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

Mindfulness meditation targets transdiagnostic symptoms implicated in stress-related disorders: Understanding relationships between changes in mindfulness, sleep quality, and physical symptoms

Mindfulness-Based Stress Reduction (MBSR) is an 8-week meditation program known to improve anxiety, depression, and psychological well-being. Other health-related effects, such as sleep quality, are less well established, as are the psychological processes associated with therapeutic change. This prospective, observational study (n=213) aimed to determine whether perseverative cognition, indicated by rumination and intrusive thoughts, and emotion regulation, measured by avoidance, thought suppression, emotion suppression, and cognitive reappraisal, partly accounted for the hypothesized relationship between changes in mindfulness and two health-related outcomes: sleep quality and stress-related physical symptoms. As expected, increased mindfulness following the MBSR program was directly correlated with decreased sleep disturbance (r=-0.21, p=0.004) and decreased stress-related physical symptoms (r=-0.38, p<0.001). Partial correlations revealed that pre-post changes in rumination, unwanted intrusive thoughts, thought suppression, experiential avoidance, emotion suppression, and cognitive reappraisal each uniquely accounted for up to 32% of the correlation between the change in mindfulness and change in sleep disturbance and up to 30% of the correlation between the change in mindfulness and change in stress-related physical symptoms. Results suggest that the stress-reducing effects of MBSR are due, in part, to improvements in perseverative cognition and emotion regulation, two “transdiagnostic” mental processes that cut across stress-related disorders

Apoptosome activation, an important molecular instigator in 6-mercaptopurine induced Leydig cell death.

Leydig cells are crucial to the production of testosterone in males. It is unknown if the cancer chemotherapeutic drug, 6-mercaptopurine (6 MP), produces Leydig cell failure among adult survivors of childhood acute lymphoblastic leukemia. Moreover, it is not known whether Leydig cell failure is due to either a loss of cells or an impairment in their function. Herein, we show, in a subset of childhood cancer survivors, that Leydig cell failure is related to the dose of 6 MP. This was extended, in a murine model, to demonstrate that 6 MP exposure induced caspase 3 activation, and the loss of Leydig cells was independent of Bak and Bax activation. The death of these non-proliferating cells was triggered by 6 MP metabolism, requiring formation of both cytosolic reactive oxygen species and thiopurine nucleotide triphosphates. The thiopurine nucleotide triphosphates (with physiological amounts of dATP) uniquely activated the apoptosome. An ABC transporter (Abcc4/Mrp4) reduced the amount of thiopurines, thereby providing protection for Leydig cells. The studies reported here demonstrate that the apoptosome is uniquely activated by thiopurine nucleotides and suggest that 6 MP induced Leydig cell death is likely a cause of Leydig cell failure in some survivors of childhood cancer

Copper mediated, heterogeneous, enantioselective intramolecular Buchner reactions of a-diazoketones using continuous flow processing

Enantioselective intramolecular Buchner reactions of α-diazoketones can be effected using heterogeneous copper−bis(oxazoline) catalysts in batch or using continuous flow processing in up to 83% ee. The catalyst can be reused up to 7 times without loss of activity. For α-diazoketones 3 and 4, the enantioselection achieved in flow with the immobilized catalyst was comparable with the standard homogeneous catalyzed process

Rapid Pole Climbing with a Quadrupedal Robot

This paper describes the development of a legged robot designed for general locomotion of complex terrain but specialized for dynamical, high-speed climbing of a uniformly convex cylindrical structure, such as an outdoor telephone pole. This robot, the RiSE V3 climbing machine—mass 5.4 kg, length 70 cm, excluding a 28 cm tail appendage—includes several novel mechanical features, including novel linkage designs for its legs and a non-backdrivable, energy-dense power transmission to enable high-speed climbing. We summarize the robot’s design and document a climbing behavior that achieves rapid ascent of a wooden telephone pole at 21 cm/s, a speed previously unachieved—and, we believe, heretofore impossible—with a robot of this scale. The behavioral gait of the robot employs the mechanical design to propel the body forward while passively maintaining yaw, pitch, and roll stability during climbing locomotion. The robot’s general-purpose legged design coupled with its specialized ability to quickly gain elevation and park at a vertical station silently with minimal energy consumption suggest potential applications including search and surveillance operations as well as ad hoc networking

