On the Informational Role of Term Structure in the U.S. Monetary Policy Rule

This paper uses a structural approach based on the indirect inference principle to estimate a standard version of the new Keynesian monetary (NKM) model augmented with term structure using both revised and real-time data. The estimation results show that the term spread and policy inertia are both important determinants of the U.S. estimated monetary policy rule whereas the persistence of shocks plays a small but significant role when revised and real-time data of output and inflation are both considered. More importantly, the relative importance of term spread and persistent shocks in the policy rule and the shock transmission mechanism drastically change when it is taken into account that real-time data are not well behaved.

The Metabolic Core and Catalytic Switches Are Fundamental Elements in the Self-Regulation of the Systemic Metabolic Structure of Cells

19 p.

A stationary visual census technique for quantitatively assessing community structure of coral reef fishes

A new method is described and evaluated for visually sampling reef fish community structure in environments with highly diverse and abundant reef fish populations. The method is based on censuses of reef fishes taken within a cylinder of 7.5 m radius by a diver at randomly selected, stationary points. The method provides quantitative data on frequency of occnrrence, fish length, abundance, and community composition, and is simple, fast, objective, and repeatable. Species are accumulated rapidly for listing purposes, and large numbers of samples are easily obtained for statistical treatment. The method provides an alternative to traditional visual sampling methods. Observations showed that there were no significant differences in total numbers of species or individuals censused when visibility ranged between 8 and 30 m. The reefs and habitats sampled were significant sources of variation in number of species and individuals censused, but the diver was not a significant influence. Community similarity indices were influenced significantly by the specific sampling site and the reef sampled, but were not significantly affected by the habitat or diver (PDF file contains 21 pages.)

Defects structure characterization of NiMnGa alloys by PALS

16th International Conference on Positron Annihilation (ICPA) Univ Bristol, H H Wills Phys Lab, Bristol, ENGLAND AUG 19-24, 2012 Edited by:Alam, A; Coleman, P; Dugdale, S; Roussenova, M

Phosphorylation of the carboxy-terminal domain of histone H1: effects on secondary structure and DNA condensation

Linker histone H1 plays an important role in chromatin folding. Phosphorylation by cyclin-dependent kinases is the main post-translational modification of histone H1. We studied the effects of phosphorylation on the secondary structure of the DNA-bound H1 carboxy-terminal domain (CTD), which contains most of the phosphorylation sites of the molecule. The effects of phosphorylation on the secondary structure of the DNA-bound CTD were site-specific and depended on the number of phosphate groups. Full phosphorylation significantly increased the proportion of -structure and decreased that of -helix. Partial phosphorylation increased the amount of undefined structure and decreased that of -helix without a significant increase in -structure. Phosphorylation had a moderate effect on the affinity of the CTD for the DNA, which was proportional to the number of phosphate groups. Partial phosphorylation drastically reduced the aggregation of DNA fragments by the CTD, but full phosphorylation restored to a large extent the aggregation capacity of the unphosphorylated domain. These results support the involvement of H1 hyperphosphorylation in metaphase chromatin condensation and of H1 partial phosphorylation in interphase chromatin relaxation. More generally, our results suggest that the effects of phosphorylation are mediated by specific structural changes and are not simply a consequence of the net charge.

Nonlinear Fluid Damping In Structure-Wake Oscillators In Modeling Vortex-Induced Vibrations

A Nonlinear Fluid Damping (NFD) in the form of the square-velocity is applied in the response analysis of Vortex-induced Vibrations (VIV). Its nonlinear hydrodynamic effects oil the coupled wake and structure oscillators are investigated. A comparison between the coupled systems with the linear and nonlinear fluid dampings and experiments shows that the NFD model can well describe response characteristics, such as the amplification of body displacement at lock-in and frequency lock-ill, both at high and low mass ratios. Particularly, the predicted peak amplitude of the body in the Griffin plot is ill good agreement with experimental data and empirical equation, indicating the significant effect of the NFD on the structure motion.

