Temperature Dependence of Blue Phosphorescent Cyclometalated Ir(III) Complexes

The photophysical properties for a series of facial (fac) cyclometalated Ir(III) complexes (fac-Ir(C^N)_3 (C^N = 2-phenylpyridyl (ppy), 2-(4,6-difluorophenyl)pyridyl (F2ppy), 1-phenylpyrazolyl (ppz), 1-(2,4-difluorophenyl)pyrazolyl) (F2ppz), and 1-(2-(9,9′-dimethylfluorenyl))pyrazolyl (flz)), fac-Ir(C^N)_2(C^N′) (C^N = ppz or F2ppz and C^N′ = ppy or F2ppy), and fac-Ir(CC′)_3 (C^C′ = 1-phenyl-3-methylbenzimidazolyl (pmb)) have been studied in dilute 2-methyltetrahydrofuran (2-MeTHF) solution in a temperature range of 77−378 K. Photoluminescent quantum yields (Φ) for the 10 compounds at room temperature vary between near zero and unity, whereas all emit with high efficiency at low temperature (77 K). The quantum yield for fac-Ir(ppy)_3 (Φ = 0.97) is temperature-independent. For the other complexes, the temperature-dependent data indicates that the luminescent efficiency is primarily determined by thermal deactivation to a nonradiative state. Activation energies and rate constants for both radiative and nonradiative processes were obtained using a Boltzmann analysis of the temperature-dependent luminescent decay data. Activation energies to the nonradiative state are found to range between 1600 and 4800 cm^−1. The pre-exponential factors for deactivation are large for complexes with C^N ligands (1011−1013 s^−1) and significantly smaller for fac-Ir(pmb)_3 (109 s^−1). The kinetic parameters for decay and results from density functional theory (DFT) calculations of the triplet state are consistent with a nonradiative process involving Ir−N (Ir−C for fac-Ir(pmb)_3) bond rupture leading to a five-coordinate species that has triplet metal-centered (^3MC) character. Linear correlations are observed between the activation energy and the energy difference calculated for the emissive and ^3MC states. The energy level for the ^3MC state is estimated to lie between 21700 and 24000 cm^−1 for the fac-Ir(C^N)_3 complexes and at 28000 cm^−1 for fac-Ir(pmb)_3

BMQ

BMQ: Boston Medical Quarterly was published from 1950-1966 by the Boston University School of Medicine and the Massachusetts Memorial Hospitals

Assessment and optimisation of STCA performance: Using the Pareto optimal receiver operating characteristic

EUROCONTROL Annual Safety R&D Seminar (2008), Southampton, UK, 22-24 October 2008Short Term Conflict Alert (STCA) systems are complex software programs, with many parameters that must be adjusted to achieve best performance. We describe a simple evolutionary algorithm for optimising the trade-off between wanted alerts and nuisance alerts. The procedure yields an estimate of the Pareto optimal Receiver Operating Characteristic for the STCA system and we discuss additional uses of this for characterising and comparing the performance of STCA systems and airspaces

The effect of various resuscitative regimens on hemorrhagic shock in puppies

Since shock secondary to hemorrhage is not infrequently encountered in the pediatric patient, a puppy model was devised to help measure and monitor cardiovascular and metabolic changes that occur before and after resuscitation from hypovolemic shock (mean arterial pressure of 50 mm Hg for 1 hr). Three resuscitation protocols were compared: whole blood (replacement: shed) 1:1, 5% albumin in Ringer's lactate 1:1, and Ringer's lactate 3:1. All dogs survived the experiment and responded similarly during the shock period. Thermal dilution cardiac output rose in all groups after resuscitation; however, in the Ringer's lactate and 5% albumin groups, cardiac output was statistically greater than that observed in the blood group. In all groups, pH and blood pressure approached but did not return completely to baseline levels after resuscitation. In addition, early resuscitation demonstrated a further decrease in pH ("hidden acidosis") before it began to return toward normal as resuscitation progressed. This study suggests that the infusion of large volumes of Ringer's lactate or 5% albumin in Ringer's lactate are equally efficacious in the treatment of hemorrhage. However, 5% albumin seems to be preferable because it allows infusion of a smaller quantity of electrolyte solution with equivalent physiologic benefits.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/22801/1/0000358.pd

Discriminating Between Children With ADHD and Classmates Using Peer Variables

Objective: Impaired peer relationships have long been recognized as one of the major functional problems of children with ADHD, but no specific guidelines on clinical levels of impairment in this domain exist. Method: This study used Receiver Operating Characteristics methodology to determine what aspects of peer functioning best discriminate between children with ADHD and their classmates. Optimal cutoffs indicative of clinical levels of impairment associated with ADHD diagnosis were determined for all variables. The participants were 165 children with AD/HD who were part of the Multimodal Treatment Study of Children With ADHD and their 1,298 classmates. Results: Variables that best discriminated between children with ADHD and their classmates included peer rejection and negative imbalance between given and received liking ratings (i.e., children with ADHD liked others more than they were liked). Conclusion: Peer rejection and negative imbalance show most promise for identifying clinically significant levels of peer relationship impairment in children with ADHD. (J. of Att. Dis. 2009; 12(4) 372-380)

