The Effects of Grass Carp on Aquatic Plants, Plankton and Benthos in Ponds

The effects of the grass carp (Ctenopharyngodon idella Val.)on aquatic plant biomass, water quality, phytoplankton, chlorophyll a, zooplankton and benthic fauna were investigated between May and September 2000 in earthen ponds at Cifteler- Sakaryabasi Aquaculture and Research Station. (PDF has 8 pages)

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

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The design and synthesis of a true, heterogeneous, asymmetric catalyst

This work describes the design and synthesis of a true, heterogeneous, asymmetric catalyst. The catalyst consists of a thin film that resides on a high-surface- area hydrophilic solid and is composed of a chiral, hydrophilic organometallic complex dissolved in ethylene glycol. Reactions of prochiral organic reactants take place predominantly at the ethylene glycol-bulk organic interface.

The synthesis of this new heterogeneous catalyst is accomplished in a series of designed steps. A novel, water-soluble, tetrasulfonated 2,2'-bis (diphenylphosphino)-1,1'-binaphthyl (BINAP-4S0_3Na) is synthesized by direct sulfonation of 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP). The rhodium (I) complex of BINAP-4SO_3Na is prepared and is shown to be the first homogeneous catalyst to perform asymmetric reductions of prochiral 2-acetamidoacrylic acids in neat water with enantioselectivities as high as those obtained in non-aqueous solvents. The ruthenium (II) complex, [Ru(BINAP-4SO_3Na)(benzene)Cl]Cl is also synthesized and exhibits a broader substrate specificity as well as higher enantioselectivities for the homogeneous asymmetric reduction of prochiral 2-acylamino acid precursors in water. Aquation of the ruthenium-chloro bond in water is found to be detrimental to the enantioselectivity with some substrates. Replacement of water by ethylene glycol results in the same high e.e's as those found in neat methanol. The ruthenium complex is impregnated onto a controlled pore-size glass CPG-240 by the incipient wetness technique. Anhydrous ethylene glycol is used as the immobilizing agent in this heterogeneous catalyst, and a non-polar 1:1 mixture of chloroform and cyclohexane is employed as the organic phase.

Asymmetric reduction of 2-(6'-methoxy-2'-naphthyl)acrylic acid to the non-steroidal anti-inflammatory agent, naproxen, is accomplished with this heterogeneous catalyst at a third of the rate observed in homogeneous solution with an e.e. of 96% at a reaction temperature of 3°C and 1,400 psig of hydrogen. No leaching of the ruthenium complex into the bulk organic phase is found at a detection limit of 32 ppb. Recycling of the catalyst is possible without any loss in enantioselectivity. Long-term stability of this new heterogeneous catalyst is proven by a self-assembly test. That is, under the reaction conditions, the individual components of the present catalytic system self-assemble into the supported-catalyst configuration.

The strategies outlined here for the design and synthesis of this new heterogeneous catalyst are general, and can hopefully be applied to the development of other heterogeneous, asymmetric catalysts.

Structure-Guided Design and Biophysical Characterization of Novel Anti-HIV Reagents

Despite over 30 years of effort, an HIV-1 vaccine that elicits protective antibodies still does not exist. Recent clinical studies have identified that during natural infection about 20% of the population is capable of mounting a potent and protective antibody response. Closer inspection of these individuals reveal that a subset of these antibodies, recently termed potent VRC01-like (PVL), derive exclusively from a single human germline heavy chain gene. Induced clonal expansion of the B cell encoding this gene is the first step through which PVL antibodies may be elicited. Unfortunately, naturally occurring HIV gp120s fail to bind to this germline, and as a result cannot be used as the initial prime for a vaccine regimen. We have determined the crystal structure of an important germline antibody that is a promising target for vaccine design efforts, and have set out to engineer a more likely candidate using computationally-guided rational design.

In addition to prevention efforts on the side of vaccine design, recently characterized broadly neutralizing anti-HIV antibodies have excellent potential for use in gene therapy and passive immunotherapy. The separation distance between functional Fabs on an antibody is important due to the sparse distribution of envelop spikes on HIV compared to other viruses. We set out to build and characterize novel antibody architectures by incorporating structured linkers into the hinge region of an anti-HIV antibody b12. The goal was to observe whether these linkers increased the arm-span of the IgG dimer. When incorporated, flexible Gly4Ser repeats did not result in detectable extensions of the IgG antigen binding domains, by contrast to linkers including more rigid domains such as β2-microglobulin, Zn-α2-glycoprotein, and tetratricopeptide repeats (TPRs). This study adds an additional set of linkers with varying lengths and rigidities to the available linker repertoire, which may be useful for the modification and construction of antibodies and other fusion proteins.