TUNPOP: A simulation of the dynamics and structure of the yellowfin tuna stock and surface fishery of the Eastern Pacific Ocean

ENGLISH: Three distinct versions of TUNP0P, an age-structured computer simulation model of the eastern Pacific yellowfin tuna, Thunnus albacores, stock and surface tuna fishery, are used to reveal mechanisms which appear to have a significant effect on the fishery dynamics. Real data on this fishery are used to make deductions on the distribution of the fish and to show how that distribution might influence events in the fishery. The most important result of the paper is that the concept of the eastern Pacific yellowfin tuna stock as a homogeneous unit is inadequate to represent the recent history of the fishery. Inferences are made on the size and distribution of the underlying stock as well as its potential yield to the surface fishery as a result of alterations in the level and distribution of the effort. SPANISH: Se han empleado tres versiones diferentes de TUNP0P, un modelo de simulación de la computadora (basado en la estructura de la edad) de la población y la pesca epipelágica del atún aleta amarilla, Tbunnus albacares, del Pacífico oriental, para revelar los mecanismos que parecen tener un efecto importante en la dinámica pesquera. Se emplean los datos verdaderos de esta pesca para hacer deducciones sobre la distribución de los peces y para mostrar cómo puede influir esta distribución en los eventos de pesca. La conclusión más importante de este estudio es que el concepto de que la población del aleta amarilla del Pacífico oriental es una unidad homogénea, es inadecuado para representar la historia reciente de pesca. Se teoriza sobre la talla y distribución de la población subyacente como también sobre su producción potencial en la pesca epipelágica al cambiar el nivel y distribución del esfuerzo.

Crustal structure in Southern California from array data

Crustal structure in Southern California is investigated using travel times from over 200 stations and thousands of local earthquakes. The data are divided into two sets of first arrivals representing a two-layer crust. The Pg arrivals have paths that refract at depths near 10 km and the Pn arrivals refract along the Moho discontinuity. These data are used to find lateral and azimuthal refractor velocity variations and to determine refractor topography.

In Chapter 2 the Pn raypaths are modeled using linear inverse theory. This enables statistical verification that static delays, lateral slowness variations and anisotropy are all significant parameters. However, because of the inherent size limitations of inverse theory, the full array data set could not be processed and the possible resolution was limited. The tomographic backprojection algorithm developed for Chapters 3 and 4 avoids these size problems. This algorithm allows us to process the data sequentially and to iteratively refine the solution. The variance and resolution for tomography are determined empirically using synthetic structures.

The Pg results spectacularly image the San Andreas Fault, the Garlock Fault and the San Jacinto Fault. The Mojave has slower velocities near 6.0 km/s while the Peninsular Ranges have higher velocities of over 6.5 km/s. The San Jacinto block has velocities only slightly above the Mojave velocities. It may have overthrust Mojave rocks. Surprisingly, the Transverse Ranges are not apparent at Pg depths. The batholiths in these mountains are possibly only surficial.

Pn velocities are fast in the Mojave, slow in Southern California Peninsular Ranges and slow north of the Garlock Fault. Pn anisotropy of 2% with a NWW fast direction exists in Southern California. A region of thin crust (22 km) centers around the Colorado River where the crust bas undergone basin and range type extension. Station delays see the Ventura and Los Angeles Basins but not the Salton Trough, where high velocity rocks underlie the sediments. The Transverse Ranges have a root in their eastern half but not in their western half. The Southern Coast Ranges also have a thickened crust but the Peninsular Ranges have no major root.

Functional genomic studies of the structure and regulation of eukaryotic transcriptomes

The main focus of this thesis is the use of high-throughput sequencing technologies in functional genomics (in particular in the form of ChIP-seq, chromatin immunoprecipitation coupled with sequencing, and RNA-seq) and the study of the structure and regulation of transcriptomes. Some parts of it are of a more methodological nature while others describe the application of these functional genomic tools to address various biological problems. A significant part of the research presented here was conducted as part of the ENCODE (ENCyclopedia Of DNA Elements) Project.

