Does the Term Spread play a role in the FED's reaction function? An Empirical Investigation

Using US data for the period 1967:5-2002:4, this paper empirically investigates the performance of a Fed’s reaction function (FRF) that (i) allows for the presence of switching regimes, (ii) considers the long-short term spread in addition to the typical variables, (iii) uses an alternative monthly indicator of general economic activity suggested by Stock and Watson (1999), and (iv) considers interest rate smoothing. The estimation results show the existence of three switching regimes, two characterized by low volatility and the remaining regime by high volatility. Moreover, the scale of the responses of the Federal funds rate to movements in the rate of inflation and the economic activity index depends on the regime. The estimation results also show robust empirical evidence that the importance of the term spread in the FRF has increased over the sample period and the FRF has been more stable during the term of office of Chairman Greenspan than in the pre-Greenspan period.

Innovative reaction systems for acetal (1,1 diethoxy butane) production from renewable sources

370 p.: il., graf.

Student Engagement in the School: Interpersonal and Inter-Center Differences

Traducido al castellano e inglés

An Improved molecular tool for distinguishing monoecious and dioedious Hydrilla

Two biotypes of hydrilla [Hydrilla verticillata(L.f.) Royle] occur in the United States, a dioecious type centered in the southeast and a monoecious type in the central Atlantic and northeastern states. Ecosystem managers need tools to distinguish the types as the ranges of each type expand and begin to overlap. A molecular tool using the randomly amplified polymorphic DNA (RAPD) procedure is available but its use is limited by a need for reference samples. We describe an alternative molecular tool which uses “universal primers” to sequence the trnL intron and trnL-F intergenic spacer of the chloroplast genome. This sequence yields three differences between the biotypes (two gaps and one single nucleotide polymorphism). A primer has been designed which ends in a gap that shows up only in the dioecious plant. A polymerase chain reaction (PCR) using this primer produces a product for the monoecious but not the dioecious plant.

A scientific forum on the Gulf of Mexico: The Islands in the Stream Concept. Proceedings of the Forum: 23 January 2008, Keating Education Center, Mote Marine Laboratory, Sarasota, Florida

The Scientific Forum on the Gulf of Mexico: The Islands in the Stream Concept took place in January 2008 in Sarasota, Florida. The purpose of the meeting was to bring together scientists and managers from around the Gulf of Mexico to discuss a range of topics on our knowledge of the Gulf of Mexico, from its geology to larger-scale connectivity to the Caribbean region, and their applications to the concept of a more integrated approach to area-based management. The forum included six panels of invited experts who spoke on the oceanographic and biological features in the Gulf of Mexico, including connections with Mexico and the Mesoamerican barrier reef system, and the legal and regulatory structure currently in place. The charge to the group was to share information, identify gaps in our knowledge, identify additional potential areas for protection, and discuss available science about connectivity and the potential value of establishing a marine protected area network in the Gulf of Mexico. (PDF has 108 pages.)

Atlas of abundance and distribution patterns of ichthyoplankton from the Northeast Pacific Ocean and Bering Sea ecosystems: based on research conducted by the Alaska Fisheries Science Center (1972–1996)

This regional atlas summarizes and illustrates the distribution and abundance patterns of fish eggs and larvae of 102 taxa within 34 families found in the Northeast Pacific Ocean including the Bering Sea, Gulf of Alaska, and U.S. west coast ecosystems. Data were collected over a 20+ year period (1972–1996) by the Recruitment Processes Program of the Alaska Fisheries Science Center (AFSC). Ichthyoplankton catch records used in this atlas were generated from 11,379 tows taken during 100 cruises. For each taxon, general life history data are briefly summarized from the literature. Published information on distribution patterns of eggs and larvae are reviewed for the study area. Data from AFSC ichthyoplankton collections were combined to produce an average spatial distribution for each taxon. These data were also used to estimate mean abundance and percent occurrence by year and month, and relative abundance by larval length and season. Abundance from each tow was measured as catch per 10 m2 surface area. A larval distribution and abundance map was produced with a geographic information system using ArcInfo software. For taxa with identifiable pelagic eggs, distribution maps showing presence or absence of eggs are presented. Presence or absence of adults in the study area is mapped based on recent literature and data from AFSC groundfish surveys. Distributional records for adults and early life history stages revealed several new range extensions. (PDF file contains 288 pages.)

Rapid identification of European (Anguilla anguilla) and North American eel (Anguilla rostrata) by polymerase chain reaction.

A rapid and cost effective DNA test is described to identify European eel (Anguilla anguilla) and North American eel (Anguilla rostrata). By means of polymerase chain reaction (PCR) technique parts of the mitochondrial cytochrome b gene are amplified with species specific primers which are designed to produce PCR fragments of different characteristic sizes for European and American eel. The size differences can easily be made visible by agarose gel electrophoresis

Wassertiefenabhängige Auftriebsschwerpunktregelung für seitlich versetzt geschleppte Schwingerträger

The noise emission of the vessel, especially in shallow waters, causes a fright reaction of the fishes near the vessel. To reduce the uncertainty of hydroacoustic measurements connected with that fact, a side shifted towed body is used for the hydroacoustic stock estimation in the Baltic sea. If the towed body was running close to the surface it was quite sensitive to waves. To make the running properties of the side shifted towed body more robust a control of the center of buoyancy depending on the diving depth was introduced. The goal was set to control the towed body without additional energy supply. First results are shown.

