Quantum mechanical calculations of reactive scattering cross sections in bimolecular encounters

Study applies the nonequilibrium collision theory of reaction rates to the estimation of rate constants for simple reactions. The complications in the quantum mechanical description of chemical reactions and the care needed in approximating the exact wave function for the collision are shown

Design of a Martian Communication Constellation of CubeSats

Spacecraft operating on the Martian surface have used relay satellites as a means of improving communication capabilities, mainly in terms of bandwidth and availability. However, the spacecraft used to achieve this have been large spacecraft (1000s of kilograms) and were not designed with relay capability as the design priority. This thesis explores the possibility of using a CubeSat-based constellation as a communications network for spacecraft operating on the Martian surface. Brute-force techniques are employed to explore the design space of possible constellations. An analysis of constellation configurations that provide complete, continuous coverage of the Martian surface is presented. The stability of these constellations are analyzed, and recommendations are made for stable configurations and the orbital maintenance thereof. Link budget analysis is used to determine the communications capability of each constellation, and recommendations are made for sizing each communication element. The results of these three analyses are synthesized to create an architecture generation tool. This tool is used to identify mission architectures that suit a variety of mission requirements, and these architectures are presented. The primary recommended architecture utilizes 18 CubeSats in three orbital planes with six additional larger relay satellites to provide an average of over one terabit/sol downlink and 100 kbps uplink capability

Feasiblity study for a 34 GHz (Ka band) gyroamplifier

The feasibility of using a gyroklystron power tube as the final amplifier in a 400 kW CW 34 GHz transmitter on the Goldstone Antenna is investigated. A conceptual design of the gyroklystron and the transmission line connecting it with the antenna feed horn is presented. The performance characteristics of the tube and transmission line are compared to the transmitter requirements for a deep space radar system. Areas of technical risk for a follow-on hardware development program for the gyroklystron amplifier and overmoded transmission line components are discussed

Structural and stereogenic properties of spiro- and ansa-substituted 1,3-propanedioxy derivatives of a spermine-bridged cyclotriphosphazene

Reaction of 1,3-propanediol with the achiral spermine-bridged cyclophosphazene 1 at various molar ratios in THF gives a number of spiro-and ansa-derivatives that exhibit different stereogenic properties, viz. racemic, meso or achiral forms. As expected, spiro forms are preferred (giving mono-, di-, tri- and tetra-substitution), although significant amounts of mono- and di-substituted ansa derivatives also occur. A number of new structures have been characterized by NMR spectroscopy and X-ray crystallography in this work; mono-spiro 2, di-mono-ansa 6 and di-spiro/mono-ansa 8. The mono-ansa compound 3 was observed in solution by NMR spectroscopy but no evidence was found for the monospiro/monoansa 5, a necessary precursor of compound 8. The tri-spiro derivative 7 has been isolated and characterized by 31P NMR spectroscopy, whereas the structures of the di-monospiro 4 (meso) and tetra-spiro 9 have been characterized previously. The stereogenic properties of many of the products have been confirmed by X-ray crystallography and/or by 31P NMR spectroscopy on addition of the chiral solvating agent, (S)-(+)-2,2,2-trifluoro-1-(9-anthryl)ethanol. Although the starting compound 1 is achiral, it is found that unsymmetrically-substituted derivatives with 1,3-propanediol give racemic mixtures for the mono-spiro 2 and tri-spiro 7 derivatives, whereas symmetrically-substituted derivatives such as di-mono-ansa 6 and di-spiro/mono-ansa 8 are meso. It is found that care must taken in interpreting the 'splitting' of 31P NMR signals on addition of CSA in terms of 'chirality' of molecules, because some meso compounds give false positive results due to changes from A2X-like to A2B or ABX spin systems

Racial and Ethnic Differences in Serum Cotinine Levels of Cigarette Smokers Third National Health and Nutrition Examination Survey, 1988-1991

Context.— Cotinine, a metabolite of nicotine, is a marker of exposure to tobacco smoke. Previous studies suggest that non-Hispanic blacks have higher levels of serum cotinine than non-Hispanic whites who report similar levels of cigarette smoking. Objective.— To investigate differences in levels of serum cotinine in black, white, and Mexican American cigarette smokers in the US adult population. Design.— Third National Health and Nutrition Examination Survey, 1988-1991. Participants.— A nationally representative sample of persons aged 17 years or older who participated in the survey. Outcome Measures.— Serum cotinine levels by reported number of cigarettes smoked per day and by race and ethnicity. Results.— A total of 7182 subjects were involved in the study; 2136 subjects reported smoking at least 1 cigarette in the last 5 days. Black smokers had cotinine concentrations substantially higher at all levels of cigarette smoking than did white or Mexican American smokers (P\u3c.001). Serum cotinine levels for blacks were 125 nmol/L (22 ng/mL) (95% confidence interval [CI], 79-176 nmol/L [14-31 ng/mL]) to 539 nmol/L (95 ng/mL) (95% CI, 289-630 nmol/L [51-111 ng/mL]) higher than for whites and 136 nmol/L (24 ng/mL) (95% CI, 85-182 nmol/L [15-32 ng/mL]) to 641 nmol/L (113 ng/mL) (95% CI, 386-897 nmol/L [68-158 ng/mL]) higher than for Mexican Americans. These differences do not appear to be attributable to differences in environmental tobacco smoke exposure or in number of cigarettes smoked. Conclusions.— To our knowledge, this study provides the first evidence from a national study that serum cotinine levels are higher among black smokers than among white or Mexican American smokers. If higher cotinine levels among blacks indicate higher nicotine intake or differential pharmacokinetics and possibly serve as a marker of higher exposure to cigarette carcinogenic components, they may help explain why blacks find it harder to quit and are more likely to experience higher rates of lung cancer than white smokers

Urinary Perchlorate and Thyroid Hormone Levels in Adolescent and Adult Men and Women Living in the United States

BACKGROUND: Perchlorate is commonly found in the environment and known to inhibit thyroid function at high doses. Assessing the potential effect of low-level exposure to perchlorate on thyroid function is an area of ongoing research. OBJECTIVES: We evaluated the potential relationship between urinary levels of perchlorate and serum levels of thyroid stimulating hormone (TSH) and total thyroxine (T(4)) in 2,299 men and women, ≥ 12 years of age, participating in the National Health and Nutrition Examination Survey (NHANES) during 2001–2002. METHODS: We used multiple regression models of T(4) and TSH that included perchlorate and covariates known to be or likely to be associated with T(4) or TSH levels: age, race/ethnicity, body mass index, estrogen use, menopausal status, pregnancy status, premenarche status, serum C-reactive protein, serum albumin, serum cotinine, hours of fasting, urinary thiocyanate, urinary nitrate, and selected medication groups. RESULTS: Perchlorate was not a significant predictor of T(4) or TSH levels in men. For women overall, perchlorate was a significant predictor of both T(4) and TSH. For women with urinary iodine < 100 μg/L, perchlorate was a significant negative predictor of T(4) (p < 0.0001) and a positive predictor of TSH (p = 0.001). For women with urinary iodine ≥ 100 μg/L, perchlorate was a significant positive predictor of TSH (p = 0.025) but not T(4) (p = 0.550). CONCLUSIONS: These associations of perchlorate with T(4) and TSH are coherent in direction and independent of other variables known to affect thyroid function, but are present at perchlorate exposure levels that were unanticipated based on previous studies