The first part of the thesis focuses on the structure and diversity of the human transcriptome. Chapter 1 contains an analysis of the diversity of the human polyadenylated transcriptome based on RNA-seq data generated for the ENCODE Project. Chapter 2 presents a simulation-based examination of the performance of some of the most popular computational tools used to assemble and quantify transcriptomes. Chapter 3 includes a study of variation in gene expression, alternative splicing and allelic expression bias on the single-cell level and on a genome-wide scale in human lymphoblastoid cells; it also brings forward a number of critical to the practice of single-cell RNA-seq measurements methodological considerations.

The second part presents several studies applying functional genomic tools to the study of the regulatory biology of organellar genomes, primarily in mammals but also in plants. Chapter 5 contains an analysis of the occupancy of the human mitochondrial genome by TFAM, an important structural and regulatory protein in mitochondria, using ChIP-seq. In Chapter 6, the mitochondrial DNA occupancy of the TFB2M transcriptional regulator, the MTERF termination factor, and the mitochondrial RNA and DNA polymerases is characterized. Chapter 7 consists of an investigation into the curious phenomenon of the physical association of nuclear transcription factors with mitochondrial DNA, based on the diverse collections of transcription factor ChIP-seq datasets generated by the ENCODE, mouseENCODE and modENCODE consortia. In Chapter 8 this line of research is further extended to existing publicly available ChIP-seq datasets in plants and their mitochondrial and plastid genomes.

The third part is dedicated to the analytical and experimental practice of ChIP-seq. As part of the ENCODE Project, a set of metrics for assessing the quality of ChIP-seq experiments was developed, and the results of this activity are presented in Chapter 9. These metrics were later used to carry out a global analysis of ChIP-seq quality in the published literature (Chapter 10). In Chapter 11, the development and initial application of an automated robotic ChIP-seq (in which these metrics also played a major role) is presented.

The fourth part presents the results of some additional projects the author has been involved in, including the study of the role of the Piwi protein in the transcriptional regulation of transposon expression in Drosophila (Chapter 12), and the use of single-cell RNA-seq to characterize the heterogeneity of gene expression during cellular reprogramming (Chapter 13).

The last part of the thesis provides a review of the results of the ENCODE Project and the interpretation of the complexity of the biochemical activity exhibited by mammalian genomes that they have revealed (Chapters 15 and 16), an overview of the expected in the near future technical developments and their impact on the field of functional genomics (Chapter 14), and a discussion of some so far insufficiently explored research areas, the future study of which will, in the opinion of the author, provide deep insights into many fundamental but not yet completely answered questions about the transcriptional biology of eukaryotes and its regulation.

Experimental and theoretical developments in extended x-ray absorption fine structure (EXAFS) spectroscopy

To obtain accurate information from a structural tool it is necessary to have an understanding of the physical principles which govern the interaction between the probe and the sample under investigation. In this thesis a detailed study of the physical basis for Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy is presented. A single scattering formalism of EXAFS is introduced which allows a rigorous treatment of the central atom potential. A final state interaction formalism of EXAFS is also discussed. Multiple scattering processes are shown to be significant for systems of certain geometries. The standard single scattering EXAFS analysis produces erroneous results if the data contain a large multiple scattering contribution. The effect of thermal vibrations on such multiple scattering paths is also discussed. From symmetry considerations it is shown that only certain normal modes contribute to the Debye-Waller factor for a particular scattering path. Furthermore, changes in the scattering angles induced by thermal vibrations produces additional EXAFS components called modification factors. These factors are shown to be small for most systems.

A study of the physical basis for the determination of structural information from EXAFS data is also presented. An objective method of determining the background absorption and the threshold energy is discussed and involves Gaussian functions. In addition, a scheme to determine the nature of the scattering atom in EXAFS experiments is introduced. This scheme is based on the fact that the phase intercept is a measure of the type of scattering atom. A method to determine bond distances is also discussed and does not require the use of model compounds or calculated phase shifts. The physical basis for this method is the absence of a linear term in the scattering phases. Therefore, it is possible to separate these phases from the linear term containing the distance information in the total phase.