Design for an 8 Meter Monolithic UV/OIR Space Telescope

ATLAST-8 is an 8-meter monolithic UV/optical/NIR space observatory to be placed in orbit at Sun-Earth L2 by NASA's planned Ares V cargo launch vehicle. The ATLAST-8 will yield fundamental astronomical breakthroughs. The mission concept utilizes two enabling technologies: planned Ares-V launch vehicle (scheduled for 2019) and autonomous rendezvous and docking (AR&D). The unprecedented Ares-V payload and mass capacity enables the use of a massive, monolithic, thin-meniscus primary mirror - similar to a VLT or Subaru. Furthermore, it enables simple robust design rules to mitigate cost, schedule and performance risk. AR&D enables on-orbit servicing, extending mission life and enhancing science return

Synthesis, Characterization, and Molecular Structure of Bis(tetraphenylcyclopentdienyl)rhodium(II)⊗

A 5 day diglyme reflux of Rh(acac)3 and K(C5HPh4), followed by treatment with aqueous HPF6, produces orange-yellow [(C5HPh4)2Rh]PF66 in 40 - 50% yield. Reduction of [(C5HPh4)2Rh]PF6 with sodium amalgam in THF yields olive green (C5HPh4)2Rh in 70% yield. (C5HPh4)2Rh crystallizes in the triclinic [Error : unloaded OLE object or mail attachment]space group with unit-cell parameters of a = 8.622 (3) Å, b = 10.778 (4) Å, c = 12.894 (5) Å, a = 65.58 (3)°, b = 72.66 (3)°, g = 83.52 (3)°, and Z = 1. The least squares data refined to RF = 7.63% and RwF = 10.12% for the 2479 independent observed reflections with Fo \u3e 5s(Fo ). The metal-centroid distance is 1.904 Å and all other bond lengths and angles are similar to known octaphenylmetallocenes. ESR spectra of (C5HPh4)2Rh in low-temperature glasses display a rhombic g-tensor with resolution of Rh hyperfine splitting on one-g-component. Analysis of the spectral parameters is consistent with a d7 configuration derived from a nearly degenerate dxz, dyz ground state. Voltammetry and coulometry establish the electron-transfer series (C5HPh4)2Rh1+/0/1- with E° values of -1.44 V and -2.13 V vs ferrocene. The heterogeneous charge transfer rate of the second reduction is about three orders of magnitude lower than that of the first

Research on atmospheric volcanic emissions: An overview

The project Research on Atmospheric Volcanic Emissions is a unique effort by NASA and university scientists to investigate the detailed chemical nature of plumes from volcanic eruptions. The major goals of the project are to: 1) understand the impact major eruptions will have on atmospheric chemistry processes, 2) understand the importance of volcanic emissions in the atmospheric geochemical cycles of selected species, 3) use knowledge of the plume chemical composition to diagnose and predict magmatic processes. Project RAVE\u27S first mission used the NASA Lockheed Orion P-3 outfitted with equipment to measure concentrations of the gases SO2, OCS, H2S, CS2, NO, O3and trace elements in particles in Mt. St. Helens\u27 plume on September 22, 1980. Measurements of SO2 column densities in the plume permitted calculations of SO2 fluxes. This article is an overview of the first experimental design factors and performance of the initial RAVE experiment

Considerations for Studying Sex as a Biological Variable in Spinal Cord Injury

In response to NIH initiatives to investigate sex as a biological variable in preclinical animal studies, researchers have increased their focus on male and female differences in neurotrauma. Inclusion of both sexes when modeling neurotrauma is leading to the identification of novel areas for therapeutic and scientific exploitation. Here, we review the organizational and activational effects of sex hormones on recovery from injury and how these changes impact the long-term health of spinal cord injury (SCI) patients. When determining how sex affects SCI it remains imperative to expand outcomes beyond locomotor recovery and consider other complications plaguing the quality of life of patients with SCI. Interestingly, the SCI field predominately utilizes female rodents for basic science research which contrasts most other male-biased research fields. We discuss the unique caveats this creates to the translatability of preclinical research in the SCI field. We also review current clinical and preclinical data examining sex as biological variable in SCI. Further, we report how technical considerations such as housing, size, care management, and age, confound the interpretation of sex-specific effects in animal studies of SCI. We have uncovered novel findings regarding how age differentially affects mortality and injury-induced anemia in males and females after SCI, and further identified estrus cycle dysfunction in mice after injury. Emerging concepts underlying sexually dimorphic responses to therapy are also discussed. Through a combination of literature review and primary research observations we present a practical guide for considering and incorporating sex as biological variable in preclinical neurotrauma studies