Selectivity, activity, and stability of ruthenium-carbene based olefin metathesis initiators

The olefin metathesis reaction has found many applications in polymer synthesis and more recently in organic synthesis. The use of single component late metal olefin metathesis catalysts has expanded the scope of the reaction to many new applications and has allowed for detailed study of the catalytic species.

The metathesis of terminal olefins of different steric bulk, different geometry as well as electronically different para-substituted styrenes was studied with the ruthenium based metathesis initiators, trans-(PCy₃)₂Cl₂Ru=CHR, of different carbene substituents. Increasing olefin bulk was found to slow the rate of reaction and trans internal olefins were found to be slower to react than cis internal olefins. The kinetic product of a11 reactions was found to be the alkylidene, rather than the methylidene, suggesting the intermediacy of a 2,4-metallacycle. The observed effects were used to explain the mechanism of ring opening cross metathesis and acyclic diene metathesis polymerization. No linear electronic effects were observed.

In studying the different carbene ligands, a series of ester-carbene complexes was synthesized. These complexes were found to be highly active for the metathesis of olefinic substrates, including acrylates and trisubstituted olefins. In addition, the estercarbene moiety is thermodynamically high in energy. As a result, these complexes react to ring-open cyclohexene by metathesis to alleviate the thermodynamic strain of the ester-carbene ligand. However, ester-carbene complexes were found to be thermolytically unstable in solution.

Thermolytic decomposition pathways were studied for several ruthenium-carbene based olefin metathesis catalysts. Substituted carbenes were found to decompose through bimolecular pathways while the unsubstituted carbene (the methylidene) was found to decompose unimolecularly. The stability of several derivatives of the bis-phosphine ruthenium based catalysts was studied for its implications to ring-closing metathesis. The reasons for the activity and stability of the different ruthenium-based catalysts is discussed.

The difference in catalyst activity and initiation is discussed for the bis-phosphine based and mixed N-heterocyclic carbene/phosphine based ruthenium olefin metathesis catalysts. The mixed ligand catalysts initiate far slower than the bis-phosphine catalysts but are far more metathesis active. A scheme is proposed to explain the difference in reactivity between the two types of catalysts.

Estimation of growth and financial analysis through the application of Ipil ipil (Leucaena leucocephala) leaf meal as supplements to soybean and fish meal in the diet of juvenile monosex tilapia (Oreochromis niloticus)

Among plant protein ingredients,ipil ipil (Leucaena leucocephala) leafmeal (ILLM) is considered the most nutritive plant protein source after soybean meal in aquatic feeds. That was proven in a 21-day experiment conducted to assess the response of juvenile Monosex Nile tilapia Oreochromis niloticus with four iso-nitrogenous formulated diets: One control diet was formulated based on fishmeal, one on soybean meal and one on rice bran, ipil ipil leafmeal was also included in experimental diets.

Essays on Correlated Equilibrium and Voter Turnout

This thesis consists of three essays in the areas of political economy and game theory, unified by their focus on the effects of pre-play communication on equilibrium outcomes.

Communication is fundamental to elections. Chapter 2 extends canonical voter turnout models, where citizens, divided into two competing parties, choose between costly voting and abstaining, to include any form of communication, and characterizes the resulting set of Aumann's correlated equilibria. In contrast to previous research, high-turnout equilibria exist in large electorates and uncertain environments. This difference arises because communication can coordinate behavior in such a way that citizens find it incentive compatible to follow their correlated signals to vote more. The equilibria have expected turnout of at least twice the size of the minority for a wide range of positive voting costs.

In Chapter 3 I introduce a new equilibrium concept, called subcorrelated equilibrium, which fills the gap between Nash and correlated equilibrium, extending the latter to multiple mediators. Subcommunication equilibrium similarly extends communication equilibrium for incomplete information games. I explore the properties of these solutions and establish an equivalence between a subset of subcommunication equilibria and Myerson's quasi-principals' equilibria. I characterize an upper bound on expected turnout supported by subcorrelated equilibrium in the turnout game.

