecules can be irradiated through a mask to remove the protecting group from selected regions and thus generate lateral chemical patterns of active and inert regions on the substrate. The synthesis of an azide-reactive alkoxysilane was successfully accomplished. Silanisation conditions were carefully optimised as to guarantee a smooth surface layer, without formation of micellar clusters. NMR and DLS experiments corroborated the absence of clusters when using neither water nor NaOH as catalysts during hydrolysis, but only the organic solvent itself. Upon irradiation of the azide layer, the resulting nitrene may undergo a variety of reactions depending on the irradiation conditions. Contact angle measurements demonstrated that the irradiated surfaces were more hydrophilic than the non-irradiated azide layer and therefore the formation of an amine upon irradiation was postulated. Successful photoactivation could be demonstrated using condensation patterns, which showed a change in wettability on the wafer surface upon irradiation. Colloidal deposition with COOH functionalised particles further underlined the formation of more hydrophilic species. Orthogonal photoreactive silanes are described in the third part of this thesis. The advantage of orthogonal photosensitive silanes is the possibility of having a coexistence of chemical functionalities homogeneously distributed in the same layer, by using appropriate protecting groups. For this purpose, a 3',5'-dimethoxybenzoin protected carboxylic acid silane was successfully synthesised and the kinetics of its hydrolysis and condensation in solution were analysed in order to optimise the silanisation conditions. This compound was used together with a nitroveratryl protected amino silane to obtain bicomponent surface layers. The optimum conditions for an orthogonal deprotection of surfaces modified with this two groups were determined. A 2-step deprotection process through a mask generated a complex pattern on the substrate by activating two different chemistries at different sites. This was demonstrated by colloidal adsorption and fluorescence labelling of the resulting substrates. Moreover, two different single stranded oligodeoxynucleotides were immobilised onto the two different activated areas and then hybrid captured with their respective complementary, fluorescent labelled strand. Selective hybridisation could be shown, although non-selective adsorption issues need to be resolved, making this technique attractive for possible DNA microarrays.

Development and application of an analytical method for the determination of total atmospheric biogenic non-methane organic carbon

