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At least 199 records · Page 11

Lewis Acidity of the SbCl 3 / o ‐chloranil System

Abstract While SbCl 3 is typically inert toward oxidation by ortho ‐quinones, we use o ‐chloranil to show that the outcome of such reactions may be altered by the presence of a donor such as triphenylphosphine oxide, which readily traps the SbCl 3 (cat Cl ) synthon (cat Cl = tetrachlorocatecholate) in the form of the corresponding adduct Ph 3 PO→SbCl 3 (cat Cl ). The same reaction in the presence of a chloride salt affords the corresponding antimonate anion [Cl 4 Sb(cat Cl )] − . Computational studies indicate that the putative SbCl 3 (cat Cl ) synthon has a higher chloride ion affinity than SbCl 5 , suggesting significant Lewis acidity. This property is further demonstrated by the use of the SbCl 3 / o ‐chloranil system for both THF polymerization and a Friedel–Crafts‐type alkylation of benzene using 1‐fluorooctane. Finally, the reaction of E ‐stilbene with o ‐chloranil in the presence of SbCl 3 affords the corresponding benzodioxene, suggesting that SbCl 3 may also operate as a redox‐active catalyst.

Şit, Ferit [Department of Chemistry Texas A&amp,M ↗

Lewis Acidity of the SbCl 3 /o-chloranil System

While SbCl 3 is typically inert toward oxidation by ortho-quinones, we use o-chloranil to show that the outcome of such reactions may be altered by the presence of a donor such as triphenylphosphine oxide, which readily traps the SbCl 3 (cat Cl ) synthon (cat Cl = tetrachlorocatecholate) in the form of the corresponding adduct Ph 3 PO→SbCl 3 (cat Cl ). The same reaction in the presence of a chloride salt affords the corresponding antimonate anion [Cl 4 Sb(cat Cl )] − . Computational studies indicate that the putative SbCl 3 (cat Cl ) synthon has a higher chloride ion affinity than SbCl 5 , suggesting significant Lewis acidity. This property is further demonstrated by the use of the SbCl 3 /o-chloranil system for both THF polymerization and a Friedel–Crafts-type alkylation of benzene using 1-fluorooctane. Finally, the reaction of E-stilbene with o-chloranil in the presence of SbCl 3 affords the corresponding benzodioxene, suggesting that SbCl 3 may also operate as a redox-active catalyst.

Antimony↗

Flash Communication: Properties and Applications of a Pentavalent Bromoantimony Lewis Acid

While normally reluctant toward oxidation, SbBr 3 can be oxidized with 3,4,5,6-tetrachloro-1,2-benzoquinone (o-chloranil) in the presence of a Lewis base like the bromide anion or triphenylphosphine oxide (PPh 3 O) to form the tetrachlorocatecholate (cat Cl ) derivatives [SbBr 4 (cat Cl )] − ([2-Br] − ) and SbBr 3 (cat Cl )•OPPh 3 (2•OPPh 3 ), respectively. Structural, spectroscopic, and computational data indicate that the SbBr 3 (cat Cl ) fragment is similarly, if slightly less, Lewis acidic than the previously reported SbCl 3 (cat Cl ) fragment. The SbBr 3 /o-chloranil system, as well as its previously reported counterpart SbCl 3 /o-chloranil, were tested as Lewis acid catalysts for C−O bond metathesis and polycarbonate depolymerization. These results identified SbX 3 /o-chloranil pairs (X = Cl, Br) as simple main-group platforms for C−O bond cleavage chemistry.

Anions↗

Forecasting of Clear Air Turbulence using a Diagnostic Richardson Number Tendency formulation

The results of several case studies of Clear Air Turbulence (CAT) using the Diagnostic Richardson Number Tendency (DRT) formulation are highlighted. The performance of this technique in resolving regions of documented CAT encounters is encouraging. Its operational adaptability seems particularly attractive in that the input data can be supplied by the currently operational Rawinsonde system. A CAT index is calculated deterministically, sensing synoptic-scale changes in static stability and vertical wind shear conducive for supporting meso-scale CAT layers. This index reveals volumes of the troposphere which act as 'source regions' of Kelvin-Helmholtz instabilities. The results suggest that these regions are particularly efficient with respect to the synoptic/meso-scale energetical coupling necessary for supporting significantly turbulent layers. The output highlights specific regions of the atmosphere which can be interpreted operationally in terms of CAT-encounter probabilities.

