964 resultados para TRYPTOPHAN SIDE-CHAINS


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In September 2002, side scan sonar was used to image a portion of the sea floor in the northern OCNMS and was mosaiced at 1-meter pixel resolution using 100 kHz data collected at 300-meter range scale. Video from a remotely-operated vehicle (ROV), bathymetry data, sedimentary samples, and sonar mapping have been integrated to describe geological and biological aspects of habitat and polygon features have been created and attributed with a hierarchical deep-water marine benthic classification scheme (Greene et al. 1999). The data can be used with geographic information system (GIS) software for display, query, and analysis. Textural analysis of the sonar images provided a relatively automated method for delineating substrate into three broad classes representing soft, mixed sediment, and hard bottom. Microhabitat and presence of certain biologic attributes were also populated into the polygon features, but strictly limited to areas where video groundtruthing occurred. Further groundtruthing work in specific areas would improve confidence in the classified habitat map. (PDF contains 22 pages.)

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As part of a multibeam and side scan sonar (SSS) benthic survey of the Marine Conservation District (MCD) south of St. Thomas, USVI and the seasonal closed areas in St. Croix—Lang Bank (LB) for red hind (Epinephelus guttatus) and the Mutton Snapper (MS) (Lutjanus analis) area—we extracted signals from water column targets that represent individual and aggregated fish over various benthic habitats encountered in the SSS imagery. The survey covered a total of 18 km2 throughout the federal jurisdiction fishery management areas. The complementary set of 28 habitat classification digital maps covered a total of 5,462.3 ha; MCDW (West) accounted for 45% of that area, and MCDE (East) 26%, LB 17%, and MS the remaining 13%. With the exception of MS, corals and gorgonians on consolidated habitats were significantly more abundant than submerged aquatic vegetation (SAV) on unconsolidated sediments or unconsolidated sediments. Continuous coral habitat was the most abundant consolidated habitat for both MCDW and MCDE (41% and 43% respectively). Consolidated habitats in LB and MS predominantly consisted of gorgonian plain habitat with 95% and 83% respectively. Coral limestone habitat was more abundant than coral patch habitat; it was found near the shelf break in MS, MCDW, and MCDE. Coral limestone and coral patch habitats only covered LB minimally. The high spatial resolution (0.15 m) of the acquired imagery allowed the detection of differing fish aggregation (FA) types. The largest FA densities were located at MCDW and MCDE over coral communities that occupy up to 70% of the bottom cover. Counts of unidentified swimming objects (USOs), likely representing individual fish, were similar among locations and occurred primarily over sand and shelf edge areas. Fish aggregation school sizes were significantly smaller at MS than the other three locations (MCDW, MCDE, and LB). This study shows the advantages of utilizing SSS in determining fish distributions and density.

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In order to analyse the possibilities of improving grid stability on island systems by local demand response mechanisms,a multi-agent simulation model is presented. To support the primary reserve, an under-frequency load shedding (UFLS)using refrigerator loads is modelled. The model represents the system at multiple scales, by recreating each refrigerator individually, and coupling the whole population of refrigerators to a model which simulates the frequency response of the energy system, allowing for cross-scale interactions. Using a simple UFLS strategy, emergent phenomena appear in the simulation. Synchronisation e ects among the individual loads were discovered, which can have strong, undesirable impacts on the system such as oscillations of loads and frequency. The phase transition from a stable to an oscillating system is discussed.

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An EU funded research project was started in 1998 by institutes from Ireland, Belgium, the Netherlands and Germany to reduce the adverse environmental impact of demersal trawls. In the frame of this project the Institute for Fishery Technique of the Federal Research Centre for Fisheries, Hamburg, is developing a jet beamtrawl replacing the heavy tickler chains of a traditional flatfish beam trawl by water jet nozzles placed at the lower side of the beam with the jets directed towards the sea bottom. First trials on the dutch research vessel “Tridens” were performed in March 1998. Catch and bycatch of a jet beamtrawl and a traditional beamtrawl were compared. The efficiency of the jet beamtrawl was not satisfactory and will have to be improved.

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Pyrroloindoline and unnatural tryptophan motifs are important targets for synthesis based on their incorporation into a diverse array of biologically active natural products. Both types of alkaloids have also found applications as chiral catalysts and tryptophan derivatives are commonly employed as biological probes. On account of their applications, these frameworks have inspired the development of numerous enantioselective, catalytic reactions. In particular, the past few years have witnessed an impressive number of novel approaches for pyrroloindoline formation.

The first project described herein involves our contribution to pyrroloindoline research. We have developed an (R)-BINOL•SnCl4-catalyzed formal (3 + 2) cycloaddition reaction between 3-substituted indoles and 2-amidoacrylates that affords pyrroloindoline-2-carboxylates bearing an all-carbon quaternary center. Mechanistic studies have elucidated that the enantiodetermining step is a highly face-selective catalyst-controlled protonation reaction. The subsequent application of this asymmetric protonation strategy to the synthesis of a variety of enantioenriched tryptophan derivatives is also discussed.

