Recent advances at NASA in calculating the electronic spectra of diatomic molecules

Advanced entry vehicles, such as the proposed Aero-assisted Orbital Transfer Vehicle, provide new and challenging problems for spectroscopy. Large portions of the flow field about such vehicles will be characterized by chemical and thermal nonequilibrium. Only by considering the actual overlap of the atomic and rotational lines emitted by the species present can the impact of radiative transport within the flow field be assessed correctly. To help make such an assessment, a new computer program is described that can generate high-resolution, line-by-line spectra for any spin-allowed transitions in diatomic molecules. The program includes the matrix elements for the rotational energy and distortion to the fourth order; the spin-orbit, spin-spin, and spin-rotation interactions to first order; and the lambda splitting by a perturbation calculation. An overview of the Computational Chemistry Branch at Ames Research Center is also presented

Science objectives and performance of a radiometer and window design for atmospheric entry experiments

This paper describes the techniques developed for measuring stagnation-point radiation in NASA's cancelled Aeroassist Flight Experiment (AFE). It specifies the need for such a measurement; the types and requirements for the needed instruments; the Radiative Heating Experiment (RHE) developed for the AFE; the requirements, design parameters, and performance of the window developed for the RHE; the procedures and summary of the technique; and results of the arc-jet wind tunnel experiment conducted to demonstrate the overall concept. Subjects emphasized are the commercial implications of the knowledge to be gained by this experiment in connection with the Aeroassisted Space Transfer Vehicle (ASTV), the nonequilibrium nature of the radiation, concerns over the contribution of vacuum-ultraviolet radiation to the overall radiation, and the limit on the flight environment of the vehicle imposed by the limitations on the window material. Results show that a technique exists with which the stagnation-point radiation can be measured in flight in an environment of interest to commercial ASTV applications

NEQAIR96,Nonequilibrium and Equilibrium Radiative Transport and Spectra Program: User's Manual

This document is the User's Manual for a new version of the NEQAIR computer program, NEQAIR96. The program is a line-by-line and a line-of-sight code. It calculates the emission and absorption spectra for atomic and diatomic molecules and the transport of radiation through a nonuniform gas mixture to a surface. The program has been rewritten to make it easy to use, run faster, and include many run-time options that tailor a calculation to the user's requirements. The accuracy and capability have also been improved by including the rotational Hamiltonian matrix formalism for calculating rotational energy levels and Hoenl-London factors for dipole and spin-allowed singlet, doublet, triplet, and quartet transitions. Three sample cases are also included to help the user become familiar with the steps taken to produce a spectrum. A new user interface is included that uses check location, to select run-time options and to enter selected run data, making NEQAIR96 easier to use than the older versions of the code. The ease of its use and the speed of its algorithms make NEQAIR96 a valuable educational code as well as a practical spectroscopic prediction and diagnostic code

Dilute, derivatise and shoot: Measurement of urinary free metanephrines and catecholamines as ethyl derivatives by LC-MSMS

This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ This author accepted manuscript is made available following 24 month embargo from date of publication (Sept 2017) in accordance with the publisher’s archiving policyBackground The measurement of catecholamines and their metabolites in either urine or plasma is an important diagnostic test used to exclude the presence of neuroendocrine tumours. Because of weak chromatographic retention and potential ion-suppression, reverse-phase LC-MSMS is not ideal for analysis of these polar molecules. Here, we investigate derivatisation by ethylation as an alternative approach. Methods A simple and rapid method involving acetaldehyde and a reducing agent was used to convert urine free metanephrines and catecholamines, and their deuterated analogues as internal standards, to mono-ethyl or diethyl- derivatives. Using an Agilent 6460 triple-quadrupole mass spectrometer, precursor and product ion mass spectra were recorded to allow comparison of multiple reaction monitoring methods for both derivatised and non-derivatised analytes under reverse-phase LC-MSMS conditions with positive electrospray ionization. Results Conversion of biogenic amines to less polar ethyl derivatives increased their mass and enhanced the intensity of their molecular ions and fragments. Ethylation also improved the chromatographic properties of the amines, with greater retention and elution from reverse-phase HPLC columns with a methanol or acetonitrile gradient. The signal response of tandem mass spectrometric detection was increased up to 50-fold for ethyl metanephrines compared to non-derivatised compounds. This increase allowed for the omission of solid-phase extraction of urine as a clean-up step prior to analysis. The ‘dilute-derivatise-shoot’ method maintained analytical performance with respect to between-run imprecision (CV < 6%) and accuracy in an external quality assurance program. Gender-related ranges for free metanephrines in early-morning spot urines, collected from adult patients, were similar using either derivatised or non-derivatised samples. Conclusions The LC-MSMS detection of free urine biogenic amines can be greatly enhanced by ethyl derivatisation, which is easy and rapid to perform. Advantages include improved chromatography and lower limits of quantitation, that negate the requirement for solid-phase clean-up of urine prior to analysis. A disadvantage is the potential toxicity of the derivatising agents used if they are not handled appropriately

