Attempts to Synthesize Cyclic Group 8 Metallaesters

In studying a proposed carbon monoxide reduction scheme an attempt has been made to synthesize bifunctional group 8 transition metal carbonyl complexes containing intramolecular nucleophiles. The incorporation of alkoxide nucleophiles through cyclopentadienyl ligands was hoped to encourage attack on carbonyl ligands thereby forming cyclic metallaesters. The attempts to synthesize these substituted cyclopentadienyl group 8 transition metal complexes have thus far been unsuccessful.

Synthesis of (±)-7,8-epoxy-4-basmen-6-one by a transannular cyclization strategy

The first synthesis of the cembranoid natural product (±)-7,8-epoxy-4-basmen-6- one (1) is described. Key steps of the synthetic route include the cationic cyclization of the acid chloride from 15 to provide the macrocycle 16, and the photochemical transannular radical cyclization of the ester 41 to form the tricyclic product 50. Product 50 was transformed into 1 in ten steps. Transition-state molecular modeling studies were found to provide accurate predictions of the structural and stereochemical outcomes of cyclization reactions explored experimentally in the development of the synthetic route to 1. These investigations should prove valuable in the development of transannular cyclization as a strategy for synthetic simplification.

1. Astronomical photometry at wavelengths of 8.5, 10.5, and 11.6 µm. 2. Infrared emission from asteroids at wavelengths of 8.5, 10.5, and 11.6 µm

The purpose of this thesis is to present new observations of thermal-infrared radiation from asteroids. Stellar photometry was performed to provide standards for comparison with the asteroid data. The details of the photometry and the data reduction are discussed in Part 1. A system of standard stars is derived for wavelengths of 8.5, 10.5 and 11.6 µm and a new calibration is adopted. Sources of error are evaluated and comparisons are made with the data of other observers.

The observations and analysis of the thermal-emission observations of asteroids are presented in Part 2. Thermal-emission lightcurve and phase effect data are considered. Special color diagrams are introduced to display the observational data. These diagrams are free of any model-dependent assumptions and show that asteroids differ in their surface properties.

On the basis of photometric models, (4) Vesta is thought to have a bolometric Bond albedo of about 0.1, an emissivity greater than 0.7 and a true radius that is close to the model value of 300^(+50)_(-30)km. Model albedos and model radii are given for asteroids 1, 2, 4, 5, 6, 7, 15, 19, 20, 27, 39, 44, 68, 80, 324 and 674. The asteroid (324) Bamberga is extremely dark with a model (~bolometric Bond) albedo in the 0.01 - 0.02 range, which is thought to be the lowest albedo yet measured for any solar-system body. The crucial question about such low-albedo asteroids is their number and the distribution of their orbits.

Geological evolution of two crustal scale shear zones. Part I. The Rand thrust complex, northwestern Mojave Desert, California. Part II. The Magdalena metamorphic core complex, north central Sonora, Mexico

The geology and structure of two crustal scale shear zones were studied to understand the partitioning of strain within intracontinental orogenic belts. Movement histories and regional tectonic implications are deduced from observational data. The two widely separated study areas bear the imprint of intense Late Mesozoic through Middle Cenozoic tectonic activity. A regional transition from Late Cretaceous-Early Tertiary plutonism, metamorphism, and shortening strain to Middle Tertiary extension and magmatism is preserved in each area, with contrasting environments and mechanisms. Compressional phases of this tectonic history are better displayed in the Rand Mountains, whereas younger extensional structures dominate rock fabrics in the Magdalena area.

In the northwestern Mojave desert, the Rand Thrust Complex reveals a stack of four distinctive tectonic plates offset along the Garlock Fault. The lowermost plate, Rand Schist, is composed of greenschist facies metagraywacke, metachert, and metabasalt. Rand Schist is structurally overlain by Johannesburg Gneiss (= garnet-amphibolite grade orthogneisses, marbles and quartzites), which in turn is overlain by a Late Cretaceous hornblende-biotite granodiorite. Biotite granite forms the fourth and highest plate. Initial assembly of the tectonic stack involved a Late Cretaceous? south or southwest vergent overthrusting event in which Johannesburg Gneiss was imbricated and attenuated between Rand Schist and hornblende-biotite granodiorite. Thrusting postdated metamorphism and deformation of the lower two plates in separate environments. A post-kinematic stock, the Late Cretaceous Randsburg Granodiorite, intrudes deep levels of the complex and contains xenoliths of both Rand Schist and mylonitized Johannesburg? gneiss. Minimum shortening implied by the map patterns is 20 kilometers.