Structure-, stereochemistry-, and metal-regulated DNA binding/cleaving molecules

In the cell, the binding of proteins to specific sequences of double helical DNA is essential for controlling the processes of protein synthesis (at the level of DNA transcription) and cell proliferation (at the level of DNA replication). In the laboratory, the sequence-specific DNA binding/cleaving properties of restriction endonuclease enzymes (secreted by microorganisms to protect them from foreign DNA molecules) have helped to fuel a revolution in molecular biology. The strength and specificity of a protein:DNA interaction depend upon structural features inherent to the protein and DNA sequences, but it is now appreciated that these features (and therefore protein:DNA complexation) may be altered (regulated) by other protein:DNA complexes, or by environmental factors such as temperature or the presence of specific organic molecules or inorganic ions. It is also now appreciated that molecules much smaller than proteins (including antibiotics of molecular weight less than 2000 and oligonucleotides) can bind to double-helical DNA in sequence-specific fashion. Elucidation of structural motifs and microscopic interactions responsible for the specific molecular recognition of DNA leads to greater understanding of natural processes and provides a basis for the design of novel sequence-specific DNA binding molecules. This thesis describes the synthesis and DNA binding/cleaving characteristics of molecules designed to probe structural, stereochemical, and environmental factors that regulate sequence-specific DNA recognition.

Chapter One introduces the DNA minor groove binding antibiotics Netropsin and Distamycin A, which are di- and tri(N-methylpyrrolecarboxamide) peptides, respectively. The method of DNA affinity cleaving, which has been employed to determine DNA binding properties of designed synthetic molecules is described. The design and synthesis of a series of Netropsin dimers linked in tail-to-tail fashion (by oxalic, malonic, succinic, or fumaric acid), or in head-to-tail fashion (by glycine, β-alanine, and γ-aminobutanoic acid (Gaba)) are presented. These Bis(Netropsin)s were appended with the iron-chelating functionality EDTA in order to make use of the technique of DNA affinity cleaving. Bis(Netropsin)-EDTA compounds are analogs of penta(N-methylpyrrolecarboxamide)-EDTA (P5E), which may be considered a head-to-tail Netropsin dimer linked by Nmethylpyrrolecarboxamide. Low- and high-resolution analysis of pBR322 DNA affinity cleaving by the iron complexes of these molecules indicated that small changes in the length and nature of the linker had significant effects on DNA binding/cleaving efficiency (a measure of DNA binding affinity). DNA binding/cleaving efficiency was found to decrease with changes in the linker in the order β-alanine > succinamide > fumaramide > N-methylpyrrolecarboxamide > malonamide >glycine, γ-aminobutanamide > oxalamide. In general, the Bis(Netropsin)-EDTA:Fe compounds retained the specificity for seven contiguous A:T base pairs characteristic of P5E:Fe binding. However, Bis(Netropsin)Oxalamide- EDTA:Fe exhibited decreased specificity for A:T base pairs, and Bis(Netropsin)-Gaba-EDT A:Fe exhibited some DNA binding sites of less than seven base pairs. Bis(Netropsin)s linked with diacids have C₂-symmmetrical DNA binding subunits and exhibited little DNA binding orientation preference. Bis(Netropsin)s linked with amino acids lack C₂-symmetrical DNA binding subunits and exhibited higher orientation preferences. A model for the high DNA binding orientation preferences observed with head-to-tail DNA minor groove binding molecules is presented.