Ein wesentlicher Anteil an organischem Kohlenstoff, der in der Atmosphäre vorhanden ist, wird als leichtflüchtige organische Verbindungen gefunden. Diese werden überwiegend durch die Biosphäre freigesetzt. Solche biogenen Emissionen haben einen großen Einfluss auf die chemischen und physikalischen Eigenschaften der Atmosphäre, indem sie zur Bildung von bodennahem Ozon und sekundären organischen Aerosolen beitragen. Um die Bildung von bodennahem Ozon und von sekundären organischen Aerosolen besser zu verstehen, ist die technische Fähigkeit zur genauen Messung der Summe dieser flüchtigen organischen Substanzen notwendig. Häufig verwendete Methoden sind nur auf den Nachweis von spezifischen Nicht-Methan-Kohlenwasserstoffverbindungen fokussiert. Die Summe dieser Einzelverbindungen könnte gegebenenfalls aber nur eine Untergrenze an atmosphärischen organischen Kohlenstoffkonzentrationen darstellen, da die verfügbaren Methoden nicht in der Lage sind, alle organischen Verbindungen in der Atmosphäre zu analysieren. Einige Studien sind bekannt, die sich mit der Gesamtkohlenstoffbestimmung von Nicht-Methan-Kohlenwasserstoffverbindung in Luft beschäftigt haben, aber Messungen des gesamten organischen Nicht-Methan-Verbindungsaustauschs zwischen Vegetation und Atmosphäre fehlen. Daher untersuchten wir die Gesamtkohlenstoffbestimmung organische Nicht-Methan-Verbindungen aus biogenen Quellen. Die Bestimmung des organischen Gesamtkohlenstoffs wurde durch Sammeln und Anreichern dieser Verbindungen auf einem festen Adsorptionsmaterial realisiert. Dieser erste Schritt war notwendig, um die stabilen Gase CO, CO2 und CH4 von der organischen Kohlenstofffraktion zu trennen. Die organischen Verbindungen wurden thermisch desorbiert und zu CO2 oxidiert. Das aus der Oxidation entstandene CO2 wurde auf einer weiteren Anreicherungseinheit gesammelt und durch thermische Desorption und anschließende Detektion mit einem Infrarot-Gasanalysator analysiert. Als große Schwierigkeiten identifizierten wir (i) die Abtrennung von CO2 aus der Umgebungsluft von der organischen Kohlenstoffverbindungsfaktion während der Anreicherung sowie (ii) die Widerfindungsraten der verschiedenen Nicht-Methan-Kohlenwasserstoff-verbindungen vom Adsorptionsmaterial, (iii) die Wahl des Katalysators sowie (iiii) auftretende Interferenzen am Detektor des Gesamtkohlenstoffanalysators. Die Wahl eines Pt-Rd Drahts als Katalysator führte zu einem bedeutenden Fortschritt in Bezug auf die korrekte Ermittlung des CO2-Hintergrund-Signals. Dies war notwendig, da CO2 auch in geringen Mengen auf der Adsorptionseinheit während der Anreicherung der leichtflüchtigen organischen Substanzen gesammelt wurde. Katalytische Materialien mit hohen Oberflächen stellten sich als unbrauchbar für diese Anwendung heraus, weil trotz hoher Temperaturen eine CO2-Aufnahme und eine spätere Abgabe durch das Katalysatormaterial beobachtet werden konnte. Die Methode wurde mit verschiedenen leichtflüchtigen organischen Einzelsubstanzen sowie in zwei Pflanzenkammer-Experimenten mit einer Auswahl an VOC-Spezies getestet, die von unterschiedlichen Pflanzen emittiert wurden. Die Pflanzenkammer-messungen wurden durch GC-MS und PTR-MS Messungen begleitet. Außerdem wurden Kalibrationstests mit verschiedenen Einzelsubstanzen aus Permeations-/Diffusionsquellen durchgeführt. Der Gesamtkohlenstoffanalysator konnte den tageszeitlichen Verlauf der Pflanzenemissionen bestätigen. Allerdings konnten Abweichungen für die Mischungsverhältnisse des organischen Gesamtkohlenstoffs von bis zu 50% im Vergleich zu den begleitenden Standardmethoden beobachtet werden.

In situ dehydration behavior of zeolite-like cavansite: A single-crystal X-ray study

To track dehydration behavior of cavansite, Ca(VO)(Si4O10)·4H2O space group Pnma, a = 9.6329(2), b = 13.6606(2), c = 9.7949(2) Å, V = 1288.92(4) Å3 single-crystal X-ray diffraction data on a crystal from Wagholi quarry, Poona district (India) were collected up to 400 °C in steps of 25 °C up to 250 °C and in steps of 50 °C between 250 and 400 °C. The structure of cavansite is characterized by layers of silicate tetrahedra connected by V4+O5 square pyramids. This way a porous framework structure is formed with Ca and H2O as extraframework occupants. At room temperature, the hydrogen bond system was analyzed. Ca is eightfold coordinated by four bonds to O of the framework structure and four bonds to H2O molecules. H2O linked to Ca is hydrogen bonded to the framework and also to adjacent H2O molecules. The dehydration in cavansite proceeds in four steps.At 75 °C, H2O at O9 was completely expelled leading to 3 H2O pfu with only minor impact on framework distortion and contraction V = 1282.73(3) Å3. The Ca coordination declined from originally eightfold to sevenfold and H2O at O7 displayed positional disorder.At 175 °C, the split O7 sites approached the former O9 position. In addition, the sum of the three split positions O7, O7a, and O7b decreased to 50% occupancy yielding 2 H2O pfu accompanied by a strong decrease in volume V = 1206.89(8) Å3. The Ca coordination was further reduced from sevenfold to sixfold.At 350 °C, H2O at O8 was released leading to a formula with 1 H2O pfu causing additional structural contraction (V = 1156(11) Å3). At this temperature, Ca adopted fivefold coordination and O7 rearranged to disordered positions closer to the original O9 H2O site.At 400 °C, cavansite lost crystallinity but the VO2+ characteristic blue color was preserved. Stepwise removal of water is discussed on the basis of literature data reporting differential thermal analyses, differential thermo-gravimetry experiments and temperature dependent IR spectra in the range of OH stretching vibrations.