The Design and Synthesis of Transition Metal Complexes Supported by Non-innocent Ligand Scaffolds for Small Molecule Activation

This dissertation focuses on the incorporation of non-innocent or multifunctional moieties into different ligand scaffolds to support one or multiple metal centers in close proximity. Chapter 2 focuses on the initial efforts to synthesize hetero- or homometallic tri- or dinuclear metal carbonyl complexes supported by para-terphenyl diphosphine ligands. A series of [M₂M’(CO)₄]-type clusters (M = Ni, Pd; M’ = Fe, Co) could be accessed and used to relate the metal composition to the properties of the complexes. During these studies it was also found that non-innocent behavior was observed in dinuclear Fe complexes that result from changes in oxidation state of the cluster. These studies led to efforts to rationally incorporate central arene moieties capable managing both protons and electrons during small molecule activation.

Chapter 3 discusses the synthesis of metal complexes supported by a novel para-terphenyl diphosphine ligand containing a non-innocent 1,4-hydroquinone moiety as the central arene. A Pd⁰-hydroquinone complex was found to mediate the activation of a variety of small molecules to form the corresponding Pd⁰-quinone complexes in a formal two proton ⁄ two electron transformation. Mechanistic investigations of dioxygen activation revealed a metal-first activation process followed by subsequent proton and electron transfer from the ligand. These studies revealed the capacity of the central arene substituent to serve as a reservoir for a formal equivalent of dihydrogen, although the stability of the M-quinone compounds prevented access to the PdII-quinone oxidation state, thus hindering of small molecule transformations requiring more than two electrons per equivalent of metal complex.

Chapter 4 discusses the synthesis of metal complexes supported by a ligand containing a 3,5-substituted pyridine moiety as the linker separating the phenylene phosphine donors. Nickel and palladium complexes supported by this ligand were found to tolerate a wide variety of pyridine nitrogen-coordinated electrophiles which were found to alter central pyridine electronics, and therefore metal-pyridine π-system interactions, substantially. Furthermore, nickel complexes supported by this ligand were found to activate H-B and H-Si bonds and formally hydroborate and hydrosilylate the central pyridine ring. These systems highlight the potential use of pyridine π-system-coordinated metal complexes to reversibly store reducing equivalents within the ligand framework in a manner akin to the previously discussed 1,4-hydroquinone diphosphine ligand scaffold.

Chapter 5 departs from the phosphine-based chemistry and instead focuses on the incorporation of hydrogen bonding networks into the secondary coordination sphere of [Fe₄(μ₄-O)]-type clusters supported by various pyrazolate ligands. The aim of this project is to stabilize reactive oxygenic species, such as oxos, to study their spectroscopy and reactivity in the context of complicated multimetallic clusters. Herein is reported this synthesis and electrochemical and Mössbauer characterization of a series of chloride clusters have been synthesized using parent pyrazolate and a 3-aminophenyl substituted pyrazolate ligand. Efforts to rationally access hydroxo and oxo clusters from these chloride precursors represents ongoing work that will continue in the group.

Appendix A discusses attempts to access [Fe₃Ni]-type clusters as models of the enzymatic active site of [NiFe] carbon monoxide dehydrogenase. Efforts to construct tetranuclear clusters with an interstitial sulfide proved unsuccessful, although a (μ₃-S) ligand could be installed through non-oxidative routes into triiron clusters. While [Fe₃Ni(μ₄-O)]-type clusters could be assembled, accessing an open heterobimetallic edge site proved challenging, thus prohibiting efforts to study chemical transformations, such as hydroxide attack onto carbon monoxide or carbon dioxide coordination, relevant to the native enzyme. Appendix B discusses the attempts to synthesize models of the full H-cluster of [FeFe]-hydrogenase using a bioinorganic approach. A synthetic peptide containing three cysteine donors was successfully synthesized and found to chelate a preformed synthetic [Fe₄S₄] cluster. However, efforts to incorporate the diiron subsite model complex proved challenging as the planned thioester exchange reaction was found to non-selectively acetylate the peptide backbone, thus preventing the construction of the full six-iron cluster.

I. Fundamental limitations in microelectronics. II. Power Schottky diode design and comparison with the junction diode. III. Permittivity of strontium titanate

Part I

The physical phenomena which will ultimately limit the packing density of planar bipolar and MOS integrated circuits are examined. The maximum packing density is obtained by minimizing the supply voltage and the size of the devices. The minimum size of a bipolar transistor is determined by junction breakdown, punch-through and doping fluctuations. The minimum size of a MOS transistor is determined by gate oxide breakdown and drain-source punch-through. The packing density of fully active bipolar or static non-complementary MOS circuits becomes limited by power dissipation. The packing density of circuits which are not fully active such as read-only memories, becomes limited by the area occupied by the devices, and the frequency is limited by the circuit time constants and by metal migration. The packing density of fully active dynamic or complementary MOS circuits is limited by the area occupied by the devices, and the frequency is limited by power dissipation and metal migration. It is concluded that read-only memories will reach approximately the same performance and packing density with MOS and bipolar technologies, while fully active circuits will reach the highest levels of integration with dynamic MOS or complementary MOS technologies.