Keller, J. L.↗

Air Traffic Complexity Measurement Environment (ACME): Software User's Guide

A user's guide for the Air Traffic Complexity Measurement Environment (ACME) software is presented. The ACME consists of two major components, a complexity analysis tool and user interface. The Complexity Analysis Tool (CAT) analyzes complexity off-line, producing data files which may be examined interactively via the Complexity Data Analysis Tool (CDAT). The Complexity Analysis Tool is composed of three independently executing processes that communicate via PVM (Parallel Virtual Machine) and Unix sockets. The Runtime Data Management and Control process (RUNDMC) extracts flight plan and track information from a SAR input file, and sends the information to GARP (Generate Aircraft Routes Process) and CAT (Complexity Analysis Task). GARP in turn generates aircraft trajectories, which are utilized by CAT to calculate sector complexity. CAT writes flight plan, track and complexity data to an output file, which can be examined interactively. The Complexity Data Analysis Tool (CDAT) provides an interactive graphic environment for examining the complexity data produced by the Complexity Analysis Tool (CAT). CDAT can also play back track data extracted from System Analysis Recording (SAR) tapes. The CDAT user interface consists of a primary window, a controls window, and miscellaneous pop-ups. Aircraft track and position data is displayed in the main viewing area of the primary window. The controls window contains miscellaneous control and display items. Complexity data is displayed in pop-up windows. CDAT plays back sector complexity and aircraft track and position data as a function of time. Controls are provided to start and stop playback, adjust the playback rate, and reposition the display to a specified time.

Source record↗

Dual reporter transgene driven by 2.3Col1a1 promoter is active in differentiated osteoblasts

AIM: As quantitative and spatial analyses of promoter reporter constructs are not easily performed in intact bone, we designed a reporter gene specific to bone, which could be analyzed both visually and quantitatively by using chloramphenicol acetyltransferase (CAT) and a cyan version of green fluorescent protein (GFPcyan), driven by a 2.3-kb fragment of the rat collagen promoter (Col2.3). METHODS: The construct Col2.3CATiresGFPcyan was used for generating transgenic mice. Quantitative measurement of promoter activity was performed by CAT analysis of different tissues derived from transgenic animals; localization was performed by visualized GFP in frozen bone sections. To assess transgene expression during in vitro differentiation, marrow stromal cell and neonatal calvarial osteoblast cultures were analyzed for CAT and GFP activity. RESULTS: In mice, CAT activity was detected in the calvaria, long bone, teeth, and tendon, whereas histology showed that GFP expression was limited to osteoblasts and osteocytes. In cell culture, increased activity of CAT correlated with increased differentiation, and GFP activity was restricted to mineralized nodules. CONCLUSION: The concept of a dual reporter allows a simultaneous visual and quantitative analysis of transgene activity in bone.

Non-NASA Center↗

Statistically Resolved Planetary Boundary Layer Height Diurnal Variability Using Spaceborne Lidar Data

The Planetary Boundary Layer Height (PBLH) significantly impacts weather, climate, and air quality. Understanding the global diurnal variation of the PBLH is particularly challenging due to the necessity of extensive observations and suitable retrieval algorithms that can adapt to diverse thermodynamic and dynamic conditions. This study utilized data from the Cloud-Aerosol Transport System (CATS) to analyze the diurnal variation of PBLH in both continental and marine regions. By leveraging CATS data and a modified version of the Different Thermo-Dynamics Stability (DTDS) algorithm, along with machine learning denoising, the study determined the diurnal variation of the PBLH in continental mid-latitude and marine regions. The CATS DTDS-PBLH closely matches ground-based lidar and radiosonde measurements at the continental sites, with correlation coefficients above 0.6 and well-aligned diurnal variability, although slightly overestimated at nighttime. In contrast, PBLH at the marine site was consistently overestimated due to the viewing geometry of CATS and complex cloud structures. The study emphasizes the importance of integrating meteorological data with lidar signals for accurate and robust PBLH estimations, which are essential for effective boundary layer assessment from satellite observations.

