First-Principles Study of the Effect of Organic Ligands on the Crystal Structure of CdS Nanoparticles

We show with the aid of first-principles electronic structure calculations that suitable choice of the capping ligands may be an important control parameter for crystal structure engineering of nanoparticles. Our calculations on CdS nanocrystals reveal that the binding energy of model trioctylphosphine molecules on the (001) facets of zincblende nanocrystals is larger compared to that on wurtzite facets. Similarly, the binding energy of model cis-oleic acid is found to be dominant for the (10 (1) over bar0) facets of wurtzite structure. As a consequence, trioctylphosphine as a capping agent stabilizes the zincblende structure while cis-oleic acid stabilizes the wurtzite phase by influencing the surface energy, which has a sizable contribution to the energetics of a nanocrystal. Our detailed analysis suggests that the binding of molecules on the nanocrystalline facets depends on the surface topology of the facets, the coordination of the surface atoms where the capping molecule is likely to attach, and the conformation of the capping molecule.

Anticancer Activity of Hydrogen-Bond-Stabilized Half-Sandwich RuII Complexes with Heterocycles

Neutral half-sandwich organometallic ruthenium(II) complexes of the type (?6-cymene)RuCl2(L)] (H1H10), where L represents a heterocyclic ligand, have been synthesized and characterized spectroscopically. The structures of five complexes were also established by single-crystal X-ray diffraction confirming a piano-stool geometry with ?6 coordination of the arene ligand. Hydrogen bonding between the N?H group of the heterocycle and a chlorine atom attached to Ru stabilizes the metalligand interaction. Complexes coordinated to a mercaptobenzothiazole framework (H1) or mercaptobenzoxazole (H6) showed high cytotoxicity against several cancer cells but not against normal cells. In vitro studies have shown that the inhibition of cancer cell growth involves primarily G1-phase arrest as well as the generation of reactive oxygen species (ROS). The complexes are found to bind DNA in a non-intercalative fashion and cause unwinding of plasmid DNA in a cell-free medium. Surprisingly, the cytotoxic complexes H1 and H6 differ in their interaction with DNA, as observed by biophysical studies, they either cause a biphasic melting of the DNA or the inhibition of topoisomerase IIa activity, respectively. Substitution of the aromatic ring of the heterocycle or adding a second hydrogen-bond donor on the heterocycle reduces the cytotoxicity.

Platinum Ion-Doped TiO2: High Catalytic Activity of Pt2+ with Oxide Ion Vacancy in Ti1-x4+Ptx2+O2-x Compared to Pt4+ without Oxide Ion Vacancy in Ti1-x4+Ptx4+O2

Ti0.97Pt0.032+O1.97 and Ti0.97Pt0.034+O2 have been synthesized by a solution combustion method using alanine and glycine as the fuels, respectively. Both crystallize in anatase TiO2 structure with 15 nm average crystallite size. X-ray photoelectron spectroscopy (XPS) confirmed Pt ions are in the 2+ state in Ti0.97Pt0.03O1.97 (alanine) and 4+ state in Ti0.97Pt0.03O2 (glycine). The rate of CO oxidation occurring over Ti0.97Pt0.032+O1.97 (0.76 mu mol.g(-1).s(-1)) is similar to 10, times more than that over Ti0.97Pt0.034+O2 at 60 degrees C (0.08 mu mol.g(-1).s(-1)). A large shift in 100% hydrocarbons conversion to lower temperature was observed for Pt2+ ion-substituted TiO2 relative 10 that for Pt4+ ion-substituted TiO2. After reoxidation of the reduced compound by H-2 as well as CO, Pt ions are stabilized in mixed valences, 2+ and 4+ states. The role of oxide ion vacancy has been demonstrated by CO oxidation and H-2 + O-2 recombination reactions in the presence and absence of O-2. We analyze the activated lattice oxygens upon substitution of Pt2+ and Pt4+ ions in TiO2, using first-principles density functional theory (DFT) calculations with supercells of Ti31Pt1O63, Ti30Pt2O62, and Ti29Pt3O61 for Pt2+ ion substitution and Ti31Pt1O64, Ti30Pt2O62, and Ti29Pt3O61 for Pt4+ ion substitution in TiO2. We find that the local structure of Pt2+ ion has a distorted square planar geometry and that of Pt4+ ion has an octahedral geometry similar to that of Ti4+ ion in pure TiO2. The change in coordination of Pt2+ ion gives rise to weakly bonded oxygens, and these oxygens are involved in high rates of catalytic reaction. Thus, the high catalytic activity results from synergistic roles of Pt2+ ion and oxide ion vacancy and weakly bonded lattice oxygen.