Chapter 4, co-authored with Thomas Palfrey, reports a new study of the effect of communication on voter turnout using a laboratory experiment. Before voting occurs, subjects may engage in various kinds of pre-play communication through computers. We study three communication treatments: No Communication, a control; Public Communication, where voters exchange public messages with all other voters, and Party Communication, where messages are exchanged only within one's own party. Our results point to a strong interaction effect between the form of communication and the voting cost. With a low voting cost, party communication increases turnout, while public communication decreases turnout. The data are consistent with correlated equilibrium play. With a high voting cost, public communication increases turnout. With communication, we find essentially no support for the standard Nash equilibrium turnout predictions.

Lock Acquisition and Sensitivity Analysis of Advanced LIGO Interferometers

Laser interferometer gravitational wave observatory (LIGO) consists of two complex large-scale laser interferometers designed for direct detection of gravitational waves from distant astrophysical sources in the frequency range 10Hz - 5kHz. Direct detection of space-time ripples will support Einstein's general theory of relativity and provide invaluable information and new insight into physics of the Universe.

Initial phase of LIGO started in 2002, and since then data was collected during six science runs. Instrument sensitivity was improving from run to run due to the effort of commissioning team. Initial LIGO has reached designed sensitivity during the last science run, which ended in October 2010.

In parallel with commissioning and data analysis with the initial detector, LIGO group worked on research and development of the next generation detectors. Major instrument upgrade from initial to advanced LIGO started in 2010 and lasted till 2014.

This thesis describes results of commissioning work done at LIGO Livingston site from 2013 until 2015 in parallel with and after the installation of the instrument. This thesis also discusses new techniques and tools developed at the 40m prototype including adaptive filtering, estimation of quantization noise in digital filters and design of isolation kits for ground seismometers.

The first part of this thesis is devoted to the description of methods for bringing interferometer to the linear regime when collection of data becomes possible. States of longitudinal and angular controls of interferometer degrees of freedom during lock acquisition process and in low noise configuration are discussed in details.

Once interferometer is locked and transitioned to low noise regime, instrument produces astrophysics data that should be calibrated to units of meters or strain. The second part of this thesis describes online calibration technique set up in both observatories to monitor the quality of the collected data in real time. Sensitivity analysis was done to understand and eliminate noise sources of the instrument.

Coupling of noise sources to gravitational wave channel can be reduced if robust feedforward and optimal feedback control loops are implemented. The last part of this thesis describes static and adaptive feedforward noise cancellation techniques applied to Advanced LIGO interferometers and tested at the 40m prototype. Applications of optimal time domain feedback control techniques and estimators to aLIGO control loops are also discussed.

Commissioning work is still ongoing at the sites. First science run of advanced LIGO is planned for September 2015 and will last for 3-4 months. This run will be followed by a set of small instrument upgrades that will be installed on a time scale of few months. Second science run will start in spring 2016 and last for about 6 months. Since current sensitivity of advanced LIGO is already more than factor of 3 higher compared to initial detectors and keeps improving on a monthly basis, upcoming science runs have a good chance for the first direct detection of gravitational waves.

Trapping success and population analysis of Siren lacertina and Amphiuma means

Siren and Amphiuma are two poorly known genera of aquatic salamanders that occur in the Southeastern United States. A primarily bottom-dwelling existence makes these salamanders difficult to detect with conventional sampling methodologies. Therefore, the current status of their populations is unknown. I compared the capture success of modified crayfish traps and plastic minnow traps in capturing these salamanders. In addition, a mark-recapture study of S. lacertina (Greater siren) and A. means (Two-toed amphiuma) was conducted at Okefenokee National Wildlife Refuge (southern Georgia) and at Katharine Ordway Preserve (north-central Florida) from August 2001 until September 2002. Crayfish traps were much more successful than minnow traps in catching siren and amphiuma. Crayfish traps yielded 270 captures for an overall capture success of 16%, whereas minnow traps yielded only 13 captures for an overall success rate of 0.05%. In addition, several marking techniques were evaluated, and of these, only passive integrated transponder (PIT) tags were retained for the duration of the study. Therefore, I recommend this marking technique for long-term monitoring of S. lacertina and A. means. Several variables were found to have significant effects on capture rates of salamanders. A. means were most often captured in summer and the number of captures was positively correlated with water temperature, water level, and rainfall. S. lacertina were most often captured during winter and spring. Number of captures was negatively correlated with water temperature, while no relationship was found with water level or rainfall. Trap day and baiting had no significant effect on number of A. means or S. lacertina captured. Recapture probabilities of both species were low, 0.025-0.03 for S. lacertina and 0.08-0.11 for A. means. Monthly survival rates were high, 0.77-0.97 for A. means and 0.88-1.00 for S. lacertina. Density estimates of 1.3 salamanders/m2 (S. lacertina) and 0.28 salamanders/m2 (A. means) were obtained for Lake Suggs using Jolly-Seber models. Siren and amphiuma make up a substantial part of wetland biomass and can impact many other wetland species. Thus, more attention must be focused on evaluating and monitoring their populations.