54 ENVIRONMENTAL SCIENCES↗

Role of microtubules in the contractile dysfunction of hypertrophied myocardium

OBJECTIVES: We sought to determine whether the ameliorative effects of microtubule depolymerization on cellular contractile dysfunction in pressure overload cardiac hypertrophy apply at the tissue level. BACKGROUND: A selective and persistent increase in microtubule density causes decreased contractile function of cardiocytes from cats with hypertrophy produced by chronic right ventricular (RV) pressure overloading. Microtubule depolymerization by colchicine normalizes contractility in these isolated cardiocytes. However, whether these changes in cellular function might contribute to changes in function at the more highly integrated and complex cardiac tissue level was unknown. METHODS: Accordingly, RV papillary muscles were isolated from 25 cats with RV pressure overload hypertrophy induced by pulmonary artery banding (PAB) for 4 weeks and 25 control cats. Contractile state was measured using physiologically sequenced contractions before and 90 min after treatment with 10(-5) mol/liter colchicine. RESULTS: The PAB significantly increased RV systolic pressure and the RV weight/body weight ratio in PAB; it significantly decreased developed tension from 59+/-3 mN/mm2 in control to 25+/-4 mN/mm2 in PAB, shortening extent from 0.21+/-0.01 muscle lengths (ML) in control to 0.12+/-0.01 ML in PAB, and shortening rate from 1.12+/-0.07 ML/s in control to 0.55+/-0.03 ML/s in PAB. Indirect immunofluorescence confocal microscopy showed that PAB muscles had a selective increase in microtubule density and that colchicine caused complete microtubule depolymerization in both control and PAB papillary muscles. Microtubule depolymerization normalized myocardial contractility in papillary muscles of PAB cats but did not alter contractility in control muscles. CONCLUSIONS: Excess microtubule density, therefore, is equally important to both cellular and to myocardial contractile dysfunction caused by chronic, severe pressure-overload cardiac hypertrophy.

NASA Discipline Cardiopulmonary↗

Bio-distribution and deposition of wildfire smoke chemicals into olfactory bulb and brain of rats after intranasal instillation

Epidemiological and experimental studies suggest wildfire smoke is a potential contributor to neurological dysfunction and associated with neuroinflammation. Using doses comparable to those encountered during intense wildfire events (200-300 μg/m 3 ), we explore the absorption, distribution, metabolism, and elimination (ADME) and pharmacokinetics of representative members of major chemical classes (acid, phenol, PAH, aldehyde) in inhaled wood smoke condensates. Male Sprague Dawley rats were intranasally instilled with smoldering eucalyptus woodsmoke extract (WSE) reconstituted in saline spiked with 14 C-labeled palmitic acid (PA), benzo[a]pyrene (B[a]P), catechol (CAT) or benzaldehyde (BZ). Serum was collected from 5 min to 2 weeks after exposure and tissues were collected at 0.5, 2, 4, 24 h and 2 weeks after exposure. Urine was collected over the 24 h exposure. Tissues were collected, rinsed in PBS and analyzed by accelerator mass spectrometry (AMS) for 14C-labeled chemicals. PA and B[a]P entered circulation slowly, reached maximum concentration (C max ) near 15 ng/mL at 2 h, and had circulating concentrations near 1/3 C max 24 h after exposure. CAT and BZ rapidly entered circulation and were mostly cleared at 2 h. Excess 14 C from all four chemicals was detected in olfactory bulb and brain over the first 24 h but only PA (or its metabolites) was retained in olfactory bulb, brain and kidney at 2 weeks post exposure. All excess 14 C was cleared from the lung at 2 weeks. Metabolite analysis of urine (CAT, BZ and B(a)P) dosed samples did not detect any parent compound. CAT and BZ were rapidly cleared. The slower uptake and clearance of PA or B[a]P or their reactive metabolites when dosed with WSE in brain and olfactory bulb potentially provide greater opportunity for inflammatory response. This study suggests that wildfire smoke chemicals can enter the brain directly from the nasal cavity to the olfactory bulb and via systemic circulation.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗

Comparative study of crystallization kinetics and phase segregation of triple cation and methylammonium lead iodide perovskites on moisture probing using synchrotron X-ray based radiation

3D mixed perovskites have achieved substantial success in boosting solar cell efficiency, but the complicated perovskite crystal formation pathway remains mysterious. Here we present detailed crystallization kinetics of mixed perovskites FA 0.83 MA 0.17 Pb(I 0.83 Br 0.17 ) 3 , where FA is formamidinium and MA is methylammonium, with the addition of Cs + to form a triple cation perovskite (3-CAT), in a comparison with the perovskite building block MAPbI 3 (MAPI) via static grazing-incidence wide-angle X-ray scattering (GIWAXS) and micro-diffraction measurements. Spin-coated films produced α-perovskite peaks with no PbI 2 or δ-intermediate phases, which was a promising result for the 3-CAT perovskite from micro-diffraction measurements. However, the 3-CAT did not remain stable on probing with varied relative humidity (RH) conditions as segregation back to the δ-intermediate and PbI 2 phase after 10 s of exposure to an RH value of 11% was found to occur from the GIWAXS results. When RH levels were elevated to over 100%, segregation peaks of PbI 2 and δ-intermediate (2H, 4H and 6H) became conspicuous as the α-phase intensity diminished, unlike for MAPI that remains relatively stable. The possible cause of this is hydrophilic bonds that form between the 3-CAT crystals and the small annealing window of the best composition perovskite (5% Cs + ) film.

Shatsala, Miller (ORCID:0009000927230192)↗

Temperature gradients and clear-air turbulence probabilities

In order to forecast clear-air turbulence (CAT) in jet aircraft flights, a study was conducted in which the data from a special-purpose instrument aboard a Boeing 747 jet airliner were compared with satellite-derived radiance gradients, conventional temperature gradients from analyzed maps, and temperature gradients obtained from a total air temperature sensor on the plane. The advantage of making use of satellite-derived data is that they are available worldwide without the need for radiosonde observations, which are scarce in many parts of the world. Major conclusions are that CAT probabilities are significantly higher over mountains than flat terrain, and that satellite radiance gradients appear to discriminate between CAT and no CAT better than conventional temperature gradients over flat lands, whereas the reverse is true over mountains, the differences between the two techniques being not large over mountains.

Bender, M. A.↗

An airborne sensor for the avoidance of clear air turbulence

This paper describes an airborne microwave radiometer that may be able to provide altitude guidance away from layers containing clear air turbulence, CAT. The sensor may also be able to predict upper limits for the severity of upcoming CAT. The 55 GHz radiometer is passive, not radar, and it measures the temperature of oxygen molecules in the viewing direction (averaged along a several-kilometer path). A small computer directs the viewing direction through elevation angle scans, and converts observed quantities to an 'altitude temperature profile'. The principle for CAT avoidance is that CAT is found statistically more often within inversion layers and at the tropopause, both of which are easily located from sensor-generated altitude temperature profiles.

Gary, B. L.↗

Reconstruction of a 3-dimensional transonic rotor flow field from holographic interferogram data

Holographic interferometry and computer-assisted tomography (CAT) are used to determine the transonic velocity field of a model rotor blade in hover. A pulsed ruby laser recorded 40 interferograms with a 2-ft-diam view field near the model rotor-blade tip operating at a tip Mach number of 0.90. After digitizing the interferograms and extracting fringe-order functions, the data are transferred to a CAT code. The CAT code then calculates the perturbation velocity in seeral planes above the blade surface. The values from the holography-CAT method compare favorably with previously obtained numerical computations in most locations near the blade tip. The results demonstrate the technique's potential for three-dimensional transonic rotor flow studies.

Yu, Y. H.↗

Three-dimensional, transonic rotor flow field reconstructed from holographic interferogram data

Holographic interferometry and computer-assisted tomography (CAT) are used to determine the transonic flow field of a model rotor blade in hover. A pulsed ruby laser records 40 interferograms with a 61 cm-diam view field near the model rotor-blade tip operating at a tip Mach number of 0.90. After digitizing the interferograms and extracting fringe-order functions, the data are transferred to a CAT code. The CAT code then calculates pressure coefficients in several planes above the blade surface. The values from the holography-CAT method compare favorably with previously obtained numerical computations and laser velocimeter measurements at most locations near the blade tip. The results demonstrate the technique's potential for three-dimensional transonic rotor flow studies.

