Nanoscale electrochemistry of sp2 carbon materials: from graphite and graphene to carbon nanotubes

Carbon materials have a long history of use as electrodes in electrochemistry, from (bio)electroanalysis to applications in energy technologies, such as batteries and fuel cells. With the advent of new forms of nanocarbon, particularly, carbon nanotubes and graphene, carbon electrode materials have taken on even greater significance for electrochemical studies, both in their own right and as components and supports in an array of functional composites. With the increasing prominence of carbon nanomaterials in electrochemistry comes a need to critically evaluate the experimental framework from which a microscopic understanding of electrochemical processes is best developed. This Account advocates the use of emerging electrochemical imaging techniques and confined electrochemical cell formats that have considerable potential to reveal major new perspectives on the intrinsic electrochemical activity of carbon materials, with unprecedented detail and spatial resolution. These techniques allow particular features on a surface to be targeted and models of structure–activity to be developed and tested on a wide range of length scales and time scales. When high resolution electrochemical imaging data are combined with information from other microscopy and spectroscopy techniques applied to the same area of an electrode surface, in a correlative-electrochemical microscopy approach, highly resolved and unambiguous pictures of electrode activity are revealed that provide new views of the electrochemical properties of carbon materials. With a focus on major sp2 carbon materials, graphite, graphene, and single walled carbon nanotubes (SWNTs), this Account summarizes recent advances that have changed understanding of interfacial electrochemistry at carbon electrodes including: (i) Unequivocal evidence for the high activity of the basal surface of highly oriented pyrolytic graphite (HOPG), which is at least as active as noble metal electrodes (e.g., platinum) for outer-sphere redox processes. (ii) Demonstration of the high activity of basal plane HOPG toward other reactions, with no requirement for catalysis by step edges or defects, as exemplified by studies of proton-coupled electron transfer, redox transformations of adsorbed molecules, surface functionalization via diazonium electrochemistry, and metal electrodeposition. (iii) Rationalization of the complex interplay of different factors that determine electrochemistry at graphene, including the source (mechanical exfoliation from graphite vs chemical vapor deposition), number of graphene layers, edges, electronic structure, redox couple, and electrode history effects. (iv) New methodologies that allow nanoscale electrochemistry of 1D materials (SWNTs) to be related to their electronic characteristics (metallic vs semiconductor SWNTs), size, and quality, with high resolution imaging revealing the high activity of SWNT sidewalls and the importance of defects for some electrocatalytic reactions (e.g., the oxygen reduction reaction). The experimental approaches highlighted for carbon electrodes are generally applicable to other electrode materials and set a new framework and course for the study of electrochemical and interfacial processes

Active vibration mitigation of distributed parameter, smart-type structures using Pseudo-Feedback Optimal Control (PFOC)

A new, near-optimal feedback control technique is introduced that is shown to provide excellent vibration attenuation for those distributed parameter systems that are often encountered in the areas of aeroservoelasticity and large space systems. The technique relies on a novel solution methodology for the classical optimal control problem. Specifically, the quadratic regulator control problem for a flexible vibrating structure is first cast in a weak functional form that admits an approximate solution. The necessary conditions (first-order) are then solved via a time finite-element method. The procedure produces a low dimensional, algebraic parameterization of the optimal control problem that provides a rigorous basis for a discrete controller with a first-order like hold output. Simulation has shown that the algorithm can successfully control a wide variety of plant forms including multi-input/multi-output systems and systems exhibiting significant nonlinearities. In order to firmly establish the efficacy of the algorithm, a laboratory control experiment was implemented to provide planar (bending) vibration attenuation of a highly flexible beam (with a first clamped-free mode of approximately 0.5 Hz)

Circuits, Cycles, Configurations: an Interaction Model of Web Comics

We are accustomed to thinking about multimedia technologies as a coming-together: consider the convergence of still images and sound in film, for example. This approach, however, struggles to accommodate the slippery distinction between different components in a digital space. This paper approaches new technology as a perceptually-generated matrix holding discrete components in relation to one another. These temporary formation of interacting components facilitate a unique structure which is other than the sum of its component parts. It outlines the unique lifecycle of the webcomic, and its relationship with infrastructures both of feedback and distribution, through the systematic evaluation of the specific calibration of technology-based interaction found in the medium

