Synthesis and Study of Olefin Metathesis Catalysts Supported by Redox-Switchable Diaminocarbene 3 Ferrocenophanes

A redox-switchable ligand, N,N'-dimethyldiaminocarbene[3]ferrocenophane (5), was synthesized and incorporated into a series of Ir- and Ru-based complexes. Electrochemical and spectroscopic analyses of (5) Ir(CO)(2)Cl (15) revealed that 5 displayed a Tolman electronic parameter value of 2050 cm(-1) in the neutral state and 2061 cm(-1) upon oxidation. Moreover, inspection of X-ray crystallography data recorded for (5) Ir(cis,cis-1,5-cyclooctadiene)Cl (13) revealed that 5 was sterically less bulky (%V-Bur = 28.4) than other known diaminocarbene[3]ferrocenophanes, which facilitated the synthesis of (5)(PPh3)Cl2Ru-(3-phenylindenylid-1-ene) (18). Complex 18 exhibited quasi-reversible electrochemical processes at 0.79 and 0.98 V relative to SCE, which were assigned to the Fe and Ru centers in the complex, respectively, based on UV-vis and electron pair resonance spectroscopic measurements. Adding 2,3-dichloro-5,6-dicyanoquinone over the course of a ring-opening metathesis polymerization of cis, cis-1,5-cyclooctadiene catalyzed by 18 ([monomer](0)/[18](0) = 2500) reduced the corresponding rate constant of the reaction by over an order of magnitude (pre-oxidation: k(obs) = 0.045 s(-1); post-oxidation: k(obs) = 0.0012 s(-1)). Subsequent reduction of the oxidized species using decamethylferrocene restored catalytic activity (post-reduction: k(obs) = up to 0.016 s(-1), depending on when the reductant was added). The difference in the polymerization rates was attributed to the relative donating ability of the redox-active ligand (i.e., strongly donating 5 versus weakly donating 5(+)) which ultimately governed the activity displayed by the corresponding catalyst.U. S. Army Research Office W911NF-09-1-0446Chemistr

Bounds for the adiabatic approximation with applications to quantum computation

We present straightforward proofs of estimates used in the adiabatic approximation. The gap dependence is analyzed explicitly. We apply the result to interpolating Hamiltonians of interest in quantum computing.Comment: 15 pages, one figure. Two comments added in Secs. 2 and

Disrupted functional brain network organization in patients with obstructive sleep apnea.

IntroductionObstructive sleep apnea (OSA) subjects show impaired autonomic, affective, executive, sensorimotor, and cognitive functions. Brain injury in OSA subjects appears in multiple sites regulating these functions, but the integrity of functional networks within the regulatory sites remains unclear. Our aim was to examine the functional interactions and the complex network organization of these interactions across the whole brain in OSA, using regional functional connectivity (FC) and brain network topological properties.MethodsWe collected resting-state functional magnetic resonance imaging (MRI) data, using a 3.0-Tesla MRI scanner, from 69 newly diagnosed, treatment-naïve, moderate-to-severe OSA (age, 48.3 ± 9.2 years; body mass index, 31 ± 6.2 kg/m(2); apnea-hypopnea index (AHI), 35.6 ± 23.3 events/h) and 82 control subjects (47.6 ± 9.1 years; body mass index, 25.1 ± 3.5 kg/m(2)). Data were analyzed to examine FC in OSA over controls as interregional correlations and brain network topological properties.ResultsObstructive sleep apnea subjects showed significantly altered FC in the cerebellar, frontal, parietal, temporal, occipital, limbic, and basal ganglia regions (FDR, P < 0.05). Entire functional brain networks in OSA subjects showed significantly less efficient integration, and their regional topological properties of functional integration and specialization characteristics also showed declined trends in areas showing altered FC, an outcome which would interfere with brain network organization (P < 0.05; 10,000 permutations). Brain sites with abnormal topological properties in OSA showed significant relationships with AHI scores.ConclusionsOur findings suggest that the dysfunction extends to resting conditions, and the altered FC and impaired network organization may underlie the impaired responses in autonomic, cognitive, and sensorimotor functions. The outcomes likely result from the prominent structural changes in both axons and nuclear structures, which occur in the condition

