Realization of thermally durable close-packed 2D gold nanoparticle arrays using self-assembly and plasma etching

Realization of thermally and chemically durable, ordered gold nanostructures using bottom-up self-assembly techniques are essential for applications in a wide range of areas including catalysis, energy generation, and sensing. Herein, we describe a modular process for realizing uniform arrays of gold nanoparticles, with interparticle spacings of 2 nm and above, by using RF plasma etching to remove ligands from self-assembled arrays of ligand-coated gold nanoparticles. Both nanoscale imaging and macroscale spectroscopic characterization techniques were used to determine the optimal conditions for plasma etching, namely RF power, operating pressure, duration of treatment, and type of gas. We then studied the effect of nanoparticle size, interparticle spacing, and type of substrate on the thermal durability of plasma-treated and untreated nanoparticle arrays. Plasma-treated arrays showed enhanced chemical and thermal durability, on account of the removal of ligands. To illustrate the application potential of the developed process, robust SERS (surface-enhanced Raman scattering) substrates were formed using plasma-treated arrays of silver-coated gold nanoparticles that had a silicon wafer or photopaper as the underlying support. The measured value of the average SERS enhancement factor (2 x 10(5)) was quantitatively reproducible on both silicon and paper substrates. The silicon substrates gave quantitatively reproducible results even after thermal annealing. The paper-based SERS substrate was also used to swab and detect probe molecules deposited on a solid surface.

IceCube: efficient targeted mining in data cubes

We address the problem of mining targeted association rules over multidimensional market-basket data. Here, each transaction has, in addition to the set of purchased items, ancillary dimension attributes associated with it. Based on these dimensions, transactions can be visualized as distributed over cells of an n-dimensional cube. In this framework, a targeted association rule is of the form {X -> Y} R, where R is a convex region in the cube and X. Y is a traditional association rule within region R. We first describe the TOARM algorithm, based on classical techniques, for identifying targeted association rules. Then, we discuss the concepts of bottom-up aggregation and cubing, leading to the CellUnion technique. This approach is further extended, using notions of cube-count interleaving and credit-based pruning, to derive the IceCube algorithm. Our experiments demonstrate that IceCube consistently provides the best execution time performance, especially for large and complex data cubes.

Versatility of azide in serendipitous assembly of Copper(II) Magnetic Polyclusters

Engineering at the molecular level is one of the most exciting new developments for the generation of functional materials. However, the concept of designing polynuclear extended structures from bottom up is still not mature. Although progress has been made with secondary building units (SBUs) in metal organic frameworks (MOFs), the control seems to be just an illusion when it comes to bridging ligands such as the azide ion. When we say that the azido ligand is versatile in its bridging capabilities, what we mean is that it would be difficult to predict or control its bridging properties. However, this kind of serendipity is not always bad news. For example, scientists have shown that the azido ligand can mediate magnetic exchanges between paramagnetic metals in a predictable fashion (usually depending upon the bonding geometries). Therefore, it is a well-respected ligand in polynuclear assemblies. Serendipitous assemblies offer new magnetic structures that we may not otherwise even think about synthesizing. The azido ligand forms a variety of complexes with copper(II) using different blocking amines or pyridine based ligands. Its structural nature changes upon changing the substitution on amine, as well as the amount of blocking ligand. In principle, if we take any of these complexes and provide more coordination sites to the bridging azido ligands by removing a fraction of the blocking ligands, we can get new complexes with intricate structural networks and therefore different magnetic properties with the same components as used for the parent complex. In this Account, we mainly discuss the development of a number of new topological and magnetic exchange systems synthesized using this concept. Not all of these new complexes can be grouped according to their basic building structures or even by the ratio of the metal to blocking ligand. Therefore, we divided the discussion by the nuclearity of the basic building structures. Some of the complexes with the same nuclearities have very similar or even almost identical basic structures. However, the way these building units are joined together (by the azido bridges) to form the overall extended structures differ almost in every case. The complexes having the Cu-6 core are particularly interesting from a structural point of view. Although they have almost identical basic structures, some of them are extended in three dimensions, but two of them are extended in two dimensions by two different bridging networks. In the complexes having linear Cu-4 basic units, we find that using similar ligands does not always give the same bridging networks even within the basic building structures. These complexes have also enriched the field of molecular magnetism. One of the complexes with a Cu-3 building unit has provided us with the opportunity to study the competing behavior of two different kinds of magnetic exchange mechanism (ferromagnetic and antiferromagnetic) acting simultaneously between two metal ions. Through density functional theory calculations, we showed how they work independently and their additive nature to produce the overall effect. The exciting methodology for the generation of copper(II) polyclusters presented in this Account will provide the opportunity to explore analogous serendipitous assembly of diverse structures with interesting magnetic behavior using other transition metal ions having more than one unpaired electrons.

