(Ga₁-xZnx)(N₁-xOx) nanocrystals: visible absorbers with tunable composition and absorption spectra

Bulk oxy(nitride) (Ga(1-x)Zn(x))(N(1-x)O(x)) is a promising photocatalyst for water splitting under visible illumination. To realize its solar harvesting potential, it is desirable to minimize its band gap through synthetic control of the value of x. Furthermore, improved photochemical quantum yields may be achievable with nanocrystalline forms of this material. We report the synthesis, structural, and optical characterization of nanocrystals of (Ga(1-x)Zn(x))(N(1-x)O(x)) with the values of x tunable from 0.30 to 0.87. Band gaps decreased from 2.7 to 2.2 eV over this composition range, which corresponded to a 260% increase in the fraction of solar photons that could be absorbed by the material. We achieved nanoscale morphology and compositional control by employing mixtures of ZnGa(2)O(4) and ZnO nanocrystals as synthetic precursors that could be converted to (Ga(1-x)Zn(x))(N(1-x)O(x)) under NH(3). The high quality of the resulting nanocrystals is encouraging for achieving photochemical water-splitting rates that are competitive with internal carrier recombination pathways.     

Plasmonic nanosensors with inverse sensitivity by means of enzyme-guided crystal growth

Lowering the limit of detection is key to the design of sensors needed for food safety regulations, environmental policies and the diagnosis of severe diseases. However, because conventional transducers generate a signal that is directly proportional to the concentration of the target molecule, ultralow concentrations of the molecule result in variations in the physical properties of the sensor that are tiny, and therefore difficult to detect with confidence. Here we present a signal-generation mechanism that redefines the limit of detection of nanoparticle sensors by inducing a signal that is larger when the target molecule is less concentrated. The key step to achieve this inverse sensitivity is to use an enzyme that controls the rate of nucleation of silver nanocrystals on plasmonic transducers. We demonstrate the outstanding sensitivity and robustness of this approach by detecting the cancer biomarker prostate-specific antigen down to 10(-18)?g?ml(-1) (4 × 10(-20)?M) in whole serum.     

Likelihood of a marine vessel accident from wind energy development in the Atlantic

Offshore wind energy development is planned for areas off the Atlantic coast. Many of the planned wind development areas fall within traditional commercial vessel routes. In order to mitigate possible hazards to ships and to wind turbines, it is important to understand the potential for increased risk to commercial shipping from the presence of wind farms. Risk is identified as the likelihood that an occurrence will happen, and the consequences of that occurrence, should it occur. This paper deals with the likelihood of commercial vessel accidents, because of the development of offshore wind energy along the US Atlantic coast. Using Automatic Identification System (AIS) data, historical shipping routes between ports in the Atlantic were identified, from Maine to the Florida Straits. The AIS data were also used as inputs to a numerical model that can simulate cargo, tanker and tug/towing vessel movement along typical routes. The model was used to recreate present day vessel movement, as well as to simulate future routing that may be required to avoid wind farms. By comparing the present and future routing of vessels, an analysis of potential maritime accidents was used to determine the increased marginal risk of vessel collisions, groundings and allisions with stationary objects, because of the presence of wind farms. The outcome of the analysis showed little increase in vessel collisions or allisions, and a decrease in groundings as more vessels were forced seaward by the wind farms. Copyright © 2015 John Wiley & Sons, Ltd.     

Impact of Herbivore-induced Plant Volatiles on Parasitoid Foraging Success: A Spatial Simulation of the <Emphasis Type="Italic">Cotesia rubecula,Pieris rapae,</Emphasis> and <Emphasis Type="Italic">Brassica oleracea</Emphasis> System

Many parasitoids are known to use herbivore-induced plant volatiles as cues to locate hosts. However, data are lacking on how much of an advantage a parasitoid can gain from following these plant cues and which factors can limit the value of these cues to the parasitoid. In this study, we simulate the Cotesia rubecula-Pieris rapae-Brassica oleracea system, and ask how many more hosts can a parasitoid attack in a single day of foraging by following plant signals versus randomly foraging. We vary herbivore density, plant response time, parasitoid flight distance, and available host stages to see under which conditions parasitoids benefit from herbivore-induced plant cues. In most of the parameter combinations studied, parasitoids that responded to cues attacked more hosts than those that foraged randomly. Parasitoids following plant cues attacked up to ten times more hosts when they were able to successfully attack herbivores older than first instar; however, if parasitoids were limited to first instar hosts, those following plant cues were at a disadvantage when plants took longer than a day to respond to herbivory. At low herbivore densities, only parasitoids with a larger foraging radius could take advantage of plant cues. Although preference for herbivore-induced volatiles was not always beneficial for a parasitoid, under the most likely natural conditions, the model predicts that C. rubecula gains fitness from following plant cues.     