Some low angle faults of the Rand Thrust Complex formed or were reactivated between Late Cretaceous and Early Miocene time. South-southwest directed mylonites derived from Johannesburg Gneiss are commonly overprinted by less penetrative north-northeast vergent structures. Available kinematic information at shallower structural levels indicates that late disturbance(s) culminated in northward transport of the uppermost plate. Persistence of brittle fabrics along certain structural horizons suggests a possible association of late movement(s) with regionally known detachment faults. The four plates were juxtaposed and significant intraplate movements had ceased prior to Early Miocene emplacement of rhyolite porphyry dikes.

In the Magdalena region of north central Sonora, components of a pre-Middle Cretaceous stratigraphy are used as strain markers in tracking the evolution of a long lived orogenic belt. Important elements of the tectonic history include: (1) Compression during the Late Cretaceous and Early Tertiary, accompanied by plutonism, metamorphism, and ductile strain at depth, and thrust driven? syntectonic sedimentation at the surface. (2) Middle Tertiary transition to crustal extension, initially recorded by intrusion of leucogranites, inflation of the previously shortened middle and upper crustal section, and surface volcanism. (3) Gravity induced development of a normal sense ductile shear zone at mid crustal levels, with eventual detachment and southwestward displacement of the upper crustal stratigraphy by Early Miocene time.

Elucidation of the metamorphic core complex evolution just described was facilitated by fortuitous preservation of a unique assemblage of rocks and structures. The "type" stratigraphy utilized for regional correlation and strain analysis includes a Jurassic volcanic arc assemblage overlain by an Upper Jurassic-Lower Cretaceous quartz pebble conglomerate, in turn overlain by marine strata with fossiliferous Aptian-Albian limestones. The Jurassic strata, comprised of (a) rhyolite porphyries interstratified with quartz arenites, (b) rhyolite cobble conglomerate, and (c) intrusive granite porphyries, are known to rest on Precambrian basement north and east of the study area. The quartz pebble conglomerate is correlated with the Glance Conglomerate of southeastern Arizona and northeastern Sonora. The marine sequence represents part of an isolated arm? of the Bisbee Basin.

Crosscutting structural relationships between the pre-Middle Cretaceous supracrustal section, younger plutons, and deformational fabrics allow the tectonic sequence to be determined. Earliest phases of a Late Cretaceous-Early Tertiary orogeny are marked by emplacement of the 78 ± 3 Ma Guacomea Granodiorite (U/Pb zircon, Anderson et al., 1980) as a sill into deep levels of the layered Jurassic series. Subsequent regional metamorphism and ductile strain is recorded by a penetrative schistosity and lineation, and east-west trending folds. These fabrics are intruded by post-kinematic Early Tertiary? two mica granites. At shallower crustal levels, the orogeny is represented by north directed thrust faulting, formation of a large intermontane basin, and development of a pronounced unconformity. A second important phase of ductile strain followed Middle Tertiary? emplacement of leucogranites as sills and northwest trending dikes into intermediate levels of the deformed section (surficial volcanism was also active during this transitional period to regional extension). Gravitational instabilities resulting from crustal swelling via intrusion and thermal expansion led to development of a ductile shear zone within the stratigraphic horizon occupied by a laterally extensive leucogranite sill. With continued extension, upper crustal brittle normal faults (detachment faults) enhanced the uplift and tectonic denudation of this mylonite zone, ultimately resulting in southwestward displacement of the upper crustal stratigraphy.

Strains associated with the two ductile deformation events have been successfully partitioned through a multifaceted analysis. R_f/Ø measurements on various markers from the "type" stratigraphy allow a gradient representing cumulative strain since Middle Cretaceous time to be determined. From this gradient, noncoaxial strains accrued since emplacement of the leucogranites may be removed. Irrotational components of the postleucogranite strain are measured from quartz grain shapes in deformed granites; rotational components (shear strains) are determined from S-C fabrics and from restoration of rotated dike and vein networks. Structural observations and strain data are compatable with a deformation path of: (1) coaxial strain (pure shear?), followed by (2) injection of leucogranites as dikes (perpendicular to the minimum principle stress) and sills (parallel to the minimum principle stress), then (3) southwest directed simple shear. Modeling the late strain gradient as a simple shear zone permits a minimum displacement of 10 kilometers on the Magdalena mylonite zone/detachment fault system. Removal of the Middle Tertiary noncoaxial strains yields a residual (or pre-existing) strain gradient representative of the Late Cretaceous-Early Tertiary deformation. Several partially destrained cross sections, restored to the time of leucogranite emplacement, illustrate the idea that the upper plate of the core complex bas been detached from a region of significant topographic relief. 50% to 100% bulk extension across a 50 kilometer wide corridor is demonstrated.