A Spitzer/IRAC Search for Substellar Companions of the Debris Disk Star epsilon Eridani

We have used the InfraRed Array Camera (IRAC) onboard the Spitzer Space telescope to search for low mass companions of the nearby debris disk star epsilon Eridani. The star was observed in two epochs 39 days apart, with different focal plane rotation to allow the subtraction of the instrumental Point Spread Function, achieving a maximum sensitivity of 0.01 MJy/sr at 3.6 and 4.5 um, and 0.05 MJy/sr at 5.8 and 8.0 um. This sensitivity is not sufficient to directly detect scattered or thermal radiation from the epsilon Eridani debris disk. It is however sufficient to allow the detection of Jovian planets with mass as low as 1 MJ in the IRAC 4.5 um band. In this band, we detected over 460 sources within the 5.70 arcmin field of view of our images. To test if any of these sources could be a low mass companion to epsilon Eridani, we have compared their colors and magnitudes with models and photometry of low mass objects. Of the sources detected in at least two IRAC bands, none fall into the range of mid-IR color and luminosity expected for cool, 1 Gyr substellar and planetary mass companions of epsilon Eridani, as determined by both models and observations of field M, L and T dwarf. We identify three new sources which have detections at 4.5 um only, the lower limit placed on their [3.6]-[4.5] color consistent with models of planetary mass objects. Their nature cannot be established with the currently available data and a new observation at a later epoch will be needed to measure their proper motion, in order to determine if they are physically associated to epsilon Eridani.Comment: 36 pages, to be published on The Astrophysical Journal, vol. 647, August 200

Far Infrared Prperties of M Dwarfs

We report the mid- and far-infrared properties of nearby M dwarfs. Spitzer/MIPS measurements were obtained for a sample of 62 stars at 24 um, with subsamples of 41 and 20 stars observed at 70 um and 160 um respectively. We compare the results with current models of M star photospheres and look for indications of circumstellar dust in the form of significant deviations of K-[24 um] colors and 70 um / 24 um flux ratios from the average M star values. At 24 um, all 62 of the targets were detected; 70 um detections were achieved for 20 targets in the subsample observed; and no detections were seen in the 160 um subsample. No clear far-infrared excesses were detected in our sample. The average far infrared excess relative to the photospheric emission of the M stars is at least four times smaller than the similar average for a sample of solar-type stars. However, this limit allows the average fractional infrared luminosity in the M-star sample to be similar to that for more massive stars. We have also set low limits for the maximum mass of dust possible around our stars.Comment: 28 pages, 4 figures, to be published in The Astrophysical Journa

3. Launching the New Enterprise

As the academic year of 1945-46 approached, the intensity of activity in preparation for actually opening the school in the fall term became overwhelming. Incredible though it may seem, Ives and Day were able in a period of a few weeks to assemble the nucleus of a faculty, several of whom formed a continuing source of counsel and advice both during the school’s formative years and thereafter. Includes: The First Dean and the School’s Dedication; A Participant’s View of the Early Years; Ives Moves On; Several Views of Martin P. Catherwood; The Founders

Optical linear polarization in ultra cool dwarfs: A tool to probe dust in the ultra cool dwarf atmospheres

Aims.Recent studies have detected linear polarization in L dwarfs in the optical I band. Theoretical models have been developed to explain this polarization. These models predict higher polarization at shorter wavelengths. We discuss the polarization in the R and I band of 4 ultra cool dwarfs. Methods.We report linear polarization measurements of 4 ultra cool dwarfs in the R and I bands using the Intermediate dispersion Spectrograph and Imaging System (ISIS) mounted on the 4.2m William Herschel Telescope (WHT). Results.As predicted by theoretical models, we find a higher degree of polarization in the R band when compared to polarization in the I band for 3/4 of these ultra cool dwarfs. This suggests that dust scattering asymmetry is caused by oblateness >.We also show how these measurements fit the theoretical models. A case for variability of linear polarization is found, which suggests the presence of randomly distributed dust clouds. We also discuss one case for the presence of a cold debris disk.Comment: 7 pages, 2 figure