Predicting optimal resolving power for ambient pressure ion mobility spectrometry

Although diffusion theory predicts that IMS resolving power increases with the square root of the voltage applied across the drift tube, in practice, there exists an optimum voltage above which resolving power decreases. This optimum voltage was determined to be both compound and initial ion pulse width dependent. A "conditional" resolving power equation is introduced that can be used to quickly approximate realistic resolving powers for specific instrumental operating parameters and compounds. Using four common environmental contaminants (trichloroethylene, tetrachloroethylene, methyl tert-butyl ether, methyl isobutyl ketone), diffusion-limited (theoretical), R d, conditional, R c, and actual (or measured), R m, IMS resolving powers were determined and compared for a small IMS instrument designed for subsurface measurements. Detection limits determined at the optimal resolving power for the environmental contaminants ranged from 18 parts per trillion volume-to-volume (ppt v) to 80 parts per billion volume-to-volume (ppb v). The maximal measured resolving power for our small, ambient-pressure stand-alone IMS ranged from 42 to 54, yielding an IMS resolving power efficiency, defined as R m/ R c x 100%, of 56-74% of the maximal conditional resolving power possible.     

Beta-1,3 Oligoglucans Specifically Bind to Immune Receptor CD28 and May Enhance T Cell Activation

Beta glucans are known to have immunomodulatory effects that mediated by a variety of mechanisms. In this article, we describe experiments and simulations suggesting that beta-1,3 glucans may promote activation of T cells by a previously unknown mechanism. First, we find that treatment of a T lymphoblast cell line with beta-1,3 oligoglucan significantly increases mRNA levels of T cell activation-associated cytokines, especially in the presence of the agonistic anti-CD3 antibody. This immunostimulatory activity was observed in the absence of dectin-1, a known receptor for beta-1,3 glucans. To clarify the molecular mechanism underlying this activity, we performed a series of molecular dynamics simulations and free-energy calculations to explore the interaction of beta-1,3 oligoglucans with potential immune receptors. While the simulations reveal little association between beta-1,3 oligoglucan and the immune receptor CD3, we find that beta-1,3 oligoglucans bind to CD28 near the region identified as the binding site for its natural ligands CD80 and CD86. Using a rigorous absolute binding free-energy technique, we calculate a dissociation constant in the low millimolar range for binding of 8-mer beta-1,3 oligoglucan to this site on CD28. The simulations show this binding to be specific, as no such association is computed for alpha-1,4 oligoglucan. This study suggests that beta-1,3 glucans bind to CD28 and may stimulate T cell activation collaboratively with T cell receptor activation, thereby stimulating immune function.     

Constraint hierarchies

Constraints allow programmers and users to state declaratively a relation that should be maintained, rather than requiring them to write procedures to maintain the relation themselves. They are thus useful in such applications as programming languages, user interface toolkits, and simulation packages. In many situations, it is desirable to be able to state bothrequired andpreferential constraints. The required constraints must hold. Since the other constraints are merely preferences, the system should try to satisfy them if possible, but no error condition arises if it cannot. Aconstraint hierarchy consists of a set of constraints, each labeled as either required or preferred at some strength. An arbitrary number of different strengths is allowed. In the discussion of a theory of constraint hierarchies, we present alternate ways of selecting among competing possible solutions, and prove a number of propositions about the relations among these alternatives. We then outline algorithms for satisfying constraint hierarchies, and ways in which we have used constraint hierarchies in a number of programming languages and systems.     

Antibodies to quinolinic acid and the determination of its cellular distribution within the rat immune system

Antibodies to quinolinic acid were produced in rabbits with protein-conjugated and gold particle-adsorbed quinolinic acid. Quinolinic acid immunoreactivity was below detection limits in carbodiimide-fixed rat brain. In contrast, strong quinolinic acid immunoreactivity was observed in spleen cells with variable, complex morphology located predominantly in the periarterial lymphocyte sheaths. In the thymus, quinolinic acid immunoreactivity was observed in cells with variable morphology, located almost exclusively in the medulla. Lymph nodes and gut-associated lymphoid tissue contained many, strongly stained cells of similar complex morphology in perifollicular areas. Immunoreactivity in liver and lung was restricted to widely scattered, perivascular cells and alveolar cells respectively. Additional stained cells with complex morphology were observed in bronchus-associated lymphoid tissue, in skin, and in the lamina propria of intestinal villi. Follicles in all secondary lymphoid organs were diffusely stained, ranging from mildly to moderately immunoreactive in spleen, to intensely immunoreactive in gut-associated lymphoid tissue. These results suggest that quinolinic acid is an immune system-specific molecule. Two hypothetical schemes are proposed to account for high levels of quinolinic acid in specific cells of the immune system.