A NEW SIMPLE LONG-PATH-LENGTH THIN-LAYER SPECTROELECTROCHEMICAL CELL IN VARIOUS USES

This article describes the design of a new type of long-path-length thin-layer cell (LPTLC), which is constructed by inserting two Teflon cell bodies into a standard cuvette. This cuvette holder enables the LPTLC to combine with photometric instrumentation conveniently. Gold, platinum, glassy carbon, and other materials can be used for the working electrode. Since no soluble adhesive material is used, the cell can meet various needs (in situ conventional and derivative W-vis, in situ circular dichroism, etc.) in both aqueous and nonaqueous systems.

INVESTIGATION OF CETYLPYRIDINIUM BROMIDE ADSORPTION AT A GLASSY-CARBON ELECTRODE SURFACE BY SPECTROELECTROCHEMISTRY WITH A LONG OPTICAL-PATH LENGTH THIN-LAYER CELL

The adsorption of cationic surfactant cetylpyridinium bromide (CPB) on a glassy carbon (GC) electrode surface has been studied by spectroelectrochemistry with a long optical path length thin-layer cell (LOPTLC) for the first time. A fine adsorption isotherm of CPB molecules from an aqueous solution containing 0.10 M KBr has been obtained over the range of (1.00-8.00) x 10(-5) M. From theoretical calculation and experimental data, adsorption of CPB on the GC electrode surface shows four distinct orientations and three large orientation transitions. Compared with the ordinary isotherm, the differential isotherm is more characteristic and would be suitable for the study of orientation transitions of organic compounds. With a theoretical treatment of the adsorption isotherm, four orientations of adsorbed CPB on a GC electrode surface coincide with the Frumkin-Langmuir type. From adsorption parameters the Frumkin-Langmuir equations, the adsorption free energy and, therefore, the equilibrium constants of orientation transitions of the CPB molecule can be obtained.

INVESTIGATION OF ELECTRIC DICHROISM OF CETYLPYRIDINIUM BROMIDE BY SPECTROELECTROCHEMISTRY WITH A LONG OPTICAL-PATH LENGTH THIN-LAYER CELL

In this paper, the electric dichroism of cetylpyridinium bromide (CPB) has been found and studied by spectroelectrochemistry with a long optical path length thin-layer cell (LOPTLC) for the first time. The CPB molecule with a long carbon chain and a polar pyridinium ring is anisotropic in molecular configuration or in polarizability. In the electric field of a thin-layer cell, the CPB molecule reorientates along the direction of the electric field and exhibits electric dichroism, which results in the increase of absorbance of CPB in the UV-vis range. By use of in situ measurement of spectroelectrochemistry, the order parameters of long molecular axis (S = 0.845) and short molecular axis (D = 0.155) and the angle between the long axis direction of the CPB molecule and the direction normal to the electrode surface (theta = 18-degrees 44') have been determined. These data were used to describe the state of arrangement of the molecules in the solution. The reorientation of CPB molecules is the result of the interaction between the anisotropic molecules and electric field. The effects of the concentration of CPB and of the applied electric field on the electric dichroism have been investigated.

Reaction path for oxidation of ethylene to acetic acid over Pd/WO3-ZrO2 in the presence of water

Pd-supported on WO3-ZrO2 (W/Zr atomic ratio=0.2) calcined at 1073 K was found to be highly active and selective for gas-phase oxidation of ethylene to acetic acid in the presence of water at 423 K and 0.6 MPa. Contact time dependence demonstrated that acetic acid is formed via acetaldehyde formed by a Wacker-type reaction, not through ethanol by hydration of ethylene.

Measuring Bottleneck Bandwidth of Targeted Path Segments

Accurate measurement of network bandwidth is crucial for flexible Internet applications and protocols which actively manage and dynamically adapt to changing utilization of network resources. These applications must do so to perform tasks such as distributing and delivering high-bandwidth media, scheduling service requests and performing admission control. Extensive work has focused on two approaches to measuring bandwidth: measuring it hop-by-hop, and measuring it end-to-end along a path. Unfortunately, best-practice techniques for the former are inefficient and techniques for the latter are only able to observe bottlenecks visible at end-to-end scope. In this paper, we develop and simulate end-to-end probing methods which can measure bottleneck bandwidth along arbitrary, targeted subpaths of a path in the network, including subpaths shared by a set of flows. As another important contribution, we describe a number of practical applications which we foresee as standing to benefit from solutions to this problem, especially in emerging, flexible network architectures such as overlay networks, ad-hoc networks, peer-to-peer architectures and massively accessed content servers.