Arcjet exploratory tests of ARC optical window design for the AFE vehicle

Tests were made in the 20 MW arc jet facility at the NASA ARC to determine the suitability of sapphire and fused silica as window materials for the Aeroassist Flight Experiment (AFE) entry vehicle. Twenty nine tests were made; 25 at a heating rate about 80 percent of that expected during the AFE entry and 4 at approximately the full, 100 percent AFE heating rate profile, that produces a temperature of about 2900 F on the surface of the tiles that protect the vehicle. These tests show that a conductively cooled window design using mechanical thermal contacts and sapphire is probably not practical. Cooling the window using mechanical thermal contacts produces thermal stresses in the sapphire that cause the window to crack. An insulated design using sapphire, that cools the window as little as possible, appears promising although some spectral data in the vacuum-ultra-violet (VUV) will be lost due to the high temperature reached by the sapphire. The surface of the insulated sapphire windows, tested at the 100 percent AFE heating rate, showed some slight ablation, and cracks appeared in two of three test windows. One small group of cracks were obviously caused by mechanical binding of the window in the assembly, which can be eliminated with improved design. Other cracks were long, straight, thin crystallographic cracks that have very little effect on the optical transmission of the window. Also, the windows did not fall apart along these crystallographic cracks when the windows were removed from their assemblies. Theoretical results from the thermal analysis computer program SINDA indicate that increasing the window thickness from 4 to 8 mm may enable surface ablation to be avoided. An insulated design using a fused silica window tested at the nominal AFE heating rate experienced severe ablation, thus fused silica is not considered to be an acceptable window material

Diversification and agrarian change under environmental constraints in rural China: Evidence from a poor township of Beijing municipality

Working paper du GATE 2007-11This article illustrates the impact of changes related to market reforms and environmental policies on the economic structure in rural China by providing a comparative analysis of several villages in a poor township in Beijing municipality. Two main concomitant phenomena are affecting agricultural and non-agricultural choices in the studied area. First, the introduction of market mechanisms is encouraging local population to engage in new activities that are closer to local comparative advantages. Second, rural households are facing new constraints in the form of environmental protection measures, which have weakened traditional insurance channels provided by forest resources and cattle stock. Drawing on household-level survey data and interviews with village heads conducted in ten villages of Labagoumen township in December 2003, this article analyzes households decisions in response to market reforms and environmental constraints. We find large disparities both between villages and households in the diversification process and discuss the reasons of observed inertia in the region, most households still heavily relying on corn production

Review: Transport Losses in Market Weight Pigs: I. A Review of Definitions, Incidence, and Economic Impact

Transport losses (dead and nonambulatory pigs) present animal welfare, legal, and economic challenges to the US swine industry. The objectives of this review are to explore 1) the historical perspective of transport losses; 2) the incidence and economic implications of transport losses; and 3) the symptoms and metabolic characteristics of fatigued pigs. In 1933 and 1934, the incidence of dead and nonambulatory pigs was reported to be 0.08 and 0.16%, respectively. More recently, 23 commercial field trials (n = 6,660,569 pigs) were summarized and the frequency of dead pigs, nonambulatory pigs, and total transport losses at the processing plant were 0.25, 0.44, and 0.69% respectively. In 2006, total economic losses associated with these transport losses were estimated to cost the US pork industry approximately $46 million. Furthermore, 0.37 and 0.05% of the nonambulatory pigs were classified as either fatigued (nonambulatory, noninjured) or injured, respectively, in 18 of these trials (n = 4,966,419 pigs). Fatigued pigs display signs of acute stress (open-mouth breathing, skin discoloration, muscle tremors) and are in a metabolic state of acidosis, characterized by low blood pH and high blood lactate concentrations; however, the majority of fatigued pigs will recover with rest. Transport losses are a multifactorial problem consisting of people, pig, facility design, management, transportation, processing plant, and environmental factors, and, because of these multiple factors, continued research efforts are needed to understand how each of the factors and the relationships among factors affect the well-being of the pig during the marketing process

Effects of antiplatelet therapy on stroke risk by brain imaging features of intracerebral haemorrhage and cerebral small vessel diseases: subgroup analyses of the RESTART randomised, open-label trial

Background Findings from the RESTART trial suggest that starting antiplatelet therapy might reduce the risk of recurrent symptomatic intracerebral haemorrhage compared with avoiding antiplatelet therapy. Brain imaging features of intracerebral haemorrhage and cerebral small vessel diseases (such as cerebral microbleeds) are associated with greater risks of recurrent intracerebral haemorrhage. We did subgroup analyses of the RESTART trial to explore whether these brain imaging features modify the effects of antiplatelet therapy

67202; ‡ ‡ Innovative Livestock Solutions, Blackie, Alberta, Canada T0L0J0; § § Livestock Behavior Research Unit

ABSTRAC

Psychology and aggression

Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/68264/2/10.1177_002200275900300301.pd