Chapter Two describes the design, synthesis, and DNA binding properties of a series of chiral molecules: Bis(Netropsin)-EDTA compounds with linkers derived from (R,R)-, (S,S)-, and (RS,SR)-tartaric acids, (R,R)-, (S,S)-, and (RS,SR)-tartaric acid acetonides, (R)- and (S)-malic acids, N ,N-dimethylaminoaspartic acid, and (R)- and (S)-alanine, as well as three constitutional isomers in which an N-methylpyrrolecarboxamide (P1) subunit and a tri(N-methylpyrrolecarboxamide)-EDTA (P3-EDTA) subunit were linked by succinic acid, (R ,R)-, and (S ,S)-tartaric acids. DNA binding/cleaving efficiencies among this series of molecules and the Bis(Netropsin)s described in Chapter One were found to decrease with changes in the linker in the order β-alanine > succinamide > P1-succinamide-P3 > fumaramide > (S)-malicamide > N-methylpyrrolecarboxamide > (R)-malicamide > malonamide > N ,N-dimethylaminoaspanamide > glycine = Gaba = (S,S)-tartaramide = P1-(S,S)-tanaramide-P3 > oxalamide > (RS,SR)-tartaramide = P1- (R,R)-tanaramide-P3 > (R,R)-tartaramide (no sequence-specific DNA binding was detected for Bis(Netropsin)s linked by (R)- or (S)-alanine or by tartaric acid acetonides). The chiral molecules retained DNA binding specificity for seven contiguous A:T base pairs. From the DNA affinity cleaving data it could be determined that: 1) Addition of one or two substituents to the linker of Bis(Netropsin)-Succinamide resulted in stepwise decreases in DNA binding affinity; 2) molecules with single hydroxyl substituents bound DNA more strongly than molecules with single dimethylamino substituents; 3) hydroxyl-substituted molecules of (S) configuration bound more strongly to DNA than molecules of (R) configuration. This stereochemical regulation of DNA binding is proposed to arise from the inherent right-handed twist of (S)-enantiomeric Bis(Netropsin)s versus the inherent lefthanded twist of (R)-enantiomeric Bis(Netropsin)s, which makes the (S)-enantiomers more complementary to the right-handed twist of B form DNA.

Chapter Three describes the design and synthesis of molecules for the study of metalloregulated DNA binding phenomena. Among a series of Bis(Netropsin)-EDTA compounds linked by homologous tethers bearing four, five, or six oxygen atoms, the Bis(Netropsin) linked by a pentaether tether exhibited strongly enhanced DNA binding/cleaving in the presence of strontium or barium cations. The observed metallospecificity was consistent with the known affinities of metal cations for the cyclic hexaether 18-crown-6 in water. High-resolution DNA affinity cleaving analysis indicated that DNA binding by this molecule in the presence of strontium or barium was not only stronger but of different sequence-specificity than the (weak) binding observed in the absence of metal cations. The metalloregulated binding sites were consistent with A:T binding by the Netropsin subunits and G:C binding by a strontium or barium:pentaether complex. A model for the observed positive metalloregulation and novel sequence-specificity is presented. The effects of 44 different cations on DNA affinity cleaving by P5E:Fe were examined. A series of Bis(Netropsin)-EDTA compounds linked by tethers bearing two, three, four, or five amino groups was also synthesized. These molecules exhibited strong and specific binding to A:T rich regions of DNA. It was found that the iron complexes of these molecules bound and cleaved DNA most efficiently at pH 6.0-6.5, while P5E:Fe bound and cleaved most efficiently at pH 7.5-8.0. Incubating the Bis(Netropsin) Polyamine-EDTA:Fe molecules with K₂PdCl₄ abolished their DNA binding/cleaving activity. It is proposed that the observed negative metalloregulation arises from kinetically inert Bis(Netropsin) Polyamine:Pd(II) complexes or aggregates, which are sterically unsuitable for DNA complexation. Finally, attempts to produce a synthetic metalloregulated DNA binding protein are described. For this study, five derivatives of a synthetic 52 amino acid residue DNA binding/cleaving protein were produced. The synthetic mutant proteins carried a novel pentaether ionophoric amino acid residue at different positions within the primary sequence. The proteins did not exhibit significant DNA binding/cleaving activity, but they served to illustrate the potential for introducing novel amino acid residues within DNA binding protein sequences, and for the development of the tricyclohexyl ester of EDTA as a superior reagent for the introduction of EDT A into synthetic proteins.

