Design and synthesis of biofunctional magnetic/fluorescent glyco-nanoparticles and quantum dots and their application as specific molecular imaging probes

206 p.

Nonstationary response of structures and its application to earthquake engineering

This thesis presents a simplified state-variable method to solve for the nonstationary response of linear MDOF systems subjected to a modulated stationary excitation in both time and frequency domains. The resulting covariance matrix and evolutionary spectral density matrix of the response may be expressed as a product of a constant system matrix and a time-dependent matrix, the latter can be explicitly evaluated for most envelopes currently prevailing in engineering. The stationary correlation matrix of the response may be found by taking the limit of the covariance response when a unit step envelope is used. The reliability analysis can then be performed based on the first two moments of the response obtained.

The method presented facilitates obtaining explicit solutions for general linear MDOF systems and is flexible enough to be applied to different stochastic models of excitation such as the stationary models, modulated stationary models, filtered stationary models, and filtered modulated stationary models and their stochastic equivalents including the random pulse train model, filtered shot noise, and some ARMA models in earthquake engineering. This approach may also be readily incorporated into finite element codes for random vibration analysis of linear structures.

A set of explicit solutions for the response of simple linear structures subjected to modulated white noise earthquake models with four different envelopes are presented as illustration. In addition, the method has been applied to three selected topics of interest in earthquake engineering, namely, nonstationary analysis of primary-secondary systems with classical or nonclassical dampings, soil layer response and related structural reliability analysis, and the effect of the vertical components on seismic performance of structures. For all the three cases, explicit solutions are obtained, dynamic characteristics of structures are investigated, and some suggestions are given for aseismic design of structures.

The development of an asymmetric palladium-catalyzed conjugate addition and its application toward the total syntheses of taiwaniaquinoid natural products

The asymmetric synthesis of quaternary stereocenters remains a challenging problem in organic synthesis. Past work from the Stoltz laboratory has resulted in methodology to install quaternary stereocenters α- or γ- to carbonyl compounds. Thus, the asymmetric synthesis of β-quaternary stereocenters was a desirable objective, and was accomplished by engineering the palladium-catalyzed addition of arylmetal organometallic reagents to α,β-unsaturated conjugate acceptors.

Herein, we described the rational design of a palladium-catalyzed conjugate addition reactions utilizing a catalyst derived from palladium(II) trifluoroacetate and pyridinooxazole ligands. This reaction is highly tolerant of protic solvents and oxygen atmosphere, making it a practical and operationally simple reaction. The mild conditions facilitate a remarkably high functional group tolerance, including carbonyls, halogens, and fluorinated functional groups. Furthermore, the reaction catalyzed conjugate additions with high enantioselectivity with conjugate acceptors of 5-, 6-, and 7-membered ring sizes. Extension of the methodology toward the asymmetric synthesis of flavanone products is presented, as well.

A computational and experimental investigation into the reaction mechanism provided a stereochemical model for enantioinduction, whereby the α-methylene protons adjacent the enone carbonyl clashes with the tert-butyl groups of the chiral ligand. Additionally, it was found that the addition of water and ammonium hexafluorophosphate significantly increases the reaction rate without sacrificing enantioselectivity. The synergistic effects of these additives allowed for the reaction to proceed at a lower temperature, and thus facilitated expansion of the substrate scope to sensitive functional groups such as protic amides and aryl bromides. Investigations into a scale-up synthesis of the chiral ligand (S)-tert-butylPyOx are also presented. This three-step synthetic route allowed for synthesis of the target compound of greater than 10 g scale.

Finally, the application of the newly developed conjugate addition reaction toward the synthesis of the taiwaniaquinoid class of terpenoid natural products is discussed. The conjugate addition reaction formed the key benzylic quaternary stereocenter in high enantioselectivity, joining together the majority of the carbons in the taiwaniaquinoid scaffold. Efforts toward the synthesis of the B-ring are presented.