Stable atmospheric methane in the 2000s: key-role of emissions from natural wetlands

Two atmospheric inversions (one fine-resolved and one process-discriminating) and a process-based model for land surface exchanges are brought together to analyse the variations of methane emissions from 1990 to 2009. A focus is put on the role of natural wetlands and on the years 2000-2006, a period of stable atmospheric concentrations. From 1990 to 2000, the top-down and bottom-up visions agree on the time-phasing of global total and wetland emission anomalies. The process-discriminating inversion indicates that wetlands dominate the time-variability of methane emissions (90% of the total variability). The contribution of tropical wetlands to the anomalies is found to be large, especially during the post-Pinatubo years (global negative anomalies with minima between -41 and -19 Tg yr(-1) in 1992) and during the alternate 1997-1998 El-Nino/1998-1999 La-Nina (maximal anomalies in tropical regions between +16 and +22 Tg yr(-1) for the inversions and anomalies due to tropical wetlands between +12 and +17 Tg yr(-1) for the process-based model). Between 2000 and 2006, during the stagnation of methane concentrations in the atmosphere, the top-down and bottom-up approaches agree on the fact that South America is the main region contributing to anomalies in natural wetland emissions, but they disagree on the sign and magnitude of the flux trend in the Amazon basin. A negative trend (-3.9 +/- 1.3 Tg yr(-1)) is inferred by the process-discriminating inversion whereas a positive trend (+1.3 +/- 0.3 Tg yr(-1)) is found by the process model. Although processed-based models have their own caveats and may not take into account all processes, the positive trend found by the B-U approach is considered more likely because it is a robust feature of the process-based model, consistent with analysed precipitations and the satellite-derived extent of inundated areas. On the contrary, the surface-data based inversions lack constraints for South America. This result suggests the need for a re-interpretation of the large increase found in anthropogenic methane inventories after 2000.

Green ionothermal synthesis of hierarchical nanostructures of SnS2 and their Li-ion storage properties

Flower-like hierarchical architectures of layered SnS2 have been synthesized ionothermally for the first time, using a water soluble EMIM]BF4 ionic liquid (IL) as the solvent medium. At lower reaction temperatures, the hierarchical structures are formed of few-layered polycrystalline 2D nanosheet-petals composed of randomly oriented nanoparticles of SnS2. The supramolecular networks of the IL serve as templates on which the nanoparticles of SnS2 are glued together by combined effects of hydrogen bonding, electrostatic, hydrophobic and imidazolium stacking interactions of the IL, giving rise to polycrystalline 2D nanosheet-petals. At higher reaction temperatures, single crystalline plate-like nanosheets with well-defined crystallographic facets are obtained due to rapid inter-particle diffusion across the IL. Efficient surface charge screening by the IL favors the aggregation of individual nanosheets to form hierarchical flower-like architectures of SnS2. The mechanistic aspects of the ionothermal bottom-up hierarchical assembly of SnS2 nanosheets are discussed in detail. Li-ion storage properties of the pristine SnS2 samples are examined and the electrochemical performance of the sample synthesized at higher temperatures is found to be comparable to that reported for pristine SnS2 samples in the literature.

Structure, stability and elasticity of DNA nanotubes

DNA nanotubes are tubular structures composed of DNA crossover molecules. We present a bottom up approach for the construction and characterization of these structures. Various possible topologies of nanotubes are constructed such as 6-helix, 8-helix and tri-tubes with different sequences and lengths. We have used fully atomistic molecular dynamics simulations to study the structure, stability and elasticity of these structures. Several nanosecond long MD simulations give the microscopic details about DNA nanotubes. Based on the structural analysis of simulation data, we show that 6-helix nanotubes are stable and maintain their tubular structure; while 8-helix nanotubes are flattened to stabilize themselves. We also comment on the sequence dependence and the effect of overhangs. These structures are approximately four times more rigid having a stretch modulus of similar to 4000 pN compared to the stretch modulus of 1000 pN of a DNA double helix molecule of the same length and sequence. The stretch moduli of these nanotubes are also three times larger than those of PX/JX crossover DNA molecules which have stretch moduli in the range of 1500-2000 pN. The calculated persistence length is in the range of a few microns which is close to the reported experimental results on certain classes of DNA nanotubes.