Late Cenozoic tectonics of the Magdalena region are dominated by Basin and Range style faulting. Northeast and north-northwest trending high angle normal faults have interacted to extend the crust in an east-west direction. Net extension for this period is minor (10% to 15%) in comparison to the Middle Tertiary detachment related extensional episode.

Oxygen, carbon and hydrogen isotope studies of contact metamorphism

The O¹⁸/O¹⁶, C¹³/C¹², and D/H ratios have been determined for rocks and coexisting minerals from several granitic plutons and their contact metamorphic aureoles in northern Nevada, eastern California, central Colorado, and Texas, with emphasis on oxygen isotopes. A consistent order of O¹⁸/O¹⁶, C¹³/C¹², and D/H enrichment in coexisting minerals, and a correlation between isotopic fractionations among coexisting mineral pairs are in general observed, suggesting that mineral assemblages tend to approach isotopic equilibrium during contact metamorphism. In certain cases, a correlation is observed between oxygen isotopic fractionations of a mineral pair and sample distance from intrusive contacts. Isotopic temperatures generally show good agreement with heat flow considerations. Based on the experimentally determined quartz-muscovite O¹⁸/O¹⁶ fractionation calibration curve, temperatures are estimated to be 525 to 625°C at the contacts of the granitic stocks studied.

Small-scale oxygen isotope exchange effects between intrusive and country rock are observed over distances of 0.5 to 3 feet on both sides of the contacts; the isotopic gradients are typically 2 to 3 per mil per foot. The degree of oxygen isotopic exchange is essentially identical for different coexisting minerals. This presumably occurred through a diffusion-controlled recrystallization process. The size of the oxygen isotope equilibrium systems in the small-scale exchanged zones vary from about 1.5 cm to 30 cm. A xenolith and a re-entrant of country rock projecting into on intrusive hove both undergone much more extensive isotopic exchange (to hundreds of feet); they also show abnormally high isotopic temperatures. The marginal portions of most plutons have unusually high O¹⁸/O¹⁶ ratios compared to "normal" igneous rocks, presumably due to large-scale isotopic exchange with meta-sedimentary country rocks when the igneous rocks were essentially in a molten state. The isotopic data suggest that outward horizontal movement of H₂O into the contact metamorphic aureoles is almost negligible, but upward movement of H₂O may be important. Also, direct influx and absorption of water from the country rock may be significant in certain intrusive stocks.

Except in the exchanged zones, the O¹⁸/O¹⁶ ratios of pelitic rocks do not change appreciably during contact metamorphism, even in the cordierite and sillimanite grades; this is in contrast to regional metamorphic rocks which commonly decrease in O¹⁸ with increasing grade. Low O¹⁸/O¹⁶ and C¹³/C¹² ratios of the contact metamorphic marbles generally correlate well with the presence of calc-silicate minerals, indicating that the CO₂ liberated during metamorphic decarbonation reactions is enriched in both O¹⁸ and C¹³ relative to the carbonates.

The D/H ratios of biotites in the contact metamorphic rocks and their associated intrusions show a geographic correlation that is similar to that shown by the D/H ratios of meteoric surface waters, perhaps indicating that meteoric waters were present in the rocks during crystallization of the biotites.

Extraction of CP Properties of the H(125) Boson Discovered in Proton-Proton Collisions at sqrt(s) = 7 and 8 TeV with the CMS Detector at the LHC

In this thesis we build a novel analysis framework to perform the direct extraction of all possible effective Higgs boson couplings to the neutral electroweak gauge bosons in the H → ZZ^(*) → 4l channel also referred to as the golden channel. We use analytic expressions of the full decay differential cross sections for the H → VV' → 4l process, and the dominant irreducible standard model qq ̄ → 4l background where 4l = 2e2μ,4e,4μ. Detector effects are included through an explicit convolution of these analytic expressions with transfer functions that model the detector responses as well as acceptance and efficiency effects. Using the full set of decay observables, we construct an unbinned 8-dimensional detector level likelihood function which is con- tinuous in the effective couplings, and includes systematics. All potential anomalous couplings of HVV' where V = Z,γ are considered, allowing for general CP even/odd admixtures and any possible phases. We measure the CP-odd mixing between the tree-level HZZ coupling and higher order CP-odd couplings to be compatible with zero, and in the range [−0.40, 0.43], and the mixing between HZZ tree-level coupling and higher order CP -even coupling to be in the ranges [−0.66, −0.57] ∪ [−0.15, 1.00]; namely compatible with a standard model Higgs. We discuss the expected precision in determining the various HVV' couplings in future LHC runs. A powerful and at first glance surprising prediction of the analysis is that with 100-400 fb^-1, the golden channel will be able to start probing the couplings of the Higgs boson to diphotons in the 4l channel. We discuss the implications and further optimization of the methods for the next LHC runs.