Part II

Because the Schottky diode is a one-carrier device, it has both advantages and disadvantages with respect to the junction diode which is a two-carrier device. The advantage is that there are practically no excess minority carriers which must be swept out before the diode blocks current in the reverse direction, i.e. a much faster recovery time. The disadvantage of the Schottky diode is that for a high voltage device it is not possible to use conductivity modulation as in the p i n diode; since charge carriers are of one sign, no charge cancellation can occur and current becomes space charge limited. The Schottky diode design is developed in Section 2 and the characteristics of an optimally designed silicon Schottky diode are summarized in Fig. 9. Design criteria and quantitative comparison of junction and Schottky diodes is given in Table 1 and Fig. 10. Although somewhat approximate, the treatment allows a systematic quantitative comparison of the devices for any given application.

Part III

We interpret measurements of permittivity of perovskite strontium titanate as a function of orientation, temperature, electric field and frequency performed by Dr. Richard Neville. The free energy of the crystal is calculated as a function of polarization. The Curie-Weiss law and the LST relation are verified. A generalized LST relation is used to calculate the permittivity of strontium titanate from zero to optic frequencies. Two active optic modes are important. The lower frequency mode is attributed mainly to motion of the strontium ions with respect to the rest of the lattice, while the higher frequency active mode is attributed to motion of the titanium ions with respect to the oxygen lattice. An anomalous resonance which multi-domain strontium titanate crystals exhibit below 65°K is described and a plausible mechanism which explains the phenomenon is presented.

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.

An investigation into the potential losses of fish on the filter plates at the Hodder Water Treatment Works Stocks Reservoir

Stocks Reservoir is situated amidst the Forest of Bowland in the upper reaches of the old river valley of the Hodder. The reservoir was built in 1927 for the Fylde Water Board who primarily supplied water to Blackpool. The objective of this study is to assess the degree and likelihood of fish ingress onto the fish plates at the present and proposed stocking densities. An additional aim is to evaluate the operational implications, and if necessary suggest methods of alleviating the problem. Three spheres of study have been undertaken to achieve these objectives, these being: 1. To selectively stock the reservoir and monitor the angling club catches in order to assess the total population, relating it to fish plate losses and proposed stocking densities. 2. To monitor the fish taken from the fish plates and assess the reasons for their ingress. 3. To study the draw off tower and fish plates, and suggest ways of ameliorating or halting the loss of fish and consequent operational problems.

Design and implementation of fishery modules in integrated household surveys in developing countries

Fish and other aquatic animals contribute to the food security of citizens of developing countries, both as a source of income and as a component of healthy diets, yet fishing is not currently captured in most integrated household surveys. This sourcebook provides essential technical guidance on the design of statistical modules and questionnaires aimed at collecting fishery data at the household level. Background on the main policies important to the fishery sector, information on the data needed to analyze issues of policy relevance, and methodology on the construction of survey questions to collect necessary data are also provided. The document is organized to provide essential technical guidance on how to design statistical modules and questionnaires aimed at collecting fishery data at the household level. It includes an overview of the main technical and statistical challenges related to sampling fishery-dependent households. The document starts with an introductory section identifying the potential reasons why fisheries and in particular small-scale fisheries have not been adequately included in national statistical systems in a large number of countries. The report then proposes a succinct review of what is known (and what remains unknown) about small-scale fisheries and their contribution to the livelihoods of households in sub-Saharan Africa. It also provides readers with background on the main policies that are important to the fishery sector, information on the data needed to analyze issues of policy relevance, and methodology on the construction of survey questions to collect necessary data.

A standard format for design and evaluation of pond experiments

Details are given of a standard format used by the Pond Dynamics/Aquaculture Collaborative Research Support Program of the US Agency for International Development for the communication of experimental ideas. An example is given of the "Preliminary Proposal Format," which contains a list of information categories or headings as follows: Title; Objectives: Significance; Experimental design; Pond facilities; Stocking rate; Other inputs; Sampling plan; Hypotheses; Statistical methods; Duration; Water management; and Schedule.

The design and implementation of dialogue control in voice operated database inquiry systems

This paper describes work performed as part of the U.K. Alvey sponsored Voice Operated Database Inquiry System (VODIS) project in the area of intelligent dialogue control. The principal aims of the work were to develop a habitable interface for the untrained user; to investigate the degree to which dialogue control can be used to compensate for deficiencies in recognition performance; and to examine the requirements on dialogue control for generating natural speech output. A data-driven methodology is described based on the use of frames in which dialogue topics are organized hierarchically. The concept of a dynamically adjustable scope is introduced to permit adaptation to recognizer performance and the use of historical and hierarchical contexts are described to facilitate the construction of contextually relevant output messages. © 1989.

Design and commissioning of a 30kw direct drive wave generator

The Trident Energy TE5 is a prototype wave energy converter operating on the principle of having direct-drive linear generators mounted above the water surface, coupled to floats moving under the rig deck. This paper describes aspects of the TE5 design, including its generators, power electronic systems and the conception of its marine structure.