Mass spectrometry based characterization of Hb Beckman variant in a falsely elevated HbA(1c) sample

Glycated hemoglobin (HbA(1c)) is a `gold standard' biomarker for assessing the glycemic index of an individual. HbA(1c) is formed due to nonenzymatic glycosylation at N-terminal valine residue of the P-globin chain. Cation exchange based high performance liquid chromatography (CE HPLC) is mostly used to quantify HbA(1c), in blood sample. A few genetic variants of hemoglobin and post-translationally modified variants of hemoglobin interfere with CE HPLC-based quantification,. resulting in its false positive estimation. Using mass spectrometry, we analyzed a blood sample with abnormally high HbA(1c) (52.1%) in the CE HPLC method. The observed HbA(1c) did not corroborate the blood glucose level of the patient. A mass spectrometry based bottom up proteomics approach, intact globin chain mass analysis, and chemical modification of the proteolytic peptides identified the presence of Hb Beckman, a genetic variant of hemoglobin, in the experimental sample. A similar surface area to charge ratio between HbA(1c) and Hb Beckman might have resulted in the coelution of the variant with HbA(1c) in CE HPLC. Therefore, in the screening of diabetes mellitus through the estimation of HbA(1c), it is important to look for genetic variants of hemoglobin in samples that show abnormally high glycemic index, and HbA(1c) must be estimated using an alternative method. (C) 2015 Elsevier Inc. All rights reserved.

El yo como causa

Resumen: Este trabajo pretende explicar el modo en que el yo humano se dice causa de los actos libres, en especial de los actos voluntarios corpóreos. Con este objeto se analiza la causalidad natural en el mundo, especialmente cuando se manifiesta en la vida como autoorganización, y más aún en la vida animal, en la que la conducta intencional es guiada por la cognición y las emociones. Se establece una distinción entre la causalidad downward, de los niveles superiores sobre los inferiores, y la causalidad bottom-up, que es la inversa. Además se introduce una distinción entre el “sí mismo natural” (naturaleza perfeccionada por hábitos) y el “sí mismo intencional” (sujeto dotado de conciencia y posibilidad de control de sus operaciones). Esos esquemas se aplican al hombre, cuya causalidad downward más alta es la que ejerce la persona, con su inteligencia y voluntad, sobre sus actos sensitivos y de este modo sobre su cuerpo.

PICES Press, Vol. 6, No. 1, January 1998

Highlights of PICES VI The state of the eastern North Pacific in the first half of 1997 The state of the western North Pacific in the first half of 1997 The status of the Bering Sea in the first eight month of 1997 Organization of fisheries, environmental and ocean science in Canada Richard James Beamish PICES-GLOBEC Climate Change and Carrying Capacity Program Epipelagic fish production in the open Subarctic Pacific: bottom up or self-regulating control? Activity Report of SCOR Working Group 105 Establishment of Marine Information Research Center: new strategy on oceanographic data management in Japan Bering Sea Ecosystem Biophysical Metadatabase: a collaborative research tool for fisheries-oceanography and ecosystem investigations

MIRACLE Project Plan

Social scientists have used agent-based models (ABMs) to explore the interaction and feedbacks among social agents and their environments. The bottom-up structure of ABMs enables simulation and investigation of complex systems and their emergent behaviour with a high level of detail; however the stochastic nature and potential combinations of parameters of such models create large non-linear multidimensional “big data,” which are difficult to analyze using traditional statistical methods. Our proposed project seeks to address this challenge by developing algorithms and web-based analysis and visualization tools that provide automated means of discovering complex relationships among variables. The tools will enable modellers to easily manage, analyze, visualize, and compare their output data, and will provide stakeholders, policy makers and the general public with intuitive web interfaces to explore, interact with and provide feedback on otherwise difficult-to-understand models.

