Bromophenyl functionalization of carbon nanotubes : an ab initio study

We study the thermodynamics of bromophenyl functionalization of carbon nanotubes with respect to diameter and metallic/insulating character using density-functional theory (DFT). On one hand, we show that the activation energy for the grafting of a bromophenyl molecule onto a semiconducting zigzag nanotube ranges from 0.73 eV to 0.76 eV without any clear trend with respect to diameter within numerical accuracy. On the other hand, the binding energy of a single bromophenyl molecule shows a clear diameter dependence and ranges from 1.51 eV for a (8,0) zigzag nanotube to 0.83 eV for a (20,0) zigzag nanotube. This is in part explained by the transition from sp2 to sp3 bonding occurring to a carbon atom of a nanotube when a phenyl is grafted to it and the fact that smaller nanotubes are closer to a sp3 hybridization than larger ones due to increased curvature. Since a second bromophenyl unit can attach without energy barrier next to an isolated grafted unit, they are assumed to exist in pairs. The para configuration is found to be favored for the pairs and their binding energy decreases with increasing diameter, ranging from 4.34 eV for a (7,0) nanotube to 2.27 eV for a (29,0) nanotube. An analytic form for this radius dependence is derived using a tight binding hamiltonian and first order perturbation theory. The 1/R^2 dependance obtained (where R is the nanotube radius) is verified by our DFT results within numerical accuracy. Finally, metallic nanotubes are found to be more reactive than semiconducting nanotubes, a feature that can be explained by a non-zero density of states at the Fermi level for metallic nanotubes.Comment: 7 pages, 5 figures and 3 table

An Agent Based Model of the Diel Vertical Migration Patterns of Mysis diluviana

Recent work indicates that the macro-invertebrate Mysis diluviana exhibits partial diel vertical migration (DVM), whereby one part of the population remains on the lake bottom at night while the other migrates up the water column. The drivers underlying the decision to migrate remain unknown. We developed an agent-based model that can simulate thousands of individual mysids decision-making processes at an hourly time step throughout a year. The model takes into account a daily and seasonally changing environment, including light, temperature, food availability across habitats and body con- dition. We found that the simulated Mysis population is highly sensitive to changes in the energy cost of performing migration. We have also devel- oped a graphical user interface to help disseminate the results and testing of hypotheses without the need for the researcher to edit code. In addition to testing hypotheses about migration drivers, the model, once parameters have been calibrated with real data, will help facilitate more efficient field sampling and prediction of resource availability for mysivorous fishes by evaluating the potential for seasonality in Mysis migration patterns

Sacramento River Predator Diet Analysis: A Comparative Study

This study examined diets of two predatory fish species, the native Sacramento Pikeminnow (Ptychocheilus grandis) and the introduced Striped Bass (Morone saxatilis), in the Sacramento River, California, USA. Both species have been implicated in native species declines through predation, eliciting our investigation of their diets in the Sacramento River. Sampling occurred between March and November 2017, and was conducted via hook and line on a 35-km reach near Chico, California. Habitat types sampled include engineered structures (water diversions and beam bridges), rip-rapped channel edges, and natural riverbank. Stomach contents were collected via gastric lavage and later processed using visual, gravimetric, and genetic techniques. Diets of Sacramento Pikeminnow and Striped Bass were highly similar as determined through index of relative importance and PERMANOVA modeling. Water temperature was the only variable that significantly affected diet composition. Results reflect similar dietary niches for both species in the Sacramento River

Investigation of Pyrolyzing Ablators Using a Gas Injection Probe

Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/143112/1/6.2017-0437.pd

Eyetracking metrics reveal impaired spatial anticipation in behavioural variant frontotemporal dementia.

Eyetracking technology has had limited application in the dementia field to date, with most studies attempting to discriminate syndrome subgroups on the basis of basic oculomotor functions rather than higher-order cognitive abilities. Eyetracking-based tasks may also offer opportunities to reduce or ameliorate problems associated with standard paper-and-pencil cognitive tests such as the complexity and linguistic demands of verbal test instructions, and the problems of tiredness and attention associated with lengthy tasks that generate few data points at a slow rate. In the present paper we adapted the Brixton spatial anticipation test to a computerized instruction-less version where oculomotor metrics, rather than overt verbal responses, were taken into account as indicators of high level cognitive functions. Twelve bvFTD (in whom spatial anticipation deficits were expected), six SD patients (in whom deficits were predicted to be less frequent) and 38 healthy controls were presented with a 10 × 7 matrix of white circles. During each trial (N = 24) a black dot moved across seven positions on the screen, following 12 different patterns. Participants' eye movements were recorded. Frequentist statistical analysis of standard eye movement metrics were complemented by a Bayesian machine learning (ML) approach in which raw eyetracking time series datasets were examined to explore the ability to discriminate diagnostic group performance not only on the overall performance but also on individual trials. The original pen and paper Brixton test identified a spatial anticipation deficit in 7/12 (58%) of bvFTD and in 2/6 (33%) of SD patients. The eyetracking frequentist approach reported the deficit in 11/12 (92%) of bvFTD and in none (0%) of the SD patients. The machine learning approach had the main advantage of identifying significant differences from controls in 24/24 individual trials for bvFTD patients and in only 12/24 for SD patients. Results indicate that the fine grained rich datasets obtained from eyetracking metrics can inform us about high level cognitive functions in dementia, such as spatial anticipation. The ML approach can help identify conditions where subtle deficits are present and, potentially, contribute to test optimisation and the reduction of testing times. The absence of instructions also favoured a better distinction between different clinical groups of patients and can help provide valuable disease-specific markers

Investigation of the chemocatalytic and biocatalytic valorization of a range of different lignin preparations: The importance of β-O-4 content

A set of seven different lignin preparations was generated from a range of organosolv (acidic, alkaline, ammonia-treated, and dioxane-based), ionic liquid, autohydrolysis, and Kraft pretreatments of lignocelluloses. Each lignin was characterized by 2D HSQC NMR spectroscopy, showing significant variability in the β-O-4 content of the different lignin samples. Each lignin was then valorised using three biocatalytic methods (microbial biotransformation with Rhodococcus jostii RHA045, treatment with Pseudomonas fluorescens Dyp1B or Sphingobacterium sp. T2 manganese superoxide dismutase) and two chemocatalytic methods (catalytic hydrogenation using Pt/alumina catalyst, DDQ benzylic oxidation/Zn reduction). Highest product yields for DDQ/Zn valorization were observed from poplar ammonia percolation-organosolv lignin, which had the highest β-O-4 content of the investigated lignins and also gave the highest yield of syringaldehyde (243 mg L -1 ) when using R. jostii RHA045 and the most enzymatic products using P. fluorescens Dyp1B. The highest product yield from the Pt/alumina hydrogenation was observed using oak dioxasolv lignin, which also had a high β-O-4 content. In general, highest product yields for both chemocatalytic and biocatalytic valorization methods were obtained from preparations that showed highest β-O-4 content, while variable yields were obtained with preparations containing intermediate β-O-4 content, and little or no product was obtained with preparations containing low β-O-4 content