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The solution behavior of linear polymer chains is well understood, having been the subject of intense study throughout the previous century. As plastics have become ubiquitous in everyday life, polymer science has grown into a major field of study. The conformation of a polymer in solution depends on the molecular architecture and its interactions with the surroundings. Developments in synthetic techniques have led to the creation of precision-tailored polymeric materials with varied topologies and functionalities. In order to design materials with the desired properties, it is imperative to understand the relationships between polymer architecture and their conformation and behavior. To meet that need, this thesis investigates the conformation and self-assembly of three architecturally complex macromolecular systems with rich and varied behaviors driven by the resolution of intramolecular conflicts. First we describe the development of a robust and facile synthetic approach to reproducible bottlebrush polymers (Chapter 2). The method was used to produce homologous series of bottlebrush polymers with polynorbornene backbones, which revealed the effect of side-chain and backbone length on the overall conformation in both good and theta solvent conditions (Chapter 3). The side-chain conformation was obtained from a series of SANS experiments and determined to be indistinguishable from the behavior of free linear polymer chains. Using deuterium-labeled bottlebrushes, we were able for the first time to directly observe the backbone conformation of a bottlebrush polymer which showed self-avoiding walk behavior. Secondly, a series of SANS experiments was conducted on a homologous series of Side Group Liquid Crystalline Polymers (SGLCPs) in a perdeuterated small molecule liquid crystal (5CB). Monodomain, aligned, dilute samples of SGLCP-b-PS block copolymers were seen to self-assemble into complex micellar structures with mutually orthogonally oriented anisotropies at different length scales (Chapter 4). Finally, we present the results from the first scattering experiments on a set of fuel-soluble, associating telechelic polymers. We observed the formation of supramolecular aggregates in dilute (≤0.5wt%) solutions of telechelic polymers and determined that the choice of solvent has a significant effect on the strength of association and the size of the supramolecules (Chapter 5). A method was developed for the direct estimation of supramolecular aggregation number from SANS data. The insight into structure-property relationships obtained from this work will enable the more targeted development of these molecular architectures for their respective applications.

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We consider canonical systems with singular left endpoints, and discuss the concept of a scalar spectral measure and the corresponding generalized Fourier transform associated with a canonical system with a singular left endpoint. We use the framework of de Branges’ theory of Hilbert spaces of entire functions to study the correspondence between chains of non-regular de Branges spaces, canonical systems with singular left endpoints, and spectral measures.

We find sufficient integrability conditions on a Hamiltonian H which ensure the existence of a chain of de Branges functions in the first generalized Pólya class with Hamiltonian H. This result generalizes de Branges’ Theorem 41, which showed the sufficiency of stronger integrability conditions on H for the existence of a chain in the Pólya class. We show the conditions that de Branges came up with are also necessary. In the case of Krein’s strings, namely when the Hamiltonian is diagonal, we show our proposed conditions are also necessary.

We also investigate the asymptotic conditions on chains of de Branges functions as t approaches its left endpoint. We show there is a one-to-one correspondence between chains of de Branges functions satisfying certain asymptotic conditions and chains in the Pólya class. In the case of Krein’s strings, we also establish the one-to-one correspondence between chains satisfying certain asymptotic conditions and chains in the generalized Pólya class.

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We study the behavior of granular materials at three length scales. At the smallest length scale, the grain-scale, we study inter-particle forces and "force chains". Inter-particle forces are the natural building blocks of constitutive laws for granular materials. Force chains are a key signature of the heterogeneity of granular systems. Despite their fundamental importance for calibrating grain-scale numerical models and elucidating constitutive laws, inter-particle forces have not been fully quantified in natural granular materials. We present a numerical force inference technique for determining inter-particle forces from experimental data and apply the technique to two-dimensional and three-dimensional systems under quasi-static and dynamic load. These experiments validate the technique and provide insight into the quasi-static and dynamic behavior of granular materials.

At a larger length scale, the mesoscale, we study the emergent frictional behavior of a collection of grains. Properties of granular materials at this intermediate scale are crucial inputs for macro-scale continuum models. We derive friction laws for granular materials at the mesoscale by applying averaging techniques to grain-scale quantities. These laws portray the nature of steady-state frictional strength as a competition between steady-state dilation and grain-scale dissipation rates. The laws also directly link the rate of dilation to the non-steady-state frictional strength.

At the macro-scale, we investigate continuum modeling techniques capable of simulating the distinct solid-like, liquid-like, and gas-like behaviors exhibited by granular materials in a single computational domain. We propose a Smoothed Particle Hydrodynamics (SPH) approach for granular materials with a viscoplastic constitutive law. The constitutive law uses a rate-dependent and dilation-dependent friction law. We provide a theoretical basis for a dilation-dependent friction law using similar analysis to that performed at the mesoscale. We provide several qualitative and quantitative validations of the technique and discuss ongoing work aiming to couple the granular flow with gas and fluid flows.

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Let {Ƶn}n = -∞ be a stochastic process with state space S1 = {0, 1, …, D – 1}. Such a process is called a chain of infinite order. The transitions of the chain are described by the functions

Qi(i(0)) = Ƥ(Ƶn = i | Ƶn - 1 = i (0)1, Ƶn - 2 = i (0)2, …) (i ɛ S1), where i(0) = (i(0)1, i(0)2, …) ranges over infinite sequences from S1. If i(n) = (i(n)1, i(n)2, …) for n = 1, 2,…, then i(n) → i(0) means that for each k, i(n)k = i(0)k for all n sufficiently large.

Given functions Qi(i(0)) such that

(i) 0 ≤ Qi(i(0) ≤ ξ ˂ 1

(ii)D – 1/Ʃ/i = 0 Qi(i(0)) Ξ 1

(iii) Qi(i(n)) → Qi(i(0)) whenever i(n) → i(0),

we prove the existence of a stationary chain of infinite order {Ƶn} whose transitions are given by

Ƥ (Ƶn = i | Ƶn - 1, Ƶn - 2, …) = Qin - 1, Ƶn - 2, …)

With probability 1. The method also yields stationary chains {Ƶn} for which (iii) does not hold but whose transition probabilities are, in a sense, “locally Markovian.” These and similar results extend a paper by T.E. Harris [Pac. J. Math., 5 (1955), 707-724].

Included is a new proof of the existence and uniqueness of a stationary absolute distribution for an Nth order Markov chain in which all transitions are possible. This proof allows us to achieve our main results without the use of limit theorem techniques.