The effect of major depression on participation in preventive health care activities

<p>Abstract</p> <p>Background</p> <p>The objective of this study was to determine whether major depressive episodes (MDE) contribute to a lower rate of participation in three prevention activities: blood pressure checks, mammograms and Pap tests.</p> <p>Methods</p> <p>The data source for this study was the Canadian National Population Health Survey (NPHS), a longitudinal study that started in 1994 and has subsequently re-interviewed its participants every two years. The NPHS included a short form version of the Composite International Diagnostic Interview (CIDI-SF) to assess past year MDE and also collected data on participation in preventive activities. Initially, we examined whether respondents with MDE in a particular year were less likely to participate in screening during that same year. In order to assess whether MDE negatively altered the pattern of participation, those successfully screened at the baseline interview in 1994 were identified and divided into cohorts depending on their MDE status. Proportional hazard models were used to quantify the effect of MDE on subsequent participation in screening.</p> <p>Results</p> <p>No effect of MDE on participation in the three preventive activities was identified either in the cross-sectional or longitudinal analysis. Adjustment for a set of relevant covariates did not alter this result.</p> <p>Conclusion</p> <p>Whereas MDE might be expected to reduce the frequency of participation in screening activities, no evidence for this was found in the current analysis. Since people with MDE may contact the health system more frequently, this may offset any tendency of the illness itself to reduce participation in screening.</p

Cross-sectional survey of users of internet depression communities

Background: Internet-based depression communities provide a forum for individuals to communicate and share information and ideas. There has been little research into the health status and other characteristics of users of these communities. Methods: Online cross-sectional survey of Internet depression communities to identify depressive morbidity among users of Internet depression communities in six European countries; to investigate whether users were in contact with health services and receiving treatment; and to identify user perceived effects of the communities. Results: Major depression was highly prevalent among respondents (varying by country from 40% to 64%). Forty-nine percent of users meeting criteria for major depression were not receiving treatment, and 35% had no consultation with health services in the previous year. Thirty-six percent of repeat community users who had consulted a health professional in the previous year felt that the Internet community had been an important factor in deciding to seek professional help. Conclusions: There are high levels of untreated and undiagnosed depression in users of Internet depression communities. This group represents a target for intervention. Internet communities can provide information and support for stigmatizing conditions that inhibit more traditional modes of information seeking

The dermal skeleton of the jawless vertebrate Tremataspis mammilata (Osteostraci, stem-Gnathostomata)

Osteostracans are the closest jawless relatives of jawed vertebrates, informing the gradual assembly of the vertebrate mineralised skeleton. Conflicting interpretations of their dermal skeletal histology arise from failure to account for topological variation, obscuring their significance in elucidating vertebrate skeletal evolution. To resolve this, we characterize the cranial and trunk dermal skeleton of a single individual of Tremataspis mammilata (Osteostraci, Thyestiida) at submicron resolution using synchrotron tomography. Our results show that the architecture of the Tremataspis dermal skeleton is, for the most part, conserved over the skeleton and is broadly consistent with previous histological hypotheses based on 2-dimensional thin section study. We resolve debate over the homology of the basal layer, identifying it as osteogenic acellular isopedin rather than odontogenic elasmodine or metaplastic ossification of the stratum compactum of the dermis. We find topological variation between all dermal skeletal elements studied, and particularly between the cranial and postcranial dermal skeleton. This variation can be largely explained by reduction in differentiation due to geometric constraints imposed within smaller skeletal elements, such as scales. Our description of the dermal skeleton of Tremataspis mammilata provides a foundation for interpreting data from cursory topological samples of dermal skeletal diversity obtained in other osteostracans. This reveals general aspects of histological structure that must be primitive for osteostracans and, likely, ancestral jawed vertebrates. Finally, we draw the distinction between hypotheses and descriptions in palaeohistology