Multi-agent modelling for the simulation of a simple smart microgrid

The smart grid is a highly complex system that is being formed from the traditional power grid, adding new and sophisticated communication and control devices. This will enable integrating new elements for distributed power generation and also achieving an increasingly automated operation so for actions of the utilities as for customers. In order to model such systems a bottom-up method is followed, using only a few basic elements which are structured into two layers: a physical layer for the electrical power transmission, and one logical layer for element communication. A simple case study is presented to analyse the possibilities of simulation. It shows a microgrid model with dynamic load management and an integrated approach that can process both electrical and communication flows.

The Siem Reap Meet Proceedings: Asserting Rights, Defining Responsibilities: Perspectives from Small-scale Fishing Communities on Coastal and Fisheries Management in Asia

This publication is a record of the proceedings of the Siem Reap Workshop and Symposium. It provides a bottom-up perspective on how rights are understood, and what rights are seen as important by small-scale fishing communities, if they are to fulfil their responsibilities for managing resources in a sustainable and equitable manner. It is hoped that these proceedings, and the Statement from the Workshop-the Siem Reap Statement-are found useful by those engaged in policy making and advocacy in support of small-scale fisheries, as well as researchers, non-governmental organizations (NGOs), fishworker organizations, and multilateral and regional organizations

The Zanzibar Workshop Proceedings: Asserting Rights, Defining Responsibilities:Perspectives from Small-scale Fishing Communities on Coastal and Fisheries Management in Eastern and Southern Africa

The Zanzibar Workshop Proceedings consists of the report and the Statement of the Workshop and provides a rich understanding of the dynamics of traditional, indigenous, small-scale and artisanal fisheries and fishing communities in the Eastern and Southern African (ESA) context. The issues covered include: the saga of rights denied to coastal lands, fishing, and threats to livelihood arising from lack of recognition of traditional rights and the livelihood needs of people in the region; the aspirations of coastal and inland communities to maintain or improve their livelihoods; and a bottom-up perspective on access rights to fishing, post-harvest rights and economic and social rights. This report will be a valuable source of information for community organizers, trade union leaders, government officials and the donor community, including multilateral organizations, researchers and for all those who are interested in the well-being of ESA fishing communities.

Cooperative management of artisanal fisheries: implementation of democratic principles in fisheries management around Lake Kainji

Kainji Lake, the first man-made lake in Nigeria is one of the most researched water bodies in Africa. Earlier studies indicated that there was no systematic management of the lake fisheries involving the participation of the fishers in the decision-making processes before 1993. In 1993, the Nigeria-German Kainji Lake Fisheries Promotion Project (KLFPP) started the introduction of a bottom-up approach in the management of the fishery resources through a random selection of some fishers representatives for the decision making body of the project. The paper traces the democratization process of the management approach to the lake fisheries culminating in the systematic selection, appointment, training and assignment of responsibilities to twenty-four Wakilis covering the 316 fishing communities around Lake Kainji

Neural routing circuits for forming invariant representations of visual objects

This thesis presents a biologically plausible model of an attentional mechanism for forming position- and scale-invariant representations of objects in the visual world. The model relies on a set of control neurons to dynamically modify the synaptic strengths of intra-cortical connections so that information from a windowed region of primary visual cortex (Vl) is selectively routed to higher cortical areas. Local spatial relationships (i.e., topography) within the attentional window are preserved as information is routed through the cortex, thus enabling attended objects to be represented in higher cortical areas within an object-centered reference frame that is position and scale invariant. The representation in V1 is modeled as a multiscale stack of sample nodes with progressively lower resolution at higher eccentricities. Large changes in the size of the attentional window are accomplished by switching between different levels of the multiscale stack, while positional shifts and small changes in scale are accomplished by translating and rescaling the window within a single level of the stack. The control signals for setting the position and size of the attentional window are hypothesized to originate from neurons in the pulvinar and in the deep layers of visual cortex. The dynamics of these control neurons are governed by simple differential equations that can be realized by neurobiologically plausible circuits. In pre-attentive mode, the control neurons receive their input from a low-level "saliency map" representing potentially interesting regions of a scene. During the pattern recognition phase, control neurons are driven by the interaction between top-down (memory) and bottom-up (retinal input) sources. The model respects key neurophysiological, neuroanatomical, and psychophysical data relating to attention, and it makes a variety of experimentally testable predictions.