Advancing the Application of Design of Experiments to Synthetic Theater Operations Research Model Data

NPS NRP Executive SummaryNavy leadership is interested in initiatives that can potentially increase the responsiveness of campaign analysis. Simulation-based campaign analysis is used to measure risk for investment options in how best to equip, organize, supply, maintain, train, and employ our naval forces. The Synthetic Theater Operations Research Model (STORM) is a stochastic simulation model used to support campaign analysis by the U.S. Navy, Marine Corps, and Air Force. Building, testing, running, and analyzing campaign scenarios in STORM is a complex, time-consuming process. A simulated campaign may span months, involve scores of ships and battalions, hundreds of aircraft and installations, all executing thousands of interconnected missions involving numerous events in time and space. Creating, testing, and approving the inputs for a single design point (DP) requires a significant investment in analysts’ time and computing resources. Consequently, there are limits on the number of DPs that can be produced, executed, and analyzed during a study’s timeframe.N8 - Integration of Capabilities & ResourcesThis research is supported by funding from the Naval Postgraduate School, Naval Research Program (PE 0605853N/2098).Approved for public release. Distribution is unlimited

Survival of the Fattest: How Body Fat and Migration Influence Survival in Highly Seasonal Environments

1. Energy stores and migration are important adaptations for animals in seasonal environments, but their roles may vary relative to an animal\u27s endogenous and exogenous environment. In partially migratory populations, migrants and residents experience different seasonal environments; thus, the influence of energy stores on survival may differ relative to migratory tactic, with potential consequences to survival and fitness. 2. Using data from Sierra Nevada bighorn sheep (Ovis canadensis sierrae; hereafter, Sierra bighorn), we tested the hypothesis that body fat (energy stores) buffers animals against their environment, but that buffering capacity differs across environments experienced by high-elevation residents (using a single range year round), traditional migrants (making 1 round-trip movement between high- and low-elevation ranges during winter) and vacillating migrants (making ≥2 round trips between high- and low-elevation ranges during winter). We predicted that: for animals with high levels of body fat, survival would be high regardless of migratory tactic; residents would require larger stores of body fat to survive than migrants; energy stores would be least influential to survival for vacillating migrants. 3. High levels of body fat in autumn (≥14% for females and ≥19% for males) largely buffered animals against harsh environments (survival \u3e0.90) regardless of migratory tactic. At lower levels of body fat, traditional migrants had higher survival than residents. Vacillating migrants exhibited nearly 100% survival with no detectable effect of body fat on survival. 4. Collectively, these results support the hypothesis that body fat buffers animals against harsh environments but that the buffering capacity differed relative to the environment and highly flexible behaviours (i.e. vacillating migration) can allow animals to decouple survival from body fat. 5. Our work reveals that synergies between physiological and behavioural adaptations of animals in highly seasonal environments carry potential fitness consequences for individuals and demographic consequences for populations

The Key Role of Heavy Precipitation Events in Climate Model Disagreements of Future Annual Precipitation Changes in California

Climate model simulations disagree on whether future precipitation will increase or decrease over California, which has impeded efforts to anticipate and adapt to human-induced climate change. This disagreement is explored in terms of daily precipitation frequency and intensity. It is found that divergent model projections of changes in the incidence of rare heavy (\u3e60 mm day−1) daily precipitation events explain much of the model disagreement on annual time scales, yet represent only 0.3% of precipitating days and 9% of annual precipitation volume. Of the 25 downscaled model projections examined here, 21 agree that precipitation frequency will decrease by the 2060s, with a mean reduction of 6–14 days yr−1. This reduces California\u27s mean annual precipitation by about 5.7%. Partly offsetting this, 16 of the 25 projections agree that daily precipitation intensity will increase, which accounts for a model average 5.3% increase in annual precipitation. Between these conflicting tendencies, 12 projections show drier annual conditions by the 2060s and 13 show wetter. These results are obtained from 16 global general circulation models downscaled with different combinations of dynamical methods [Weather Research and Forecasting (WRF), Regional Spectral Model (RSM), and version 3 of the Regional Climate Model (RegCM3)] and statistical methods [bias correction with spatial disaggregation (BCSD) and bias correction with constructed analogs (BCCA)], although not all downscaling methods were applied to each global model. Model disagreements in the projected change in occurrence of the heaviest precipitation days (\u3e60 mm day−1) account for the majority of disagreement in the projected change in annual precipitation, and occur preferentially over the Sierra Nevada and Northern California. When such events are excluded, nearly twice as many projections show drier future conditions