Brand image and lexicographic analysis: an application to shopping malls

[EN] The concept of image in its different aspects is very important in today s society as well as in the business management field. Some authors reports that most of the studies that measure image do not take into account neither previous theoretical and conceptual models nor other possible empirical evidence alternatives. Given this need, a research regarding the concept of brand image applied to shopping malls was conducted based on the conceptual model of the consumer cognitive response in order to empirically explore and contrast it. For this reason, a survey was applied to 420 consumers in five shopping malls in Bogotá, achieving a database of 3.749 cases. The results show attribute-shopping mall associations expressed in unique, differentiated, and notorious vocabulary obtained applying lexicometric and multivariate analysis techniques. Attribute-shopping mall associations such as spacious , good location , good variety of stores , and the existence of movie theaters . Finally, this research aims to potentially improve the management of shopping malls and increase their attractiveness and customer loyalty by applying the development of service quality systems, integral communication, segmentation, and positioning.

Numerical and experimental analysis on green laser crystallization of amorphous silicon thin films

The effect of laser fluence on the crystallization of amorphous silicon irradiated by a frequency-doubled Nd:YAG laser is studied both theoretically and experimentally. An effective numerical model is set up to predict the melting threshold and the optimized laser fluence for the crystallization of 200-nm-thick amorphous silicon. The variation of the temperature distribution with time and the melt depth is analyzed. Besides the model, the Raman spectra of thin films treated with different fluences are measured to confirm the phase transition and to determine the optimized fluence. The calculating results accord well with those obtained from the experimental data in this research. (C) 2008 Elsevier Ltd. All rights reserved.

Workshop on turtle bycatch mitigation for longline fisheries: experimental design and data analysis, 7-8 November 2007, San Ramón de Alajuela, Costa Rica

Large numbers of fishing vessels operating from ports in Latin America participate in surface longline fisheries in the eastern Pacific Ocean (EPO), and several species of sea turtles inhabit the grounds where these fleets operate. The endangered status of several sea turtle species, and the success of circle hooks (‘treatment’ hooks) in reducing turtle hookings in other ocean areas, as compared to J-hooks and Japanese-style tuna hooks (‘control’ hooks), prompted the initiation of a hook exchange program on the west coast of Latin America, the Eastern Pacific Regional Sea Turtle Program (EPRSTP)1. One of the goals of the EPRSTP is to determine if circle hooks would be effective at reducing turtle bycatch in artisanal fisheries of the EPO without significantly reducing the catch of marketable fish species. Participating fishers were provided with circle hooks at no cost and asked to replace the J/Japanese-style tuna hooks on their longlines with circle hooks in an alternating manner. Data collected by the EPRSTP show differences in longline gear and operational characteristics within and among countries. These aspects of the data, in addition to difficulties encountered with implementation of the alternating-hook design, pose challenges for analysis of these data.

Spectral properties and stability of Er3+-doped TeO2-WO3 glass

Er3+-doped TeO2-WO3 glass was fabricated and characterized by absorption spectrum, fluorescence spectrum, Raman spectrum and stability. The Judd-Ofelt parameter ohm(t)(t = 2, 4, 6) were calculated from the absorption spectrum by the Judd-Ofelt theory. The fluorescence spectrum indicates that the fluorescence width at half-maximum (FWHM) is 66nm. The stimulated emission cross-section of Er3+ in TeO2-WO3 glass at 1532 nm was calculated to be 0.80 x 10(-20) cm(2) by McCumber theory. The phonon energy of TeO2-WO3 glass is found to be 931 cm(-1). The difference between crystallization onset temperature and glass transition temperature Delta T is 112 degrees C. These results show that Er3+-doped TeO2-WO3 glass has higher stability and good spectral properties, which were useful for broadband amplifier. (c) 2005 Elsevier B.V. All rights reserved.