Group 14 Metallocene Catalysts for Carbonyl Hydroboration and Cyanosilylation

A series of six Group 14 metallocene compounds (M = Ge, Sn, Pb) were studied as catalysts for carbonyl hydroboration and cyanosilylation reactions at room temperature. Both bis(pentamethylcyclopentadienyl) and tetramethyldisiloxa[3]metallocenophane compounds were compared. The tin and lead metallocenophanes exhibited the highest reactivity in hydroboration and cyanosilylation reactions. Hammett analysis of aldehyde hydroboration provided a ρ value of 0.73, suggesting a buildup of negative charge during the turnover-limiting step, consistent with the transition state for hydride transfer to the carbonyl center. NMR studies of Lewis acidity indicate that the Ge, Sn, and Pb tetramethyldisiloxa[3]metallocenophane compounds are weak Lewis acids

Enhanced Transmission Through Disordered Potential Barrier

Effect of weak disorder on tunneling through a potential barrier is studied analytically. A diagrammatic approach based on the specific behavior of subbarrier wave functions is developed. The problem is shown to be equivalent to that of tunneling through rectangular barriers with Gaussian distributed heights. The distribution function for the transmission coefficient $T$ is derived, and statistical moments \left are calculated. The surprising result is that in average disorder increases both tunneling conductance and resistance.Comment: 10 pages, REVTeX 3.0, 2 figures available upon reques

Stay and Play with Mickey Mouse: Familiar Characters Increase Children’s Exploratory Play

When children are introduced to a novel toy, they explore to discover how the toy works, but do not always discover all of the functions (Bonawitz et al., 2011). Research has shown that children prefer objects with a familiar character on them (Danovitch & Mills, 2014). This study investigates whether the presence of a familiar character’s image on a novel toy encourages exploratory play. Four- and 5-year-olds (n = 40) were presented with a novel toy, containing 5 different functions, that either displayed an image of their favorite familiar character or an image of that character’s color scheme. Children were given up to 5 minutes to play with the toy. Children’s play was coded for the number of functions they discovered and how long they played with the toy. Results showed no significant difference between conditions for number of functions discovered. However, children who were given a toy with their favorite character’s image on it spent significantly more time exploring the toy than children who had a toy with the character’s color scheme on it. These findings suggest that seeing a familiar character on an object promotes children’s exploration of that object.https://ir.library.louisville.edu/uars/1010/thumbnail.jp

Are non-allergic drug reactions commonly documented as medication “allergies”? A national cohort of Veterans\u27 admissions from 2000 to 2014

Purpose: Adverse drug reactions (ADRs) including medication allergies are not well-described among large national cohorts. This study described the most common documented medication allergies and their reactions among a national cohort of Veterans Affairs (VA) inpatients. Methods: We evaluated inpatient admissions in any VA Medical Center from 1 January 2000 to 31 December 2014. Each admission was linked with allergy history preceding or upon admission. Individual drugs were aggregated into drug class category including: penicillins, sulfonamides, angiotensin converting enzyme (ACE) inhibitors, opiates, HMG-CoA reductase inhibitors (“statins”) and non-steroidal anti-inflammatory inhibitors (NSAID). Results were reported in aggregate and over time. Results: Approximately ~10.8 million inpatient admissions occurred from 2000 to 2014. We found the most commonly reported allergy drug classes were penicillins (13%, n = 1 410 080), opiates (9.1%, n = 984 978), ACE inhibitors (5.7%, n = 618 075) sulfonamides (5.1%, n = 558 653), NSAIDs (5.1%, n = 551 216) and statins (3.6%, n  = 391 983). Several allergy histories increased over time including opiates (6.2 to 11.2%), ACE inhibitors (1.3 to 10.2%), statins (0.3 to 7.3%) and NSAIDs (3.9 to 6.0%). Rash was the most commonly documented reaction on reports for penicillins (25.5%, n = 371 825), sulfonamides (25.6%, n = 165 954) and NSAIDs (10.3%, n = 65 741). The most common reaction for opiates was nausea/vomiting (17.9%, n = 211 864), cough/coughing for ACE inhibitors (41.0%, n = 270 537) and muscle pain/myalgia for statins (34.1%, n = 186 565). Conclusions: We report that penicillins and opiates are the most commonly documented drug allergies among VA inpatients, but other drug classes such as ACE inhibitors, statins and NSAIDs are becoming increasingly common. Clinicians also commonly document non-allergic ADRs in the allergy section such as cough or myalgia. Copyright © 2016 John Wiley & Sons, Ltd

Design of hidden thermodynamic driving for non-equilibrium systems via mismatch elimination during DNA strand displacement

Recent years have seen great advances in the development of synthetic self-assembling molecular systems. Designing out-of-equilibrium architectures, however, requires a more subtle control over the thermodynamics and kinetics of reactions. We propose a mechanism for enhancing the thermodynamic drive of DNA strand-displacement reactions whilst barely perturbing forward reaction rates: the introduction of mismatches within the initial duplex. Through a combination of experiment and simulation, we demonstrate that displacement rates are strongly sensitive to mismatch location and can be tuned by rational design. By placing mismatches away from duplex ends, the thermodynamic drive for a strand-displacement reaction can be varied without significantly affecting the forward reaction rate. This hidden thermodynamic driving motif is ideal for the engineering of non-equilibrium systems that rely on catalytic control and must be robust to leak reactions