Residential radon-222 exposure and lung cancer: exposure assessment methodology

Although occupational epidemiological studies and animal experimentation provide strong evidence that radon-222 (222Rn) progeny exposure causes lung cancer, residential epidemiological studies have not confirmed this association. Past residential epidemiological studies have yielded contradictory findings. Exposure misclassification has seriously compromised the ability of these studies to detect whether an association exists between 222Rn exposure and lung cancer. Misclassification of 222Rn exposure has arisen primarily from: 1) detector measurement error; 2) failure to consider temporal and spatial 222Rn variations within a home; 3) missing data from previously occupied homes that currently are inaccessible; 4) failure to link 222Rn concentrations with subject mobility; and 5) measuring 222Rn gas concentration as a surrogate for 222Rn progeny exposure. This paper examines these methodological dosimetry problems and addresses how we are accounting for them in an ongoing, population-based, case-control study of 222Rn and lung cancer in Iowa

2-[3-(Methyl­diphenyl­silyl)prop­yl]isoindoline-1,3-dione

In the title compound, C24H23NO2Si, the dihedral angle between the planes of the phenyl rings attached to the Si atom is 80.78 (10)°. In the crystal, the mol­ecules form sheets lying perpendicular to [101] via C—H⋯O inter­actions. These sheets are stacked and linked in a three-dimensional framework by additional C—H⋯O inter­actions in the [10] direction

The Precision Array for Probing the Epoch of Reionization: 8 Station Results

We are developing the Precision Array for Probing the Epoch of Reionization (PAPER) to detect 21cm emission from the early Universe, when the first stars and galaxies were forming. We describe the overall experiment strategy and architecture and summarize two PAPER deployments: a 4-antenna array in the low-RFI environment of Western Australia and an 8-antenna array at our prototyping site in Green Bank, WV. From these activities we report on system performance, including primary beam model verification, dependence of system gain on ambient temperature, measurements of receiver and overall system temperatures, and characterization of the RFI environment at each deployment site. We present an all-sky map synthesized between 139 MHz and 174 MHz using data from both arrays that reaches down to 80 mJy (4.9 K, for a beam size of 2.15e-5 steradians at 154 MHz), with a 10 mJy (620 mK) thermal noise level that indicates what would be achievable with better foreground subtraction. We calculate angular power spectra ($C_\ell$) in a cold patch and determine them to be dominated by point sources, but with contributions from galactic synchrotron emission at lower radio frequencies and angular wavemodes. Although the cosmic variance of foregrounds dominates errors in these power spectra, we measure a thermal noise level of 310 mK at $\ell=100$ for a 1.46-MHz band centered at 164.5 MHz. This sensitivity level is approximately three orders of magnitude in temperature above the level of the fluctuations in 21cm emission associated with reionization.Comment: 13 pages, 14 figures, submitted to AJ. Revision 2 corrects a scaling error in the x axis of Fig. 12 that lowers the calculated power spectrum temperatur

X-RHex: A Highly Mobile Hexapedal Robot for Sensorimotor Tasks

We report on the design and development of X-RHex, a hexapedal robot with a single actuator per leg, intended for real-world mobile applications. X-RHex is an updated version of the RHex platform, designed to offer substantial improvements in power, run-time, payload size, durability, and terrain negotiation, with a smaller physical volume and a comparable footprint and weight. Furthermore, X-RHex is designed to be easier to build and maintain by using a variety of commercial off-the-shelf (COTS) components for a majority of its internals. This document describes the X-RHex architecture and design, with a particular focus on the new ability of this robot to carry modular payloads as a laboratory on legs. X-RHex supports a variety of sensor suites on a small, mobile robotic platform intended for broad, general use in research, defense, and search and rescue applications. Comparisons with previous RHex platforms are presented throughout, with preliminary tests indicating that the locomotive capabilities of X-RHex can meet or exceed the previous platforms. With the additional payload capabilities of X-RHex, we claim it to be the first robot of its size to carry a fully programmable GPU for fast, parallel sensor processing

Characterization of Laptop Fires in Spacecraft

An accidental fire involving the Lithium-Ion (Li-ion) battery in a laptop computer is one of the most likely fire scenarios on-board a spacecraft. These fires can occur from a defect in the battery that worsens with time, over-charging the battery and leading to failure or accidental damage caused by thermal runaway. While this is a relatively likely fire scenario, very little is known about the how a laptop computer fire would impact a sealed spacecraft. The heat release would likely cause a pressure rise, possibly exceeding the pressure limit of the vehicle and causing a relief valve to open. The combustion products from the fire could pose a short-term and long-term health hazard to the crew and the fire itself could cause injury to the crew and damage to the spacecraft. Despite the hazard posed by a laptop fire, there is little quantitative data on the fire size, heat release and toxic product formation. This paper presents the results of initial attempts to quantify the fire resulting from a failed laptop fire tested at the NASA White Sands Test Facility (WSTF). The data from the testing is useful to attempt to determine the fire size and characteristics such as maximum heat release rate, total heat release, maximum temperatures and fire duration are determined. Using existing models and correlations for fires, the measured fire characteristics are extrapolated to laptop fires on a vehicle the approximate size of the Orion spacecraft