Chapter Four describes the discovery and characterization of a new DNA binding/cleaving agent, [SalenMn(III)]OAc. This metal complex produces single- and double-strand cleavage of DNA, with specificity for A:T rich regions, in the presence of oxygen atom donors such as iodosyl benzene, hydrogen peroxide, or peracids. Maximal cleavage by [SalenMn(III)]OAc was produced at pH 6-7. A comparison of DNA singleand double-strand cleavage by [SalenMn(III)]⁺ and other small molecules (Methidiumpropyl-EDTA:Fe, Distamycin-EDTA:Fe, Neocarzinostatin, Bleomycin:Fe) is presented. It was found that DNA cleavage by [SalenMn(III)]⁺ did not require the presence of dioxygen, and that base treatment of DNA subsequent to cleavage by [SalenMn(III)]⁺ afforded greater cleavage and alterations in the cleavage patterns. Analysis of DNA products formed upon DNA cleavage by [SalenMn(III)] indicated that cleavage was due to oxidation of the sugar-phosphate backbone of DNA. Several mechanisms consistent with the observed products and reaction requirements are discussed.

Chapter Five describes progress on some additional studies. In one study, the DNA binding/cleaving specificities of Distamycin-EDTA derivatives bearing pyrrole N-isopropyl substituents were found to be the same as those of derivatives bearing pyrrole N-methyl substituents. In a second study, the design of and synthetic progress towards a series of nucleopeptide activators of transcription are presented. Five synthetic plasmids designed to test for activation of in vitro run-off transcription by DNA triple helix-forming oligonucleotides or nucleopeptides are described.

Chapter Six contains the experimental documentation of the thesis work.

I. The crystal structure of a new dimer of triphenylfluorocyclobutadiene. II. A low temperature refinement of the cyanuric triazide structure

I. THE CRYSTAL STRUCTURE OF A NEW DIMER OF TRIPHENYLFLUOROCYCLOBUTADIENE

The crystal structure of thermal isomer of the “head-to-head” dimer of triphenylfluorocyclobutadiene was determined by the direct method. The Σ₂ relationship involving the low angle reflections with the largest E’s were found and solved for the signs by the symbolic method of Zachariasen. The structure was seen in the electron density map and the E-map, and was refined antisotropically by the method of least squares. The residual R was 0.065.

The structure is a gem-difluorohexaphenyldihydropentalene. All of the phenyl groups are planar as it is the cyclopentadiene ring of the dihydropentalene skeleton. Overcrowding at the position of the flourines causes some deviations from the normal bond angles in the cyclopentene ring.

The list of observed and calculated structure factors on pages 32-34 will not be legible on the microfilm. Photographic copies may be obtained from the California Institute of Technology.

II. A LOW TEMPERATURE REFINEMENT OF THE CYANURIC TRIAZIDE STRUCTURE

The structure of cyanuric triazide was refined anisotropically by the method of least squares. Three-dimensional intensity data, which has been collected photographically with MoK_α radiation at -110˚C, were used in the refinement. The residual R was reduced to 0.081.

The structure is completely planar, and there is no significant bond alternation in the cyanuric ring. The packing of the molecules causes the azide groups to deviate from linearity by 8 degrees.

Regional variations in upper mantle structure beneath North America

Several types of seismological data, including surface wave group and phase velocities, travel times from large explosions, and teleseismic travel time anomalies, have indicated that there are significant regional variations in the upper few hundred kilometers of the mantle beneath continental areas. Body wave travel times and amplitudes from large chemical and nuclear explosions are used in this study to delineate the details of these variations beneath North America.