Explaining the Chemical Inventory of Orion KL through Machine Learning

The interplay of the chemistry and physics that exists within astrochemically relevant sources can only be fully appreciated if we can gain a holistic understanding of their chemical inventories. Previous work by Lee et al. (2021) demonstrated the capabilities of simple regression models to reproduce the abundances of the chemical inventory of the Taurus Molecular Cloud 1 (TMC-1), as well as provide abundance predictions for new candidate molecules. It remains to be seen, however, to what degree TMC-1 is a ``unicorn'' in astrochemistry, where the simplicity of its chemistry and physics readily facilitates characterization with simple machine learning models. Here we present an extension in chemical complexity to a heavily studied high-mass star forming region: the Orion Kleinmann-Low (Orion KL) nebula. Unlike TMC-1, Orion KL is composed of several structurally distinct environments that differ chemically and kinematically, wherein the column densities of molecules between these components can have non-linear correlations that cause the unexpected appearance or even lack of likely species in various environments. This proof-of-concept study used similar regression models sampled by Lee et al. (2021) to accurately reproduce the column densities from the XCLASS fitting program presented in Crockett et al. (2014).Comment: 14 pages; 6 figures, 1 table in the main text. 0 figures, 1 table in the appendix. Accepted for publication in The Astrophysical Journal. Molecular dataset for machine learning can be found in the Zenodo repository here: https://zenodo.org/record/767560

Memory CD8⁺ T cells exhibit tissue imprinting and non-stable exposure-dependent reactivation characteristics following blood-stage Plasmodium berghei ANKA infections

Experimental cerebral malaria (ECM) is a severe complication of Plasmodium berghei ANKA (PbA) infection in mice, characterized by CD8(+) T‐cell accumulation within the brain. Whilst the dynamics of CD8(+) T‐cell activation and migration during extant primary PbA infection have been extensively researched, the fate of the parasite‐specific CD8(+) T cells upon resolution of ECM is not understood. In this study, we show that memory OT‐I cells persist systemically within the spleen, lung and brain following recovery from ECM after primary PbA‐OVA infection. Whereas memory OT‐I cells within the spleen and lung exhibited canonical central memory (Tcm) and effector memory (Tem) phenotypes, respectively, memory OT‐I cells within the brain post‐PbA‐OVA infection displayed an enriched CD69(+)CD103(−) profile and expressed low levels of T‐bet. OT‐I cells within the brain were excluded from short‐term intravascular antibody labelling but were targeted effectively by longer‐term systemically administered antibodies. Thus, the memory OT‐I cells were extravascular within the brain post‐ECM but were potentially not resident memory cells. Importantly, whilst memory OT‐I cells exhibited strong reactivation during secondary PbA‐OVA infection, preventing activation of new primary effector T cells, they had dampened reactivation during a fourth PbA‐OVA infection. Overall, our results demonstrate that memory CD8(+) T cells are systemically distributed but exhibit a unique phenotype within the brain post‐ECM, and that their reactivation characteristics are shaped by infection history. Our results raise important questions regarding the role of distinct memory CD8(+) T‐cell populations within the brain and other tissues during repeat Plasmodium infections

A Micromechanical INS/GPS System for Small Satellites

The cost and complexity of large satellite space missions continue to escalate. To reduce costs, more attention is being directed toward small lightweight satellites where future demand is expected to grow dramatically. Specifically, micromechanical inertial systems and microstrip global positioning system (GPS) antennas incorporating flip-chip bonding, application specific integrated circuits (ASIC) and MCM technologies will be required. Traditional microsatellite pointing systems do not employ active control. Many systems allow the satellite to point coarsely using gravity gradient, then attempt to maintain the image on the focal plane with fast-steering mirrors. Draper's approach is to actively control the line of sight pointing by utilizing on-board attitude determination with micromechanical inertial sensors and reaction wheel control actuators. Draper has developed commercial and tactical-grade micromechanical inertial sensors, The small size, low weight, and low cost of these gyroscopes and accelerometers enable systems previously impractical because of size and cost. Evolving micromechanical inertial sensors can be applied to closed-loop, active control of small satellites for micro-radian precision-pointing missions. An inertial reference feedback control loop can be used to determine attitude and line of sight jitter to provide error information to the controller for correction. At low frequencies, the error signal is provided by GPS. At higher frequencies, feedback is provided by the micromechanical gyros. This blending of sensors provides wide-band sensing from dc to operational frequencies. First order simulation has shown that the performance of existing micromechanical gyros, with integrated GPS, is feasible for a pointing mission of 10 micro-radians of jitter stability and approximately 1 milli-radian absolute error, for a satellite with 1 meter antenna separation. Improved performance micromechanical sensors currently under development will be suitable for a range of micro-nano-satellite applications