Fast Shortest Path Distance Estimation in Large Networks

We study the problem of preprocessing a large graph so that point-to-point shortest-path queries can be answered very fast. Computing shortest paths is a well studied problem, but exact algorithms do not scale to huge graphs encountered on the web, social networks, and other applications. In this paper we focus on approximate methods for distance estimation, in particular using landmark-based distance indexing. This approach involves selecting a subset of nodes as landmarks and computing (offline) the distances from each node in the graph to those landmarks. At runtime, when the distance between a pair of nodes is needed, we can estimate it quickly by combining the precomputed distances of the two nodes to the landmarks. We prove that selecting the optimal set of landmarks is an NP-hard problem, and thus heuristic solutions need to be employed. Given a budget of memory for the index, which translates directly into a budget of landmarks, different landmark selection strategies can yield dramatically different results in terms of accuracy. A number of simple methods that scale well to large graphs are therefore developed and experimentally compared. The simplest methods choose central nodes of the graph, while the more elaborate ones select central nodes that are also far away from one another. The efficiency of the suggested techniques is tested experimentally using five different real world graphs with millions of edges; for a given accuracy, they require as much as 250 times less space than the current approach in the literature which considers selecting landmarks at random. Finally, we study applications of our method in two problems arising naturally in large-scale networks, namely, social search and community detection.

The transformation of Ireland 1958 - 93: the role of ideas in punctuating institutional path dependency at critical junctures

Ireland experienced two critical junctures when its economic survival was threatened: 1958/9 and 1986/7. Common to both crises was the supplanting of long established practices, that had become an integral part of the political culture of the state, by new ideas that ensured eventual economic recovery. In their adoption and implementation these ideas also fundamentally changed the institutions of state – how politics was done, how it was organised and regulated. The end result was the transformation of the Irish state. The main hypothesis of this thesis is that at those critical junctures the political and administrative elites who enabled economic recovery were not just making pragmatic decisions, their actions were influenced by ideas. Systematic content analysis of the published works of the main ideational actors, together with primary interviews with those actors still alive, reveals how their ideas were formed, what influenced them, and how they set about implementing their ideas. As the hypothesis assumes institutional change over time historical institutionalism serves as the theoretical framework. Central to this theory is the idea that choices made when a policy is being initiated or an institution formed will have a continuing influence long into the future. Institutions of state become ‘path dependent’ and impervious to change – the forces of inertia take over. That path dependency is broken at critical junctures. At those moments ideas play a major role as they offer a set of ready-made solutions. Historical institutionalism serves as a robust framework for proving that in the transformation of Ireland the role of ideas in punctuating institutional path dependency at critical junctures was central.

Variation among northeast Atlantic regions in the responses of zooplankton to climate change: Not all areas follow the same path

Broad scale climate forcing can interact with local environmental processes to affect the observed ecological phenomena. This causes potential problems of over-extrapolation for results from a limited number of sites or the averaging out of region-specific responses if data from too wide an area are combined. In this study, an area similar in extent to the Celtic Biscay Large Marine Ecosystem, but including off-shelf areas, was partitioned using clustering of satellite chlorophyll (chl-a) measurements. The resulting clusters were used to define areas over which to combine copepod data from the Continuous Plankton Recorder. Following filtering due to data limitations, nine regions were defined with sufficient records for analysis. These regions were consistent with known oceanographic structure in the study area. Off-shelf regions showed a progressively later timing in the seasonal peak of chl-a measurements moving northwards. Generalised additive models were used to estimate seasonal and multiannual signals in the adult and juvenile stages of Calanus finmarchicus, C. helgolandicus and the Paracalanus–Pseudocalanus group. Associations between variables (sea surface temperature (SST), phenology and annual abundance) differed among taxonomic groups, but even within taxonomic groups, relationships were not consistent across regions. For example, in the deep waters off Spain and Portugal the annual abundance of Calanus finmarchicus has a weak positive association with SST, in contrast to the pattern in most other regions. The regions defined in this study provide an objective basis for investigations into the long term dynamics of plankton populations and suggest suitable sub regions for deriving pelagic system indicators.

Transdisciplinary Science: A Path to Understanding the Interactions Among Ocean Acidification, Ecosystems, and Society

The global nature of ocean acidification (OA) transcends habitats, ecosystems, regions, and science disciplines. The scientific community recognizes that the biggest challenge in improving understanding of how changing OA conditions affect ecosystems, and associated consequences for human society, requires integration of experimental, observational, and modeling approaches from many disciplines over a wide range of temporal and spatial scales. Such transdisciplinary science is the next step in providing relevant, meaningful results and optimal guidance to policymakers and coastal managers. We discuss the challenges associated with integrating ocean acidification science across funding agencies, institutions, disciplines, topical areas, and regions, and the value of unifying science objectives and activities to deliver insights into local, regional, and global scale impacts. We identify guiding principles and strategies for developing transdisciplinary research in the ocean acidification science community.

Path-Dependency, Stocks, Switching Points, Flows: Reflections on Long-term Global Change and Local Opportunities

This paper examines the possibilities for peripheral localities to achieve upward mobility in the world-system by “hooking on” to larger processes of world-system accumulation. In particular, is it possible for economies that are dependent on foreign investment to receive a flow of investments that is high enough to overcome the negative impacts of a high stock of foreign investment, thus enabling them to cross a threshold and achieve upward mobility in the world-system? An analysis of therecent experience of the southern Irish “Celtic Tiger” economy during 1990-2000 indicates that such an upward movement is possible on the basis of massive foreign investment inflows. On closer examination, however, the Irish-type model appears to be highly deficient, because a high proportion of growth is illusionary and also on grounds of social desirability and lack of generalizability.