USEFUL EXTENSIONS OF THE HENRY REACTION: EXPEDITIOUS ROUTES TO NITROALKANES AND NITROALKENES IN AQUEOUS MEDIA

The products of the Henry nitroaldol reaction from nitromethane and several aldehydes were reduced to the corresponding nitroalkanes with (n-Bu)(3)SnH in water under microwave irradiation (80 degrees C/10 min), or dehydrated to the corresponding nitroalkenes with K2CO3 in water (generally 0-5 degrees C/20 min). Both ``one-pot'' reactions occur in excellent yields across a range of aliphatic and aromatic (including heteroaromatic) substrates. It seems likely that the deoxygenation of the nitroaldols occurs via coordination of an oxygen atom of the nitro group with a tin atom, which facilitates hydride delivery in the transition state. The elimination of water from the nitroaldols in mild base is likely driven by the stability of the conjugated nitroalkene products. The elimination required workup with 2N HCl, which likely displaces a nitroalkane-nitroalkene equilibrium towards the latter. These extensions of the Henry reaction lead to products not easily obtained otherwise.

Differential response of cholesterol based pyrimidine systems with oxyethylene type spacers to gelation and mesogen formation in the presence of alkali metal ions

A new series of lipophilic cholesteryl derivatives of 2,4,6-trichloro-pyrimidine-5-carbaldehyde has been synthesized. Oxyethylene spacers of variable lengths were inserted between the hydrogen bonding promoting pyrimidine core and the cholesteryl tail in order to understand their effect on the selfassembly of these compounds. Only compound 1a with the shortest spacer formed a gel in organic solvents such as n-butanol and n-dodecane. While other members (1b and c) having longer spacers led to sol formation and precipitation in n-butanol and n-dodecane respectively. The self-assembly phenomena associated with the gelation process were investigated using temperature-dependent UVVis and CD-spectroscopy. The morphological features of the freeze-dried gels obtained from different organic solvents were examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The solid phase behaviours of these molecules and their associated alkali metal ion complexes were explored using polarized optical microscopy (POM) and differential scanning calorimetry (DSC). The molecular arrangements in the xerogel and in the solid state were further probed using a wide-angle Xray diffraction (WAXD) technique. Analysis of the wide-angle X-ray diffraction data reveals that this class of molecules adopts a hexagonal columnar organization in the gel and in the solid state. Each slice of these hexagonal columnar structures is composed of a dimeric molecular-assembly as a building block. Significant changes in the conformation of the oxyethylene chains could be triggered via the coordination of selected alkali metal ions. This led to the production of interesting metal ion promoted mesogenic behaviour.

A stabilization approach for mesh-free simulations of systems developing shocks or extreme strain localizations

A new stabilization scheme, based on a stochastic representation of the discretized field variables, is proposed with a view to reduce or even eliminate unphysical oscillations in the mesh-free numerical simulations of systems developing shocks or exhibiting localized bands of extreme deformation in the response. The origin of the stabilization scheme may be traced to nonlinear stochastic filtering and, consistent with a class of such filters, gain-based additive correction terms are applied to the simulated solution of the system, herein achieved through the element-free Galerkin method, in order to impose a set of constraints that help arresting the spurious oscillations. The method is numerically illustrated through its Applications to inviscid Burgers' equations, wherein shocks may develop as a result of intersections of the characteristics, and to a gradient plasticity model whose response is often characterized by a developing shear band as the external load is gradually increased. The potential of the method in stabilized yet accurate numerical simulations of such systems involving extreme gradient variations in the response is thus brought forth. (C) 2014 Elsevier Ltd. All rights reserved.

Are Bar Associations Anticompetitive? An Empirical Analysis of Recommended Prices for Legal Services in Spain

The European Commission Report on Competition in Professional Services found that recommended prices by professional bodies have a significant negative effect on competition since they may facilitate the coordination of prices between service providers and/or mislead consumers about reasonable price levels. Professional associations argue, first, that a fee schedule may help their members to properly calculate the cost of services avoiding excessive charges and reducing consumers’ searching costs and, second, that recommended prices are very useful for cost appraisal if a litigant is condemned to pay the legal expenses of the opposing party. Thus, recommended fee schedules could be justified to some extent if they represented the cost of providing the services. We test this hypothesis using cross‐section data on a subset of recommended prices by 52 Spanish bar associations and cost data on their territorial jurisdictions. Our empirical results indicate that prices recommended by bar associations are unrelated to the cost of legal services and therefore we conclude that recommended prices have merely an anticompetitive effect.