Diagnosis of erosive tooth wear.

The clinical diagnosis 'erosion' is made from characteristic deviations from the original anatomical tooth morphology, thus distinguishing acid-induced tissue loss from other forms of wear. Primary pathognomonic features are shallow concavities on smooth surfaces occurring coronal from the enamel-cementum junction. Problems from diagnosing occlusal surfaces and exposed dentine are discussed. Indices for recording erosive wear include morphological as well as quantitative criteria. Currently, various indices are used, each having their virtues and flaws, making the comparison of prevalence studies difficult. The Basic Erosive Wear Examination (BEWE) is described, which is intended to provide an easy tool for research as well as for use in general dental practice. The cumulative score of this index is the sum of the most severe scores obtained from all sextants and is linked to suggestions for clinical management. In addition to recording erosive lesions, the assessment of progression is important as the indication of treatment measures depends on erosion activity. A number of evaluated and sensitive methods for in vitro and in situ approaches are available, but the fundamental problem for their clinical use is the lack of reidentifiable reference areas. Tools for clinical monitoring are described.

Pasture degradation modifies the water and carbon cycles of the Tibetan highlands

The Tibetan Plateau has a significant role with regard to atmospheric circulation and the monsoon in particular. Changes between a closed plant cover and open bare soil are one of the striking effects of land use degradation observed with unsustainable range management or climate change, but experiments investigating changes of surface properties and processes together with atmospheric feedbacks are rare and have not been undertaken in the world's two largest alpine ecosystems, the alpine steppe and the Kobresia pygmaea pastures of the Tibetan Plateau. We connected measurements of micro-lysimeter, chamber, 13C labelling, and eddy covariance and combined the observations with land surface and atmospheric models, adapted to the highland conditions. This allowed us to analyse how three degradation stages affect the water and carbon cycle of pastures on the landscape scale within the core region of the Kobresia pygmaea ecosystem. The study revealed that increasing degradation of the Kobresia turf affects carbon allocation and strongly reduces the carbon uptake, compromising the function of Kobresia pastures as a carbon sink. Pasture degradation leads to a shift from transpiration to evaporation while a change in the sum of evapotranspiration over a longer period cannot be confirmed. The results show an earlier onset of convection and cloud generation, likely triggered by a shift in evapotranspiration timing when dominated by evaporation. Consequently, precipitation starts earlier and clouds decrease the incoming solar radiation. In summary, the changes in surface properties by pasture degradation found on the highland have a significant influence on larger scales.

Abundance and biomass of phytoplankton in the western part of the Black Sea in September 1991 during the NATO Programme Hydroblack

The samples were concentrated down to 50 cm**3 by slow decantation after storage for 20 days in a cool and dark place. The species identification was done under light microscope OLIMPUS-BS41 connected to a video-interactive image analysis system at magnification of the ocular 10X and objective - 40X. A Sedgwick-Rafter camera (1ml) was used for counting. 400 specimen were counted for each sample, while rare and large species were checked in the whole sample (Manual of phytoplankton, 2005). Species identification was mainly after Carmelo T. (1997) and Fukuyo, Y. (2000). Total phytoplankton abundance was calculated as sum of taxon-specific abundances. Total phytoplankton biomass was calculated as sum of taxon-specific biomasses. The cell biovolume was determined based on morpho-metric measurement of phytoplankton units and the corresponding geometric shapes as described in detail in (Edier, 1979).