As a preliminary step in this study, theoretical P wave travel times, apparent velocities, and amplitudes have been calculated for a number of proposed upper mantle models, those of Gutenberg, Jeffreys, Lehman, and Lukk and Nersesov. These quantities have been calculated for both P and S waves for model CIT11GB, which is derived from surface wave dispersion data. First arrival times for all the models except that of Lukk and Nersesov are in close agreement, but the travel time curves for later arrivals are both qualitatively and quantitatively very different. For model CIT11GB, there are two large, overlapping regions of triplication of the travel time curve, produced by regions of rapid velocity increase near depths of 400 and 600 km. Throughout the distance range from 10 to 40 degrees, the later arrivals produced by these discontinuities have larger amplitudes than the first arrivals. The amplitudes of body waves, in fact, are extremely sensitive to small variations in the velocity structure, and provide a powerful tool for studying structural details.

Most of eastern North America, including the Canadian Shield has a Pn velocity of about 8.1 km/sec, with a nearly abrupt increase in compressional velocity by ~ 0.3 km/sec near at a depth varying regionally between 60 and 90 km. Variations in the structure of this part of the mantle are significant even within the Canadian Shield. The low-velocity zone is a minor feature in eastern North America and is subject to pronounced regional variations. It is 30 to 50 km thick, and occurs somewhere in the depth range from 80 to 160 km. The velocity decrease is less than 0.2 km/sec.

Consideration of the absolute amplitudes indicates that the attenuation due to anelasticity is negligible for 2 hz waves in the upper 200 km along the southeastern and southwestern margins of the Canadian Shield. For compressional waves the average Q for this region is > 3000. The amplitudes also indicate that the velocity gradient is at least 2 x 10^-3 both above and below the low-velocity zone, implying that the temperature gradient is < 4.8°C/km if the regions are chemically homogeneous.

In western North America, the low-velocity zone is a pronounced feature, extending to the base of the crust and having minimum velocities of 7.7 to 7.8 km/sec. Beneath the Colorado Plateau and Southern Rocky Mountains provinces, there is a rapid velocity increase of about 0.3 km/sec, similar to that observed in eastern North America, but near a depth of 100 km.

Complicated travel time curves observed on profiles with stations in both eastern and western North America can be explained in detail by a model taking into account the lateral variations in the structure of the low-velocity zone. These variations involve primarily the velocity within the zone and the depth to the top of the zone; the depth to the bottom is, for both regions, between 140 and 160 km.

The depth to the transition zone near 400 km also varies regionally, by about 30-40 km. These differences imply variations of 250 °C in the temperature or 6 % in the iron content of the mantle, if the phase transformation of olivine to the spinel structure is assumed responsible. The structural variations at this depth are not correlated with those at shallower depths, and follow no obvious simple pattern.

The computer programs used in this study are described in the Appendices. The program TTINV (Appendix IV) fits spherically symmetric earth models to observed travel time data. The method, described in Appendix III, resembles conventional least-square fitting, using partial derivatives of the travel time with respect to the model parameters to perturb an initial model. The usual ill-conditioned nature of least-squares techniques is avoided by a technique which minimizes both the travel time residuals and the model perturbations.

Spherically symmetric earth models, however, have been found inadequate to explain most of the observed travel times in this study. TVT4, a computer program that performs ray theory calculations for a laterally inhomogeneous earth model, is described in Appendix II. Appendix I gives a derivation of seismic ray theory for an arbitrarily inhomogeneous earth model.

