Anion Sensing Porphyrin Functionalized Nanoparticles

Disulfide and dithiocarbamate functionalized porphyrins have been synthesized and used as protecting ligands for gold nanoparticle formation either via ligand substitution reactions or by direct synthesis. These nanoparticles have been shown to recognize anions via changes in the absorbance spectrum of the surface adsorbed porphyrin moieties. Association constants, derived from quantitative titrations, indicate a remarkable surface enhancement effect where the surface bound porphyrins bind anions much more strongly than the free receptor in solution.     

Effect of Ammonia on the Gas-Phase Hydration of the Common Atmospheric Ion HSO4?

Hydration directly affects the mobility, thermodynamic properties, lifetime and nucleation rates of atmospheric ions. In the present study, the role of ammonia on the formation of hydrogen bonded complexes of the common atmospheric hydrogensulfate (HSO₄⁻) ion with water has been investigated using the Density Functional Theory (DFT). Our findings rule out the stabilizing effect of ammonia on the formation of negatively charged cluster hydrates and show clearly that the conventional (classical) treatment of ionic clusters as presumably more stable compared to neutrals may not be applicable to pre-nucleation clusters. These considerations lead us to conclude that not only quantitative but also qualitative assessment of the relative thermodynamic stability of atmospheric clusters requires a quantum-chemical treatment.     

An Investigation of the Reduction and Reoxidation of Isolated Vanadate Sites Supported on MCM-48

The reduction and subsequent reoxidation of isolated vanadate species supported on silica was investigated using temperature-programmed reduction and oxidation, along with in-situ XANES and Raman spectroscopy. Approximately 70–80% of the vanadium was reduced to V³⁺ after reduction in H₂ at temperatures up to 923 K. Upon reduction, the vanadyl oxygen was removed and the three remaining V–O bonds are lengthened by 0.2 Å. The vanadate species are rapidly reoxidized when exposed to O₂, with the amount of oxygen uptake matching well with the amount removed during reduction. In-situ Raman spectroscopy during reoxidation in ¹⁸O₂ showed that significant scrambling occurs between gas phase oxygen and surface oxygen species during the reoxidation of the vanadate species.     

When laws and ethics collide: What should psychologists do?

At times the laws under which psychologists function may appear to contradict generally recognized ethical values and/or good clinical care. When these circumstances arise, psychologists must determine if a conflict really exists and, if so, seek solutions that reconcile respect for the law with their ethical values. At times, psychologists may decide to follow the law despite their ethical concerns. At other times, they may determine that a conscientious objection is warranted. The authors recommend options to consider when these situations arise and offer a decision-making process. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

The relationship of attention deficit hyperactivity disorder and conduct disorder to juvenile delinquency: legal implications

Attention deficit/hyperactivity disorder (ADHD) and conduct disorder (CD) are both disorders of childhood and adolescence that all too frequently extend into adulthood. But just what is the relationship between these two disorders? This study explores the overlap between these two disorders as they relate to juvenile delinquency; both are significant risk factors for the development of antisocial behavior. But there is more significance to the presence or absence of ADHD or CD in later antisocial behavior. Higher levels of defiant and/or aggressive behavior lead to antisocial acts as compared with lower levels of defiance and antisocial acts. Boys diagnosed with ADHD have higher felony rates than normal control boys, yet ADHD is not nearly as strong a predictor of offending behavior as is CD in study subjects. The presence of both CD and ADHD contributes to illegal behavior, and it is likely that early intervention in both disorders will reduce the prevalence of antisocial behavior.     

Synthesis and Characterisation of Some New Ferrocenyl- and Ferrocenylalkynyl-[60]Fullerene Compounds

We report the synthesis and characterisation of a series of ferrocenylfullerene compounds, and some new ferrocene derivatives required as intermediates. The new fullerene species are Fc-[60]fullerene, (8); Fc-C=C-[60]fullerene, (10); Fc-C=C-C=C-[60]fullerene, (12); and (η-C₅H₄SiBu₃)Fe(η-C₅H₄)-[60]fullerene, (14).     

Rainbow smelt population responses to species invasions and change in environmental condition

Invasive species can cause major disruptions in native food webs, yet the impact of species introductions and whether they will become invasive appears to be context-dependent. Rainbow smelt and alewife co-exist as invasive species in the Laurentian Great Lakes and as native species on the Atlantic coast of North America, but in Lake Champlain rainbow smelt is the dominant native forage fish and alewife are invasive. Alewife became abundant by 2007, providing an opportunity to explore the dynamics of these two species in a system where only one is invasive. We used data from a 28-year forage fish survey to compare demographics of rainbow smelt populations in three basins of Lake Champlain with different volumes, nutrient levels, and predator abundances. Rainbow smelt catch-per-unit-effort (CPUE) remained constant in the large, deep Main Lake before and after alewife invaded, but decreased in the two smaller basins. Declines were primarily a result of increased age-0 and age-1 mortality. Predation by top piscivores, system productivity, and competition for resources alone could not explain the patterns in CPUE across the basins. The mechanisms that allow alewife and rainbow smelt to co-exist could be related to system volume and oxythermal habitat availability, and may explain why the two species do not negatively affect each other in the Great Lakes. Summer hypoxia in the smaller basins could force individuals into smaller habitat volumes with higher densities of competitors and cannibalistic adult rainbow smelt. Habitat availability may mediate the impact of invasive alewife on native rainbow smelt.     

Designing content distribution networks for optimal cost and performance

One strategy for alleviating excess latency (delay) in the Internet is the caching of web content at multiple locations. This reduces the number of hops necessary to reach the desired content. This strategy is used for web content such as html pages, images, streaming video, and Internet radio. The network of servers which store this content, and the collections of objects stored on each server, is called a content distribution network (CDN). In order to optimally design a CDN, given a network topology with available server storage capacity at various points in the network, one must decide which object collections to place on each server in order to achieve performance or cost objectives. The placements must be within the storage limits of the servers and must reflect the request patterns for each collection of objects to be cached. Researchers have suggested formulations for the CDN problem which address performance by minimizing latency (the average number of hops is a commonly accepted measure of latency) from client to content, or formulations that focus on minimizing cost of storage and/or bandwidth. In this research, we develop a model which allows for the simultaneous treatment of performance and cost, present examples to illustrate the application of the model and perform a detailed designed experiment to gain insights into cost/hops tradeoff for a variety of network parameters.