TA-CENTER 125 mandrinaketa buruaren zinematika eta erresistentzia ikerketa

Proiektu honen helburua Bilboko Ingeniaritza Eskolako tailer mekanikoan dagoen d??andrea etxeko ta-center 125 mandrinaketa buruaren zinematika eta erresistentzia ikerketa izango da.Lehenik d??andrea etxeak pasatako planoekin,buruaren modelizazioa egingo da hiru dimentsiotan, mekanismoaren funtzionamendua ulertzeko solid works 2008 programaren bitartez. Honekin mandrinaketa buruaren kalkulu zinematikoa egingo da barnean duen engranai tren epizikloidalak kalkulatuz eta konprobatuz. Amaitzeko erresistentzia kalkuluak egingo dira buruak jasaten dituen indarrekin. Nx7.5 elementu finito bidezko programaz modelizatuko da eta emaitza teorikoak proba esperimental batekin alderatuko dira

Bifurcation in a reaction diffusion system

The bifurcation and nonlinear stability properties of the Meinhardt-Gierer model for biochemical pattern formation are studied. Analyses are carried out in parameter ranges where the linearized system about a trivial solution loses stability through one to three eigenfunctions, yielding both time independent and periodic final states. Solution branches are obtained that exhibit secondary bifurcation and imperfection sensitivity and that appear, disappear, or detach themselves from other branches.

Photodissociation and reaction dynamics of chlorine-containing species important in stratospheric ozone chemistry

Chlorine oxide species have received considerable attention in recent years due to their central role in the balance of stratospheric ozone. Many questions pertaining to the behavior of such species still remain unanswered and plague the ability of researchers to develop accurate chemical models of the stratosphere. Presented in this thesis are three experiments that study various properties of some specific chlorine oxide species.

In the first chapter, the reaction between ClONO_2 and protonated water clusters is investigated to elucidate a possible reaction mechanism for the heterogeneous reaction of chlorine nitrate on ice. The ionic products were various forms of protonated nitric acid, NO_2 +(H_20)_m, m = 0, 1, 2. These products are analogous to products previously reported in the literature for the neutral reaction occurring on ice surfaces. Our results support the hypothesis that the heterogeneous reaction is acid-catalyzed.

In the second chapter, the photochemistry of ClONO_2 was investigated at two wavelengths, 193 and 248 nm, using the technique of photofragmentation translational spectroscopy. At both wavelengths, the predominant dissociation pathways were Cl + NO_3 and ClO + NO_2. Channel assignments were confirmed by momentum matching the counterfragments from each channel. A one-dimensional stratospheric model using the new 248 nm branching ratio determined how our results would affect the predicted Cl_x and NO_x partitioning in the stratosphere.

Chapter three explores the photodissociation dynamics of Cl_2O at 193, 248 and 308 nm. At 193 nm, we found evidence for the concerted reaction channel, Cl_2 + O. The ClO + Cl channel was also accessed, however, the majority of the ClO fragments were formed with sufficient internal energies for spontaneous secondary dissociation to occur. At 248 and 308 nm, we only observed only the ClO + Cl channel. . Some of the ClO formed at 248 nm was formed internally hot and spontaneously dissociated. Bimodal translational energy distributions of the ClO and Cl products indicate two pathways leading to the same product exist.

Appendix A, B and C discuss the details of data analysis techniques used in Chapters 1 and 2. The development of a molecular beam source of ClO dimer is presented in Appendix D.

Synthetic applications of intramolecular aza-Wittig reaction for the preparation of heterocyclic compound

[EN] A review focused on recent advances in intramolecular aza-Wittig reaction of phosphazenes with several carbonyl or analogous compounds is reported. Phosphazenes afford intramolecular aza-Wittig reaction with different groups within the molecule as aldehydes, ketones, esters, thioesters, amides, anhydrides and sulfimides. One of the most important applications of this reaction is the synthesis of a wide range of heterocyclic compounds, ranging from simple monocyclic compounds to complex polycyclic and macrocyclic systems.

The intramolecular Buchner reaction of α-diazo-β-ketonitriles : development and application to the total synthesis of (+)-Salvileucalin B

Since its discovery in 1896, the Buchner reaction has fascinated chemists for more than a century. The highly reactive nature of the carbene intermediates allows for facile dearomatization of stable aromatic rings, and provides access to a diverse array of cyclopropane and seven-membered ring architectures. The power inherent in this transformation has been exploited in the context of a natural product total synthesis and methodology studies.

The total synthesis work details efforts employed in the enantioselective total synthesis of (+)-salvileucalin B. The fully-substituted cyclopropane within the core of the molecule arises from an unprecedented intramolecular Buchner reaction involving a highly functionalized arene and an α-diazo-β-ketonitrile. An unusual retro-Claisen rearrangement of a complex late-stage intermediate was discovered on route to the natural product.