Gas hydrate structures and C1-C5 hydrocarbons at individual sites in the Gulf of Mexico

Gas hydrate samples from various locations in the Gulf of Mexico (GOM) differ considerably in their microstructure. Distinct microstructure characteristics coincide with discrete crystallographic structures, gas compositions and calculated thermodynamic stabilities. The crystallographic structures were established by X-ray diffraction, using both conventional X-ray sources and high-energy synchrotron radiation. The microstructures were examined by cryo-stage Field-Emission Scanning Electron Microscopy (FE-SEM). Good sample preservation was warranted by the low ice fractions shown from quantitative phase analyses. Gas hydrate structure II samples from the Green Canyon in the northern GOM had methane concentrations of 70-80% and up to 30% of C2-C5 of measured hydrocarbons. Hydrocarbons in the crystallographic structure I hydrate from the Chapopote asphalt volcano in the southern GOM was comprised of more than 98% methane. Fairly different microstructures were identified for those different hydrates: Pores measuring 200-400 nm in diameter were present in structure I gas hydrate samples; no such pores but dense crystal surfaces instead were discovered in structure II gas hydrate. The stability of the hydrate samples is discussed regarding gas composition, crystallographic structure and microstructure. Electron microscopic observations showed evidence of gas hydrate and liquid oil co-occurrence on a micrometer scale. That demonstrates that oil has direct contact to gas hydrates when it diffuses through a hydrate matrix.

Abundance and biomass of phytoplankton in the western part of the Black Sea during the R/V Akademik cruise Ak082001 in August 2001

The dataset is composed of 41 samples from 10 stations. The phytoplankton samples were collected by 5l Niskin bottles attached to the CTD system. The sampling depths were selected according to the CTD profile and the in situ fluorometer readings: surface, temperature, salinity and fluorescence gradients and 1 m above the bottom. At some stations phytoplankton net samples (20 µm mesh-size) were collected to assist species biodiversity examination. The samples (1l sea water) were preserved in 4% buffered to pH 8-8.2 with disodiumtetraborate formaldehyde solution and stored in plastic containers. On board at each station few live samples were qualitatively examined under microscope for preliminary analysis of taxonomic composition and dominant species. The taxon-specific phytoplankton abundance samples were concentrated down to 50 cm**3 by slow decantation after storage for 20 days in a cool and dark place. The species identification was done under light microscope OLIMPUS-BS41 connected to a video-interactive image analysis system at magnification of the ocular 10X and objective - 40X. A Sedgwick-Rafter camera (1ml) was used for counting. 400 specimen were counted for each sample, while rare and large species were checked in the whole sample (Manual of phytoplankton, 2005). Species identification was mainly after Carmelo T. (1997) and Fukuyo, Y. (2000). Total phytoplankton abundance was calculated as sum of taxon-specific abundances. Total phytoplankton biomass was calculated as sum of taxon-specific biomasses. The cell biovolume was determined based on morpho-metric measurement of phytoplankton units and the corresponding geometric shapes as described in detail in (Edier, 1979).

Geometric Integrability of the Camassa-Holm Equation. II

It is known that the Camassa–Holm (CH) equation describes pseudo-spherical surfaces and that therefore its integrability properties can be studied by geometrical means. In particular, the CH equation admits nonlocal symmetries of “pseudo-potential type”: the standard quadratic pseudo-potential associated with the geodesics of the pseudo-spherical surfaces determined by (generic) solutions to CH, allows us to construct a covering π of the equation manifold of CH on which nonlocal symmetries can be explicitly calculated. In this article, we present the Lie algebra of (first-order) nonlocal π-symmetries for the CH equation, and we show that this algebra contains a semidirect sum of the loop algebra over sl(2,R) and the centerless Virasoro algebra. As applications, we compute explicit solutions, we construct a Darboux transformation for the CH equation, and we recover its recursion operator. We also extend our results to the associated Camassa–Holm equation introduced by J. Schiff.