Probabilistic estimates of future changes in California temperature and precipitation usingstatistical and dynamical downscaling

Sixteen global general circulation models were used to develop probabilistic projections of temperature (T) and precipitation (P) changes over California by the 2060s. The global models were downscaled with two statistical techniques and three nested dynamical regional climate models, although not all global models were downscaled with all techniques. Both monthly and daily timescale changes in T and P are addressed, the latter being important for a range of applications in energy use, water management, and agriculture. The T changes tend to agree more across downscaling techniques than the P changes. Year-to-year natural internal climate variability is roughly of similar magnitude to the projected T changes. In the monthly average, July temperatures shift enough that that the hottest July found in any simulation over the historical period becomes a modestly cool July in the future period. Januarys as cold as any found in the historical period are still found in the 2060s, but the median and maximum monthly average temperatures increase notably. Annual and seasonal P changes are small compared to interannual or intermodel variability. However, the annual change is composed of seasonally varying changes that are themselves much larger, but tend to cancel in the annual mean. Winters show modestly wetter conditions in the North of the state, while spring and autumn show less precipitation. The dynamical downscaling techniques project increasing precipitation in the Southeastern part of the state, which is influenced by the North American monsoon, a feature that is not captured by the statistical downscaling

Trimethoprim-sulfamethoxazole in cyst fluid from autosomal dominant polycystic kidneys

Trimethoprim-sulfamethoxazole in cyst fluid from autosomal dominant polycystic kidneys. Cyst infection in patients with autosomal-dominant polycystic kidney disease (ADPKD) is often refractory to therapy, in part because of the limited entry of commonly used antibiotics into cyst fluid. To study the efficacy of trimethoprim-sulfamethoxazole in cyst infection, cyst fluid was obtained by percutaneous aspiration or at surgery from eight patients with ADPKD receiving trimethoprim-sulfamethoxazole. Cysts were categorized as nongradient or gradient by cyst-fluid sodium concentration. Trimethoprim-sulfamethoxazole concentrations within cysts were determined and cyst fluid inhibitory and bactericidal titers were assessed in vitro against Escherichia coli, Proteus mirabilis and Streptococcus fecalis. The mean cyst fluid trimethoprim and sulfamethoxazole concentrations were 15.2 µg/ml and 42.5 µg/ml, respectively. Preferential accumulation of trimethoprim was observed in gradient cysts, exceeding serum levels more than eightfold. Sulfamethoxazole penetrated cysts to a lesser extent, with. concentrations ranging from 10 to 70 percent of the serum level. Cyst fluid sampled prior to trimethoprim-sulfamethoxazole administration (control) demonstrated no antibacterial activity, while cyst fluid inhibitory and bactericidal titers following antibiotic administration were 1:32 or greater in most instances. These studies indicate that trimethoprim-sulfamethoxazole is likely to be efficacious in the treatment of cyst infection in polycystic kidneys

Entrances and exits: changing perceptions of primary teaching as a career for men

Original article can be found at: http://www.informaworld.com/smpp/title~content=t713640830~db=all Copyright Informa / Taylor and Francis. DOI: 10.1080/03004430802352087The number of men in teaching has always been small, particularly in early childhood, but those that do come into teaching usually do so for the same reasons as women, namely enjoyment of working with children, of wanting to teach and wanting to make a difference to children's lives. However, in two separate studies, the authors have shown that on beginning teacher training in 1998, and at the point of leaving the profession in 2005, men and women tend to emphasise different concerns. This article will explore those differences and seek possible explanations for how men's views of teaching might be changing over time.Peer reviewe