Oxygen isotope ratios in coexisting minerals of regionally metamorphosed rocks

The O¹⁸/O¹⁶ ratios of coexisting minerals from a number of regionally metamorphosed rocks have been measured, using a bromine pentafluoride extraction-technique. Listed in order of their increasing tendency to concentrate O¹⁸, the minerals analyzed are magnetite, ilmenite, chlorite, biotite, garnet, hornblende, kyanite, muscovite, feldspar, and quartz. The only anomalous sequence detected occurs in a xenolith of schist, in which quartz, muscovite, biotite, and ilmenite, but not garnet, have undergone isotopic exchange with surrounding trondjemite.

With few exceptions, quartz-magnetite and quartz-ilmenite fractionations decrease with increasing metamorphic grade determined by mineral paragenesis and spatial distribution. This consistency does not apply to quartz-magnetite and quartz-ilmenite fractionations obtained from rocks in which petrographic evidence of retrogradation is present.

Whereas measured isotopic fractionations among quartz, garnet, ilmenite, and magnetite are approximately related to metamorphic grade, fractionations between these minerals and biotite or muscovite show poor correlation with grade. Variations in muscovite-biotite fractionations are relatively small. These observations are interpreted to mean that muscovite and biotite are affected by retrograde re-equilibration to a greater extent than the anhydrous minerals analyzed.

Measured quartz-ilmenite fractionations range from 12 permil in the biotite zone of central Vermont to 6.5 permil in the sillimanite-orthoclase zone of southeastern Connecticut. Analyses of natural assemblages from the kyanite and sillimanite zones suggest that equilibrium quartz-ilmenite fractionations are approximately 8 percent smaller than corresponding quartz-magnetite fractionations. Employing the quartz-magnetite geothermometer calibrated by O'Neil and Clayton (1964), a temperature of 560°C was obtained for kyanite-bearing schists from Addison County, Vermont. Extending the calibration to quartz-ilmenite fractionations, a temperature of 600°C was obtained for kyanite-schists from Shoshone County, Idaho. At these temperatures kyanite is stable only at pressures exceeding 11 kbars (Bell, 1963), corresponding to lithostatic loads of over 40 km.

Report of an investigation of a plan of elimination of grade crossings on the A.T. & S.F. Ry. in the city of Pasadena, California

The problem of the Atchison, Topeka, and Santa Fe railroad in Pasadena is a very dynamic one, as is readily recognized by engineers, city officials, and laymen. The route of the railroad was first laid out in the eighties and because of certain liberal concessions granted by the City of Pasadena, the right-of-way was located through Pasadena, despite the fact that the grade coming into the city either from Los Angeles or San Bernardino was enormous. Some years later, other transcontinental routes of the Santa Fe out of Los Angles were sought, and a right-of-way was obtained by way of Fullerton and Riverside to San Bernardino, where this route joins the one from Los Angeles through Pasadena. This route, however, is ten miles longer than the one through Pasadena, which means a considerable loss of time in a short diversion of approximately only sixty miles in length.

Photoproduction of ETA mesons from hydrogen at photon energies between 0.8 and 1.45 GeV

We measured the differential cross section of the process γp → pƞ at the 1.5 GeV Caltech electron synchrotron, at photon energies from 0.8 to 1.45 GeV, at various angles between 45° and 100° in the center of mass. A counter-spark chamber array was used to determine the kinematics of all particles in the final state of the partial mode γp → pƞ (ƞ → 2γ). Analysis of 40,000 pictures yielded 6,000 events above a background which varied with energy from 5% to 30% of foreground. The cross section shows an energy dependence confirming earlier results up to 1000 MeV, but with improved statistics; it then remains roughly constant (at 50° C.M.), to 1.45 GeV. The data show a small angular variation, within the limited range covered, at energies between 1000 and 1100 MeV.