Gestión intelectual de las prácticas comunicativas en arquitectura : S, M, L, XL, el gran evento = The intellectual management of communication practices in architecture : S, M, L, XL, the big event

La tesis doctoral se centra en la posibilidad de entender que la práctica de arquitectura puede encontrar en las prácticas comunicativas un apoyo instrumental, que sobrepasa cualquier simplificación clásica del uso de los medios como una mera aplicación superficial, post-producida o sencillamente promocional. A partir de esta premisa se exponen casos del último cuarto del siglo XX y se detecta que amenazas como el riesgo de la banalización, la posible saturación de la imagen pública o la previsible asociación incorrecta con otros individuos en presentaciones grupales o por temáticas, han podido influir en un crecimiento notable de la adquisición de control, por parte de los arquitectos, en sus oportunidades mediáticas. Esto es, como si la arquitectura hubiera empezado a superar y optimizar algo inevitable, que las fórmulas expositivas y las publicaciones, o más bien del exponer(se) y publicar(se), son herramientas disponibles para activar algún tipo de gestión intelectual de la comunicación e información circulante sobre si misma. Esta práctica de “autoedición” se analiza en un periodo concreto de la trayectoria de OMA -Office for Metropolitan Architecture-, estudio considerado pionero en el uso eficiente, oportunista y personalizado de los medios. Así, la segunda parte de la tesis se ocupa del análisis de su conocida monografía S,M,L,XL (1995), un volumen que contó con gran participación por parte de sus protagonistas durante la edición, y de cuyo proceso de producción apenas se había investigado. Esta publicación señaló un punto de inflexión en su género alterando todo formato y restricciones anteriores, y se ha convertido en un volumen emblemático para la disciplina que ninguna réplica posterior ha podido superar. Aquí se presenta a su vez como el desencadenante de la construcción de un “gran evento” que concluye en la transformación de la identidad de OMA en 10 años, paradójicamente entre el nacimiento de la Fundación Groszstadt y el arranque de la actividad de AMO, dos entidades paralelas clave anexas a OMA. Este planteamiento deviene de cómo la investigación desvela que S,M,L,XL es una pieza más, central pero no independiente, dentro de una suma de acciones e individuos, así como otras publicaciones, exposiciones, eventos y también artículos ensayados y proyectos, en particular Bigness, Generic City, Euralille y los concursos de 1989. Son significativos aspectos como la apertura a una autoría múltiple, encabezada por Rem Koolhaas y el diseñador gráfico Bruce Mau, acompañados en los agradecimientos de la editora Jennifer Sigler y cerca de una centena de nombres, cuyas aportaciones no necesariamente se basan en la construcción de fragmentos del libro. La supresión de ciertos límites permite superar también las tareas inicialmente relevantes en la edición de una publicación. Un objetivo general de la tesis es también la reflexión sobre relaciones anteriormente cuestionadas, como la establecida entre la arquitectura y los mercados o la economía. Tomando como punto de partida la idea de “design intelligence” sugerida por Michael Speaks (2001), se extrae de sus argumentos que lo esencial es el hallazgo de la singularidad o inteligencia propia de cada estudio de arquitectura o diseño. Asimismo se explora si en la construcción de ese tipo de fórmulas magistrales se alojaban también combinaciones de interés y productivas entre asuntos como la eficiencia y la creatividad, o la organización y las ideas. En esta dinámica de relaciones bidireccionales, y en ese presente de exceso de información, se fundamenta la propuesta de una equivalencia más evidenciada entre la “socialización” del trabajo del arquitecto, al compartirlo públicamente e introducir nuevas conversaciones, y la relación inversa a partir del trabajo sobre la “socialización” misma. Como si la consciencia sobre el uso de los medios pudiera ser efectivamente instrumental, y contribuir al desarrollo de la práctica de arquitectura, desde una perspectiva idealmente comprometida e intelectual. ABSTRACT The dissertation argues the possibility to understand that the practice of architecture can find an instrumental support in the practices of communication, overcoming any classical simplification of the use of media, generally reduced to superficial treatments or promotional efforts. Thus some cases of the last decades of the 20th century are presented. Some threats detected, such as the risk of triviality, the saturation of the public image or the foreseeable wrong association among