Kittleson, J. K.↗

Reconstruction of a three-dimensional, transonic rotor flow field from holographic interferogram data

Holographic interferometry and computer-assisted tomography (CAT) are used to determine the transonic velocity field of a model rotor blade in hover. A pulsed ruby laser recorded 40 interferograms with a 2-ft-diam view field near the model rotor-blade tip operating at a tip Mach number of 0.90. After digitizing the interferograms and extracting fringe-order functions, the data are transferred to a CAT code. The CAT code then calculates the perturbation velocity in several planes above the blade surface. The value from the holography-CAT method compare favorably with previously obtained numerical computations in most locations near the blade tip. The results demonstrate the technique's potential for three-dimensional transonic rotor flow studies.

Yu, Y. H.↗

Vestibular system and neural correlates of motion sickness

Initial studies re-examine the role of certain central nervous system structures in the production of vestibular-induced vomiting and vomiting in general. All experiments were conducted using cats. Since these studies demonstrated that the essential role of various central structures in vestibular-induced vomiting is only poorly understood, efforts were re-directed to study the control of the effector muscles (diaphragm and abdominal muscles) that produce the pressure changes responsible for vomiting, with the goal of determining how this control mechanism is engaged during motion sickness. Experiments were conducted to localize the motoneurons that innervate the individual abdominal muscles and the portion of the diaphragm that surrounds the esophagus. A central question regarding respiratory muscle control during vomiting is whether these muscles are activated via the same brain stem pre-motor neurons that provide descending respiratory drive and/or by other descending input(s). In other experiments, the use of a combination of pitch and roll motions to produce motion sickness in unrestrained cats was evaluated. This stimulus combination can produce vomiting in only the most susceptible cats and is thus not as provacative a stimulus for cats as vertical linear acceleration.

Miller, Alan D.↗

Reconstruction of a three-dimensional, transonic rotor flow field from holographic interferogram data

Holographic interferometry and computerized aided tomography (CAT) are used to determine the transonic velocity field of a model rotor blade in hover. A pulsed ruby laser recorded 40 interferograms with a 2 ft dia view field near the model rotor blade tip operating at a tip Mach number of 0.90. After digitizing the interferograms and extracting the fringe order functions, the data are transferred to a CAT code. The CAT code then calculates the perturbation velocity in several planes above the blade surface. The values from the holography-CAT method compare favorably with previously obtained numerical computations in most locations near the blade tip. The results demonstrate the technique's potential for three dimensional transonic rotor flow studies.

Kittleson, John K.↗

Flight test evaluation of the E-systems Differential GPS category 3 automatic landing system

Test flights were conducted to evaluate the capability of Differential Global Positioning System (DGPS) to provide the accuracy and integrity required for International Civil Aviation Organization (ICAO) Category (CAT) III precision approach and landings. These test flights were part of a Federal Aviation Administration (FAA) program to evaluate the technical feasibility of using DGPS based technology for CAT III precision approach and landing applications. An IAI Westwind 1124 aircraft (N24RH) was equipped with DGPS receiving equipment and additional computing capability provided by E-Systems. The test flights were conducted at NASA Ames Research Center's Crows Landing Flight Facility, Crows Landing, California. The flight test evaluation was based on completing 100 approaches and landings. The navigation sensor error accuracy requirements were based on ICAO requirements for the Microwave Landing System (MLS). All of the approaches and landings were evaluated against ground truth reference data provided by a laser tracker. Analysis of these approaches and landings shows that the E-Systems DGPS system met the navigation sensor error requirements for a successful approach and landing 98 out of 100 approaches and landings, based on the requirements specified in the FAA CAT III Level 2 Flight Test Plan. In addition, the E-Systems DGPS system met the integrity requirements for a successful approach and landing or stationary trial for all 100 approaches and landings and all ten stationary trials, based on the requirements specified in the FAA CAT III Level 2 Flight Test Plan.

Kaufmann, David N.↗