Sustainability of Open Access Services - Phases 1 & 2

Although some services that support Open Access have developed a sustainable business model, many started as projects and continue to run on recurrent project funding or goodwill. If these are critical components of the evolving scholarly communication system the foundation of Open Access is vulnerable. Knowledge Exchange has commissioned this study as part of a larger programme of work to look at the issue of sustaining key services into the long term. This report focuses on phases one and two of the programme. Phase one was a scoping exercise, carried out mainly through a literature review and an extensive stakeholder interview exercise, to describe the services that are currently available or would be valuable in the future. It also investigated what roles stakeholders could play in this future scenario. Phase two was a stakeholder consultation and engagement exercise. The aim was to engage stakeholders with the work programme so that they could contribute their views, get involved with the work and have a voice in the thinking about future scenarios. The key services are presented for three future scenarios: ‘Gold’ Open Access, fully ‘Green’ Open Access and Green’ Open Access supplementing subscription access as ‘Gold’ OA grows. Three strategic areas are identified as having particular potential for future work. These are embedding business development expertise into service development; consideration of how to move money around the system to enable Open Access to be achieved optimally; and governance and coordination of the infrastructural foundation of Open Access. The report concludes with seven recommendations, both high-level and practical, for further work around these strategic areas.

The Value of Research Data

Scientific research revolves around the production, analysis, storage, management, and re-use of data. Data sharing offers important benefits for scientific progress and advancement of knowledge. However, several limitations and barriers in the general adoption of data sharing are still in place. Probably the most important challenge is that data sharing is not yet very common among scholars and is not yet seen as a regular activity among scientists, although important efforts are being invested in promoting data sharing. In addition, there is a relatively low commitment of scholars to cite data. The most important problems and challenges regarding data metrics are closely tied to the more general problems related to data sharing. The development of data metrics is dependent on the growth of data sharing practices, after all it is nothing more than the registration of researchers’ behaviour. At the same time, the availability of proper metrics can help researchers to make their data work more visible. This may subsequently act as an incentive for more data sharing and in this way a virtuous circle may be set in motion. This report seeks to further explore the possibilities of metrics for datasets (i.e. the creation of reliable data metrics) and an effective reward system that aligns the main interests of the main stakeholders involved in the process. The report reviews the current literature on data sharing and data metrics. It presents interviews with the main stakeholders on data sharing and data metrics. It also analyses the existing repositories and tools in the field of data sharing that have special relevance for the promotion and development of data metrics. On the basis of these three pillars, the report presents a number of solutions and necessary developments, as well as a set of recommendations regarding data metrics. The most important recommendations include the general adoption of data sharing and data publication among scholars; the development of a reward system for scientists that includes data metrics; reducing the costs of data publication; reducing existing negative cultural perceptions of researchers regarding data publication; developing standards for preservation, publication, identification and citation of datasets; more coordination of data repository initiatives; and further development of interoperability protocols across different actors.

Interdisciplinary experience in the Teacher Training College of Vitoria-Gasteiz: teaching profession module

[EN] The higher education regulation process in Europe, known as the Bologna Process, has involved many changes, mainly in relation to methodology and assessment. The paper given below relates to implementing the new EU study plans into the Teacher Training College of Vitoria-Gasteiz; it is the first interdisciplinary paper written involving teaching staff and related to the Teaching Profession module, the first contained in the structure of the new plans. The coordination of teaching staff is one of the main lines of work in the Bologna Process, which is also essential to develop the right skills and maximise the role of students as an active learning component. The use of active, interdisciplinary methodologies has opened up a new dimension in universities, requiring the elimination of the once componential, individual structure, making us look for new areas of exchange that make it possible for students' training to be developed jointly.

Relevance of the programmes of the federal fisheries schools to Nigeria's fishing industry

Nigeria's three federal fisheries schools are administered by three autonomous research institutes located in Lagos, New Bussa, and Maiduguri. The schools were established at different periods to train the required manpower for Nigeria's fishing industry which has remained predominantly artisanal since its inception in 1942 as a Second World War exigency. Despite the establishment of the schools, the industry's manpower is still being dominated by non-nationals especially in the capture fisheries sub-sector. The common features of the schools include the apparent insensitivity of their programmes to the industry's dynamic manpower needs; the absence of coordination of their programmes by a national body which would have ensured that the schools are able to communicate with one another and are willing to act and share a purpose. The need and the methodology for a change of emphasis from the on-going training of extension agents and officers to that of fishing operatives and technicians to enable Nigeria effectively harness her local fish resources towards self-sufficiency is highlighted.