individuals when they are introduced as part of thematic groups, might have encouraged a noticeable increase of command taken by architects when there is chance to intervene in a media environment. In other words, it can be argued that architecture has started to overcome and optimize the inevitable, the fact that exhibition formulas and publications, or simply the practice of (self)exhibition or (self)publication, are tools at our disposal for the activation of any kind of intellectual management of communication and circulating information about itself. This practice of “self-edition” is analyzed in a specific timeframe of OMA’s trajectory, an office that is considered as a ground-breaking actor in the efficient and opportunistic use of media. Then the second part of the thesis dissects their monograph S,M,L,XL (1995), a volume in which its main characters were deeply involved in terms of edition and design, a process barely analyzed up to now. This publication marked a turning point in its own genre, disrupting old formats and traditional restrictions. It became such an emblematic volume for the discipline that none of the following attempts of replica has ever been able to improve this precedent. Here, the book is also presented as the element that triggers the construction of a “big event” that concludes in the transformation of OMA identity in 10 years. Paradoxically, between the birth of the Groszstadt Foundation and the early steps of AMO, both two entities parallel and connected to OMA. This positions emerge from how the research unveils that S,M,L,XL is one more piece, a key one but not an unrelated element, within a sum of actions and individuals, as well as other publications, exhibitions, articles and projects, in particular Bigness, Generic City, Euralille and the competitions of 1989. Among the remarkable innovations of the monograph, there is an outstanding openness to a regime of multiple authorship, headed by Rem Koolhaas and the graphic designer Bruce Mau, who share the acknowledgements page with the editor, Jennifer Sigler, and almost 100 people, not necessarily responsible for specific fragments of the book. In this respect, the dissolution of certain limits made possible that the expected tasks in the edition of a publication could be trespassed. A general goal of the thesis is also to open a debate on typically questioned relations, particularly between architecture and markets or economy. Using the idea of “design intelligence”, outlined by Michael Speaks in 2001, the thesis pulls out its essence, basically the interest in detecting the singularity, or particular intelligence of every office of architecture and design. Then it explores if in the construction of this kind of ingenious formulas one could find interesting and useful combinations among issues like efficiency and creativity, or organization and ideas. This dynamic of bidirectional relations, rescued urgently at this present moment of excess of information, is based on the proposal for a more evident equivalence between the “socialization” of the work in architecture, anytime it is shared in public, and the opposite concept, the work on the proper act of “socialization” itself. As if a new awareness of the capacities of the use of media could turn it into an instrumental force, capable of contributing to the development of the practice of architecture, from an ideally committed and intelectual perspective.

Size-Dependent and Step-Modulated Supramolecular Electrochemical Properties of Catechol-Derived Adlayers at Pt(hkl) Surfaces

The electrochemical reactivity of catechol-derived adlayers is reported at platinum (Pt) single-crystal electrodes. Pt(111) and stepped vicinal surfaces are used as model surfaces possessing well-ordered nanometer-sized Pt(111) terraces ranging from 0.4 to 12 nm. The electrochemical experiments were designed to probe how the control of monatomic step-density and of atomic-level step structure can be used to modulate molecule–molecule interactions during self-assembly of aromatic-derived organic monolayers at metallic single-crystal electrode surfaces. A hard sphere model of surfaces and a simplified band formation model are used as a theoretical framework for interpretation of experimental results. The experimental results reveal (i) that supramolecular electrochemical effects may be confined, propagated, or modulated by the choice of atomic level crystallographic features (i.e.monatomic steps), deliberately introduced at metallic substrate surfaces, suggesting (ii) that substrate-defect engineering may be used to tune the macroscopic electronic properties of aromatic molecular adlayers and of smaller molecular aggregates.