The unique reactivity of α-diazo-β-ketonitriles toward arene cyclopropanation was then investigated in a broader methodological study. This specific di-substituted diazo moiety possesses hitherto unreported selectivity in intramolecular Buchner reactions. This technology was enables the preparation of highly functionalized norcaradienes and cyclopropanes, which themselves undergo various ring opening transformations to afford complex polycyclic structures.

Finally, an enantioselective variant of the intramolecular Buchner reaction is described. Various chiral copper and dirhodium catalysts afforded moderate stereoinduction in the cyclization event.

Reactivity of titanocene methylidene with metal halides, alkene sulfides, and alkene oxides

Titanocene metallacyclobutanes show a wide variety of reactivites with organic and inorganic reagents. Their reactions include methylene transfer to organic carbonyls, formation of enolates, electron transfer from activated alkyl chlorides, olefin metathesis, ring opening polymerization. Recently, preparations of heterobinuclear µ-methylene complexes were reported. In this thesis, mechanistic, synthetic, and structural studies of the heterobinuclear µ-methylene complexes will be described. Also, the reaction of titanocene methylidene trimethylphosphine complex with alkene sulfide and styrene sulfide will be presented.

Heterobinuclear µ-methylene-µ-methyl complexes C_(p2)Ti(µ-CH_2)( µ-CH_3)M(1,5-COD) have been prepared (M = Rh, Ir). X-ray crystallography showed that the methyl group of the complex was bonded to the rhodium and bridges to the titanium through an agostic bond. The ^(1)H,^(13)CNMR, IR spectra along with partial deuteration studies supported the structure in both solution and solid state. Activation of the agostic bond is demonstrated by the equilibration of the µ-CH_3 and µ-CH_2 groups. A nonlinear Arrhenius plot, an unusually large kinetic isotope effect (24(5)), and a large negative activation entropy (-64(3)eu) can be explained by the quantum-mechanical tunneling. Calculated rate constants with Bell-type barrier fitted well with the observed one. This equilibration was best explained by a 4e-4c mechanism (or σ bond metathesis) with the character of quantum-mechanical tunneling.

Heterobinuclear µ-methylene-µ-phenyl complexes were synthesized. Structural study of C_(p2)Ti(µ-CH_(2))(µ-p-Me_(2)NC_(6)H_(4))Rh(l,5-COD) showed that the two metal atoms are bridged by the methylene carbon and the ipso carbon of the p-N,N-dimethylarninophenyl group. The analogous structure of C_(p2))Ti(µ-CH_(2))(µ-o-MeOC_(6)H_(4))Rh(1,5-COD) has been verified by the differential NOE. The aromaticity of the phenyl group observed by ^(1)H NMR, was confirmed by the comparison of the C-C bond lengths in the crystallographic structure. The unusual downfield shifts of the ipso carbon in the ^(13)C NMR are assumed to be an indication of the interaction between the ipso carbon and electron-deficient titanium.

Titanium-platinum heterobinuclear µ-methylene complexes C_(p2)Ti(µ-CH_(2))(µ -X)Pt(Me)(PM_(2)Ph) have been prepared (X= Cl, Me). Structural studies indicate the following:(1) the Ti-CH2 bond possesses residual double bond character, (2) there is a dative Pt→Ti interaction which may be regarded as a π back donation from the platinum atom to the 'Ti=CH_(2)'' group, and (3) the µ-CH_3 group is bound to the titanium atom through a three-center, two-electron agostic bond.

Titanocene (η^(2)-thioformaldehyde)•PMe_3 was prepared from C_(p2)Ti=CH_(2)•PMe_3 and sulfur-containing organic compounds (e.g. alkene sulfide, triphenylphosphine sulfide) including elemental sulfur. Mechanistic studies utilizing trans-styrene sulfide-d_1 suggested the stepwise reaction to explain equimolar mixture of trans- and cis-styrene-d_1 as by-products. The product reacted with methyl iodide to produce cationic titanocene (η_(2)-thiomethoxymethyl) complex. Complexes having less coordinating anion like BF_4 or BPh_4 could be obtained through metathesis. Together with structural analyses, the further reactivities of the complexes have been explored.

The complex C_(p2)TiOCH_(2)CH(Ph)CH_2 was prepared from the compound C_(p2)Ti=CH_(2)-PMe_3 and styrene oxide. The product was characterized with ^(1)H-^(1)H correlated 2-dimensional NMR, selective decoupling of ^(1)H NMR, and differential NOE. Stereospecificity of deuterium in the product was lost when trans-styrene oxide-d_1 was allowed to react. Relative rates of the reaction were measured with varying substituents on the phenyl ring. Better linearity (r = -0.98, p^(+) = -0.79) was observed with σ_(p)^(+)than σ(r = -0.87, p = -1.26). The small magnitude of p^+ value and stereospecificity loss during the formation of product were best explained by the generation of biradicals, but partial generation of charge cannot be excluded. Carbonylation of the product followed by exposure to iodine yields the corresponding β-phenyl γ-lactone.

Advances in organic catalysis: the design of a novel asymmetric, organocatalytic intramolecular Diels Alder reaction

No abstract.