A simple approach for the estimation of food consumption from growth rates at different environmental conditions and its application to juvenile cod (Gadus morhua L.) of a fjordic sea loch on the west coast of Scotland

Abstract Growth and condition of fish are functions of available food and environmental conditions. This led to the idea of using fish as a “consumption sensor” for the measurement of food intake over a defined period of time. A bio-physical model for the estimation of food consumption was developed based on the von Bertalanffy model. Whereas some of the input variables of the model, the initial and final lengths and masses of a fish and the temperature within the time period considered can easily be measured, internal characteristics of the species have to be determined indirectly. Three internal parameters are used in the model: the maintenance consumption at 0°C, the temperature dependence of this consumption and the food efficiency, the percentage of the ingested food utilized. Estimates of the parameters for a given species can be determined by feeding experiments. Here, data from published feeding experiments on juvenile cod, Gadus morhua L., were used to validate the model. The average of the relative error for the food intake predicted by the model for individual fish was about 24 %, indicating that fish used the food with different efficiencies. However, grouping the fish according to size classes and temperature lowered the relative error of the predicted food intake for the group to typically 5 %. For a group containing all fish of the feeding experiment the relative prediction error was about 2 %. Zusammenfassung Wachstum und Kondition der Fische sind von der verfügbaren Nahrung und von Umweltbedingungen abhängig. Dies führte zur Idee, Fisch als „Konsum-Sensor“ für die Messung der Nahrungsaufnahme über einen definierten Zeitraum zu verwenden. Auf Grundlage des von Bertalanffy-Modells wurde ein bio-physikalisches Modell zur Schätzung der Futteraufnahme entwickelt. Während einige der Eingangsgrößen des Modells leicht gemessen werden können (Anfangs- und Endlänge und -körpermasse der Fische und die Temperatur innerhalb des betrachteten Zeitraum), können interne Parameter der betrachteten Art nur indirekt bestimmt werden. Drei interne Parameter werden in dem Modell verwendet: Die Erhaltungskonsumtion bei 0° C, die Temperaturabhängigkeit dieser Rate und der Wirkungsgrad der Nahrung (der Anteil der Nahrung ,der aufgenommen und verwendet und nicht ungenutzt wieder ausgeschieden wird). Die Modellparameter für eine bestimmte Art können durch Fütterungsversuche bestimmt werden. Um das Modell zu validieren wurden Daten aus veröffentlichten Fütterungsversuchen mit juvenilen Kabeljau (Gadus morhua L.) verwendet. Modell und Wirklichkeit weichen in der Regel voneinander ab. Der durchschnittliche relative Fehler der durch das Modell vorhergesagten Nahrungsaufnahme betrug für Einzelfische etwa 24%, was darauf hinweist, dass einzelne Fisch die Nahrung mit unterschiedlichen Wirkungsgraden verwerten. Allerdings senkte die Gruppierung der Fische nach Größenklassen und Temperatur den relativen Vorhersagefehler für die Nahrungsaufnahme der Gruppe auf etwa 5%. Für alle Fische im Fütterungsversuch ist der relative Vorhersagefehler etwa 2%.

Cascaded Fresnel digital hologram and its application to watermarking

A cascaded Fresnel digital hologram (CFDH) is proposed, together with its mathematical derivation. Its application to watermarking has been demonstrated by a simulation procedure, in which the watermark image to be hidden is encoded into the phase of the host image. The watermark image can be deciphered by the CFDH setup, the reconstructed image shows good quality and the error is almost close to zero. Compared with previous technique, this is a lensless architecture which minimizes the hardware requirement, and it is used for the encryption of digital image.

Optical near-field simulation of Sb thin film thermal lens and its application in optical recording

Using the finite-difference-time-domain method, the near-field optical distribution and properties of Sb thin film thermal lens are calculated and simulated. The results show as follows. Within the near-field distance to the output plane of thermal lens, the spot size is approximately 100 nm, and its intensity is greatly enhanced, which is higher than that of incident light. The spot shape gradually changes from ellipse to round at the distance of more than 12 nm to the output plane. The above-simulated results are further demonstrated by the static optical recording experiment. (C) 2005 American Institute of Physics.

Thiophene-fluorene derivatives with high three-photon absorption activities and their application to optical power limiting

The three-photon absorption (3PA) properties of two thiophene-fluorene derivatives (abbreviated as MOTFTBr and ATFTBr) have been determined by using a Q-switched Nd:YAG laser pumped wish 38ps pulses at 1064nm in DMF. The measured 3PA cross-sections are 152x10(-78)cm(6)s(2) and 139x10(-78)cm(6)s(2), respectively. The optimized structures were obtained by AM1 calculations and the results indicate that these two molecules show nonplanar structures, and attaching different donors has different effects on the molecular structure. The charge density distributions during the excitation were also systematically studied by using AM1 method. In addition, an obvious optical power limiting effect induced by 3PA has been demonstrated for both derivatives.

Solutions for New Terrestrial Broadcasting Systems Offering Simultaneously Stationary and Mobile Services

221 p.