Practical suggestions for the commercialisation of fishery production in Ondo State

The paper examines the fisheries resources and activities in Ondo State, Nigeria. As a result of the geographical advantage via location along the Atlantic coast the potentials and constraints of coastal artisanal fisheries in Ondo State are assessed. Practical suggestions and approaches for a successful commercialisation of fishery production are given. These include: (a) Identification of useful and reliable fisheries institutions, (b) Inauguration establishment and coordination of a fishery development agency, (c) establishment of aquaculture technology centres (ATC), (d) provision of fishery development fund, (e) Standardisation of fishery consultancy units, etc

A Trabecular Bone Explant Model of Osteocyte–Osteoblast Co-Culture for Bone Mechanobiology

The osteocyte network is recognized as the major mechanical sensor in the bone remodeling process, and osteocyte-osteoblast communication acts as an important mediator in the coordination of bone formation and turnover. In this study, we developed a novel 3D trabecular bone explant co-culture model that allows live osteocytes situated in their native extracellular matrix environment to be interconnected with seeded osteoblasts on the bone surface. Using a low-level medium perfusion system, the viability of in situ osteocytes in bone explants was maintained for up to 4 weeks, and functional gap junction intercellular communication (GJIC) was successfully established between osteocytes and seeded primary osteoblasts. Using this novel co-culture model, the effects of dynamic deformational loading, GJIC, and prostaglandin E-2 (PGE(2)) release on functional bone adaptation were further investigated. The results showed that dynamical deformational loading can significantly increase the PGE(2) release by bone cells, bone formation, and the apparent elastic modulus of bone explants. However, the inhibition of gap junctions or the PGE(2) pathway dramatically attenuated the effects of mechanical loading. This 3D trabecular bone explant co-culture model has great potential to fill in the critical gap in knowledge regarding the role of osteocytes as a mechano-sensor and how osteocytes transmit signals to regulate osteoblasts function and skeletal integrity as reflected in its mechanical properties.

The central nervous control of walking in the locust, Schistocerca Americana

Rhythmic motor behaviors in all animals appear to be under the control of "central pattern generator" circuits, neural circuits which can produce output patterns appropriate for behavior even when isolated from their normal peripheral inputs. Insects have been a useful model system in which to study the control of legged terrestrial locomotion. Much is known about walking in insects at the behavioral level, but to date there has been no clear demonstration that a central pattern generator for walking exists. The focus of this thesis is to explore the central neural basis for locomotion in the locust, Schistocerca americana.

Rhythmic motor patterns could be evoked in leg motor neurons of isolated thoracic ganglia of locusts by the muscarinic agonist pilocarpine. These motor patterns would be appropriate for the movement of single legs during walking. Rhythmic patterns could be evoked in all three thoracic ganglia, but the segmental rhythms differed in their sensitivities to pilocarpine, their frequencies, and the phase relationships of motor neuron antagonists. These different patterns could be generated by a simple adaptable model circuit, which was both simulated and implemented in VLSI hardware. The intersegmental coordination of leg motor rhythms was then examined in preparations of isolated chains of thoracic ganglia. Correlations between motor patterns in different thoracic ganglia indicated that central coupling between segmental pattern generators is likely to contribute to the coordination of the legs during walking.

The work described here clearly demonstrates that segmental pattern generators for walking exist in insects. The pattern generators produce motor outputs which are likely to contribute to the coordination of the joints of a limb, as well as the coordination of different limbs. These studies lay the groundwork for further studies to determine the relative contributions of central and sensory neural mechanisms to terrestrial walking.

The development of the South Carolina Coastal Information Network and portal site: Bringing training opportunities and educational resources to coastal community officials and the public

The South Carolina Coastal Information Network (SCCIN) emerged as a result of a number of coastal outreach institutions working in partnership to enhance coordination of the coastal community outreach efforts in South Carolina. This organized effort, led by the S.C. Sea Grant Consortium and its Extension Program, includes partners from federal and state agencies, regional government agencies, and private organizations seeking to coordinate and/or jointly deliver outreach programs that target coastal community constituents. The Network was officially formed in 2006 with the original intention of fostering intra-and inter- agency communication, coordination, and cooperation. Network partners include the S.C. Sea Grant Consortium, S.C. Department of Health and Environmental Control – Office of Ocean and Coastal Resource Management and Bureau of Water, S.C. Department of Natural Resources – ACE Basin National Estuarine Research Reserve, North Inlet-Winyah Bay National Estuarine Research Reserve, Clemson University Cooperative Extension Service and Carolina Clear, Berkeley-Charleston-Dorchester Council of Governments, Waccamaw Regional Council of Governments, Urban Land Institute of South Carolina, S.C. Department of Archives and History, the National Oceanic and Atmospheric Administration – Coastal Services Center and Hollings Marine Laboratory, Michaux Conservancy, Ashley-Cooper Stormwater Education Consortium, the Coastal Waccamaw Stormwater Education Consortium, the S.C. Chapter of the U.S. Green Building Council, and the Lowcountry Council of Governments. (PDF contains 3 pages)