Additions to a revision of the shark genus Carcharhinus: Synonymy of Aprionodon and Hypoprion, and description of a new species of Carcharhinus (Carcharhinidae)

Features of the valid nominal species of Aprionodon Gill (isodon Valenciennes) and Hypoprion Muller and Henle (hemiodon Valenciennes, macloti Muller and Henle, and signatus Poey), plus those of a previously unrecognized species here described as Carcharhinus leiodon n.sp., are examined and compared with those of Carcharhinus Blainville. Features studied include morphometrics, vertebral numbers and other vertebral characteristics, tooth numbers, color pattern, and some other aspects of external morphology. It is concluded that on these features C. leiodon n.sp. is entirely encompassed within the parameters of Carcharhinus, and that, although A. isodon, H. hemiodon, H. macloti, and H. signatus each extend the range of diversity of Carcharhinus in one or more features, A. isodon is not uniquely different from Carcharhinus, and there is no common pattern of difference between the three species of Hypoprion and Carcharhinus. Accordingly, and because the nature of the teeth of Aprionodon and Hypoprion has been found insufficient to warrant generic distinction from Carcharhinus, the genera Aprionodon and Hypoprion are synonymised with Carcharhinus. A diagnosis and description are given for each of the above species. The descriptions include measurements, counts, and line illustrations that show the whole shark in lateral view, underside of head, nostril, and teeth. The geographic distribution is summarized, as are also the meager biological data available on number of embryos, size at birth, size at sexual maturity, and maximum size. (PDF file contains 32 pages.)

Ring-opening metathesis of bulky norbornene monomers and the radical-mediated hydrophosphonation of olefins

This thesis discusses two major topics: the ring-opening metathesis polymerization (ROMP) of bulky monomers and the radical-mediated hydrophosphonation of olefins. The research into the ROMP of bulky monomers is further divided into three chapters: wedge-shaped monomers, the alternating copolymerization of 1-methyloxanorbornene derivatives with cyclooctene, and the kinetic resolution polymerization of 1-methyloxanorbornene derivatives. The wedge-shaped monomers can be polymerized into diblock copolymers that possess photonic crystal properties. The alternating copolymerization of 1-methyloxanorbornene derivatives with cyclooctene is performed with > 90% alternation via two different routes: typical alternating copolymerization and a sequence editing approach. The kinetic resolution polymerization of these same 1-methyloxanorbornene monomers achieves only modest selectivity (S=4), but there is evidence that the growing polymer chain forms a helix that influences the selectivity of the resolution. The last topic is the radical-mediated hydrophosphonation of olefins. This synthetic method provides access to Wittig reagents that are capable of highly cis-selective olefinations of aldehydes.

Cavity-enhanced spectroscopies for applications of remote sensing, chemical kinetics and detection of radical species

This thesis describes applications of cavity enhanced spectroscopy towards applications of remote sensing, chemical kinetics and detection of transient radical molecular species. Both direct absorption spectroscopy and cavity ring-down spectroscopy are used in this work. Frequency-stabilized cavity ring-down spectroscopy (FS-CRDS) was utilized for measurements of spectral lineshapes of O₂ and CO₂ for obtaining laboratory reference data in support of NASA’s OCO-2 mission. FS-CRDS is highly sensitive (> 10 km absorption path length) and precise (> 10000:1 SNR), making it ideal to study subtle non-Voigt lineshape effects. In addition, these advantages of FS-CRDS were further extended for measuring kinetic isotope effects: A dual-wavelength variation of FS-CRDS was used for measuring precise D/H and ¹³C/¹²C methane isotope ratios (sigma>0.026%) for the purpose of measuring the temperature dependent kinetic isotope effects of methane oxidation with O(¹D) and OH radicals. Finally, direct absorption spectroscopic detection of the trans-DOCO radical via a frequency combs spectrometer was conducted in collaboration with professor Jun Ye at JILA/University of Colorado.

Nature of the radical intermediates in a substituted cyclopropylcarbiny-allylcarbinyl system

We have sought to determine the nature of the free-radical precursors to ring-opened hydrocarbon 5 and ring-closed hydrocarbon 6. Reasonable alternative formulations involve the postulation of hydrogen abstraction (a) by a pair of rapidly equilibrating classical radicals (the ring-opened allylcarbinyl-type radical 3 and the ring-closed cyclopropylcarbinyl-type 4), or (b) by a nonclassical radical such as homoallylic radical 7.

[Figure not reproduced.]

Entry to the radical system is gained via degassed thermal decomposition of peresters having the ring-opened and the ring-closed structures. The ratio of 6:5 is essentially independent of the hydrogen donor concentration for decomposition of the former at 125° in the presence of triethyltin hydrdride. A deuterium labeling study showed that the α and β methylene groups in 3 (or the equivalent) are rapidly interchanged under these conditions.

Existence of two (or more) product-forming intermediates is indicated (a) by dependence of the ratio 6:5 on the tin hydride concentration for decomposition of the ring-closed perester at 10 and 35°, and (b) by formation of cage products having largely or wholly the structure (ring-opened or ring-closed) of the starting perester.

Relative rates of hydrogen abstraction by 3 could be inferred by comparison of ratios of rate constants for hydrogen abstraction and ortho-ring cyclization:

[Figure not reproduced.]