Design for Survival: Sustainability for Planet and Structure

Buildings in Port Aransas encounter drastic environmental challenges: the potential catastrophic storm surge and high winds from a hurricane, and daily conditions hostile to buildings, vehicles, and even most vegetation. Its location a few hundred feet from the Gulf of Mexico and near-tropical latitude expose buildings to continuous high humidity, winds laden with scouring sand and corrosive salt, and extremes of temperature and ultraviolet light. Building construction methods are able to address each of these, but doing so in a sustainable way creates significant challenges. The new research building at the Marine Science Institute has been designed and is being constructed to meet the demand for both survivability and sustainability. It is tracking towards formal certification as a LEED Gold structure while being robust and resistant to the harsh coastal environment. The effects of a hurricane are mitigated by elevating buildings and providing a windproof envelope. Ground-level enclosures are designed to be sacrificial and non-structural so they can wash or blow away without imposing damage on the upper portions of the building, and only non-critical functions and equipment will be supported within them. Design features that integrate survivability with sustainability include: orientation of building axis; integral shading from direct summer sunlight; light wells; photovoltaic arrays; collection of rainwater and air conditioning condensate for use in landscape irrigation; reduced impervious cover; xeriscaping and indigenous plants; recycling of waste heat from air conditioning systems; roofing system that reflects light and heat; long life, low maintenance stainless steel, high-tensile vinyl, hard-anodized aluminum and hot-dipped galvanized mountings throughout; chloride-resistant concrete; reduced visual impact; recycling of construction materials.

I. The crystal structure of potassium bis(tricyanovinyl)amine. II. Nuclear magnetic resonance studies of alkali halide solutions. III. Elucidation of the intramolecular hydrogen bond in acetylacetone by the deuterium isotope effect on the chemical shift of the bridge hydrogen

Part I

Potassium bis-(tricyanovinyl) amine, K⁺N[C(CN)=C(CN)₂]₂^-, crystallizes in the monoclinic system with the space group Cc and lattice constants, a = 13.346 ± 0.003 Å, c = 8.992 ± 0.003 Å, B = 114.42 ± 0.02°, and Z = 4. Three dimensional intensity data were collected by layers perpendicular to b* and c* axes. The crystal structure was refined by the least squares method with anisotropic temperature factor to an R value of 0.064.

The average carbon-carbon and carbon-nitrogen bond distances in –C-CΞN are 1.441 ± 0.016 Å and 1.146 ± 0.014 Å respectively. The bis-(tricyanovinyl) amine anion is approximately planar. The coordination number of the potassium ion is eight with bond distances from 2.890 Å to 3.408 Å. The bond angle C-N-C of the amine nitrogen is 132.4 ± 1.9°. Among six cyano groups in the molecule, two of them are bent by what appear to be significant amounts (5.0° and 7.2°). The remaining four are linear within the experimental error. The bending can probably be explained by molecular packing forces in the crystals.

Part II

The nuclear magnetic resonance of ⁸¹Br and ¹²⁷I in aqueous solutions were studied. The cation-halide ion interactions were studied by studying the effect of the Li⁺, Na⁺, K⁺, Mg⁺⁺, Cs⁺ upon the line width of the halide ions. The solvent-halide ion interactions were studied by studying the effects of methanol, acetonitrile, and acetone upon the line width of ⁸¹Br and ¹²⁷I in the aqueous solutions. It was found that the viscosity plays a very important role upon the halide ions line width. There is no specific cation-halide ion interaction for those ions such as Mg⁺⁺, Di⁺, Na⁺, and K⁺, whereas the Cs⁺ - halide ion interaction is strong. The effect of organic solvents upon the halide ion line width in aqueous solutions is in the order acetone ˃ acetonitrile ˃ methanol. It is suggested that halide ions do form some stable complex with the solvent molecules and the reason Cs⁺ can replace one of the ligands in the solvent-halide ion complex.

Part III

An unusually large isotope effect on the bridge hydrogen chemical shift of the enol form of pentanedione-2, 4(acetylacetone) and 3-methylpentanedione-2, 4 has been observed. An attempt has been made to interpret this effect. It is suggested from the deuterium isotope effect studies, temperature dependence of the bridge hydrogen chemical shift studies, IR studies in the OH, OD, and C=O stretch regions, and the HMO calculations, that there may probably be two structures for the enol form of acetylacetone. The difference between these two structures arises mainly from the electronic structure of the π-system. The relative population of these two structures at various temperatures for normal acetylacetone and at room temperature for the deuterated acetylacetone were calculated.