At 100° values of k_a/k_r are 0.14 for hydrogen abstraction from 1,4-cyclohexadiene and 7 for abstraction from triethyltin hydride. The ratio 6:5 at the same temperature is ~0.0035 for hydrogen abstraction from 1,4-cyclohexadiene, ~0.078 for abstraction from the tin hydride, and ≥ 5 for abstraction from cyclohexadienyl radicals. These data indicate that abstraction of hydrogen from triethyltin hydride is more rapid than from 1,4-cyclohexadiene by a factor of ~1000 for 4, but only ~50 for 3.

Measurements of product ratios at several temperatures allowed the construction of an approximate energy-level scheme. A major inference is that isomerization of 3 to 4 is exothermic by 8 ± 3 kcal/mole, in good agreement with expectations based on bond dissociation energies. Absolute rate-constant estimates are also given.

The results are nicely compatible with a classical-radical mechanism, but attempted interpretation in terms of a nonclassical radical precursor of product ratios formed even from equilibrated radical intermediates leads, it is argued, to serious difficulties.

The roles played by hydrogen abstraction from 1,4,-cyclohexadiene and from the derived cyclohexadienyl radicals were probed by fitting observed ratios of 6:5 and 5:10 in the sense of least-squares to expressions derived for a complex mechanistic scheme. Some 30 to 40 measurements on each product ratio, obtained under a variety of experimental conditions, could be fit with an average deviation of ~6%. Significant systematic deviations were found, but these could largely be redressed by assuming (a) that the rate constant for reaction of 4 with cyclohexadienyl radical is inversely proportional to the viscosity of the medium (i.e., is diffusion-controlled), and (b) that k_a/k_r for hydrogen abstraction from 1,4-cyclohexadiene depends slightly on the composition of the medium. An average deviation of 4.4% was thereby attained.

Degassed thermal decomposition of the ring-opened perester in the presence of the triethyltin hydride occurs primarily by attack on perester of triethyltin radicals, presumably at the –O-O- bond, even at 0.01 M tin hydride at 100 and 125°. Tin ester and tin ether are apparently formed in closely similar amounts under these conditions, but the tin ester predominates at room temperature in the companion air-induced decomposition, indicating that attack on perester to give the tin ether requires an activation energy approximately 5 kcal/mole in excess of that for the formation of tin ester.

História natural do comprimento peniano após prostatectomia radical: um estudo prospectivo de longo prazo

A prostatectomia radical (PR) é um dos procedimentos mais utilizados para o tratamento do câncer de próstata (CaP) localizado, porém apesar da maior compreensão da anatomia local e do desenvolvimento tecnológico, esta cirurgia permanece associada à elevada morbidade na esfera sexual. A redução do comprimento peniano após a PR é uma queixa freqüente na prática urológica, porém não há dados na literatura a respeito da variação deste comprimento em um longo período de acompanhamento. A determinação da história natural do comprimento peniano após PR, assim como possíveis fatores de risco ou de proteção é de fundamental importância para o aconselhamento e tratamento dos pacientes submetidos a esta cirurgia. O objetivo deste estudo é determinar a história natural do comprimento peniano após a PR em um acompanhamento de cinco anos, assim como avaliar o papel da função erétil na variação do comprimento peniano destes pacientes. Foram avaliados prospectivamente os comprimentos penianos de 105 pacientes com câncer de próstata localizado submetidos PR aberta. Participação em programas de reabilitação peniana e deformidades anatômicas do pênis foram considerados critérios de exclusão. A medição do comprimento real peniano sob máxima tração (CRTmax) foi realizada antes da PR e aos 3, 6, 12, 24, 36, 48 e 60 meses no pós-operatório. O domínio da função erétil do índice internacional de função erétil (IIEF-EF) foi utilizado para avaliar a função erétil. Houve redução média de 1 cm no CRTmax em 3 meses após a PR e essa diferença permaneceu até 24 meses (p<0,001). Após este período, a diferença reduziu gradativamente, deixando de ser estatisticamente significativa em 48 meses (-0,3 cm, p=0,080) e 60 meses (+0,4 cm, p=0,065). A função erétil foi um preditor para o retorno precoce do comprimento do pênis. Um encurtamento peniano médio de 1 cm é esperado nos primeiros 24 meses após PR. No entanto, há uma tendência para a recuperação deste comprimento após 24 meses de pós-operatório, com retorno ao comprimento original em 48 meses. A função erétil preservada após a PR é um preditor para a recuperação precoce do comprimento do pênis

Julio de Castilho e a república radical

Este trabalho tem por objetivo promover um estudo sobre a vida e obra política de Júlio de Castilhos, político do Rio Grande do Sul que nos primórdios da República, entre 1895 e 1898, governou aquele Estado instituindo ali um regime republicano de base autoritária segundo os preceitos da doutrina do Positivismo formulada pelo pensador francês Augusto Comte, mas que naquele momento colocava-se em aberta oposição à tradição do pensamento brasileiro fundado no ideário liberal. Uma trajetória política ainda mais significativa, pois presta-se ao estudo inicial da questão que dá sentido maior aos nossos estudos e que vem a ser as bases do autoritarismo brasileiro inscrito na História do país por dois episódios de governos autoritários em 1937 e 1964. Os governos estes que apresentam identificação com o projeto político de Júlio de Castilhos.