Bibliography: leaves 200-223.

Bibliography: leaves 213-245. Genetic control of tolerance to boron was investigated between a moderately tolerant variety, Halberd, a tolerant line G61450 and the moderately sensitive varieties Schomburgk and Condor.

Diamond is an important material in many industrial applications (e.g., machining of hard materials, bio-electronics, optics, electronics, etc.) because of its exceptional properties such as hardness, tolerance to aggressive environments, compatibility with human tissues, and high carrier mobility. However, a highly controlled method for growing artificial high-purity diamond on a range of different substrates is needed to exploit these exceptional properties. The Chemical Vapour Deposition (CVD) method is a useful tool for this purpose, but the process still needs to be developed further to achieve better control of growth. In this context, the introduction of dopant species into the gas phase has been shown to strongly influence growth rate and surface morphology. Density Functional Theory (DFT) methods are used to deepen our atomic-level understanding of the effect of dopants on the mechanism for CVD growth on diamond. More specifically, the effect of four dopants (N, P, B and S) has been studied on the important reaction steps in the growth mechanism of diamond. Substitution of N into the diamond lattice has generally been found to disfavour critical reaction steps in the growth of the 100-face in diamond. This negative effect has been related to electron transfer from the N dopant into an empty surface state, e.g., a surface carbon radical. In addition, strong surface stabilization is observed for N substitution in certain sites via a beta-scission reconstruction, with the formation of sp2 carbon. These observations correlate well with observed surface degradation and decrease in growth rate when a high concentration of nitrogen gas is introduced into the CVD growth process. The effect of co-adsorbed P, S and B onto the diamond surface has also been investigated for two reaction steps: CH3 adsorption and H abstraction. While P and B are observed to influence these reaction steps, the effect of S is rather limited.

Boron (B) is a rare element on Earth crust with a natural abundance of 0.001%. However, boron content of water and soils may be significantly high in the regions with rich boron reserves. In addition, extensive use of agrochemicals in soils as well as various natural processes increases the boron concentration in water. Despite B is an essential element for all living creatures, it may pose risks at high level exposures. World Health Organization (WHO) has recommended a daily intake of 1 to 13 mg B for adults. Turkey has almost 70% of world boron reserves principally in four regions: K&uuml / tahya, Emet / Balikesir, Bigadi&ccedil / Eskisehir, Kirka and Bursa, Kemalpasa. The boron content of water in these regions may go up to significant levels. Therefore, it is important to determine B in drinking water from these regions. Electrothermal atomic absorption spectrometry (ETAAS) is a relatively sensitive technique for determination of boron. However, the technique suffers from formation of molecular boron compounds. Therefore, use of chemical modifiers and pyrolytically coated graphite tubes modified with refractory carbide forming elements (Ta, W, Zr, Pd, Ru, Os) were utilized to develop a reliable and sensitive method. Based on optimization studies, Tantalum (Ta) coated tube and co-injection of 5.0 &micro / L 0.01 mol/L Ca(NO3)2, 5.0 &micro / L 0.05 mol/L citric acid together with 15.0 &micro / L sample solution prepared in 1000 mg/L Mg(NO3)2 have been chosen as optimum conditions. Optimum temperatures for pyrolysis and atomization temperatures were determined as 1100 and 2700 &deg / C, respectively. Under these conditions, a detection limit of 0.088 mg/L and a characteristic mass of 186 pg for 15.0 &micro / L sample volume were obtained. The accuracy of the method was checked by EnviroMAT-Waste Water EU-L-1 CRM and NIST 1573a Tomato Leaves SRM analyses. Drinking water samples were collected from Balikesir, Bigadi&ccedil / and K&uuml / tahya, Emet and analyzed by the developed method. Samples were also analyzed by more sensitive techniques / ICP-OES and ICP-MS for a comparison study. The results are compatible with each other.

Boron nitride nanotubes (BNNTs), which are structurally similar to carbon nanotubes (CNTs), were synthesized in 1995 for the first time. They are made up by folding atom sheets which consist of boron and nitrogen atoms into cylindrical form. After their discovery, BNNTs have been attracting great attention due to their extraordinary mechanical, thermal, electrical, and optical properties. In this study, BNNTs were synthesized from the reaction of ammonia gas with the boron and iron powder mixture in a tubular reactor which was connected to a mass spectrometer for on-line chemical analysis of the reactor effluent stream. The synthesized materials were purified with acid treatment. Chemical analysis results showed that nitrogen and hydrogen gases were present in addition to ammonia gas. XRD results revealed that the solid phases in the synthesized material were hexagonal boron nitride, rhombohedral boron nitride, iron, and boron-iron compounds (FeB49 and Fe3B). Reactions taking place in BNNT synthesis were proposed as the decomposition of ammonia gas which was the only gas phase reaction, the formation of boron-iron compounds from the reaction of boron with iron, and boron nitride formation from the reaction of nitrogen with boron-iron compounds. Agglomerated, hollow, multi-walled nanotubes were synthesized with an outer diameter range of 10-550 nm. Both open and close-ended nanotubes were observed. The interlayer distance between BN sheets was measured about 0.33 nm and this distance indicated the d002 plane of hexagonal boron nitride. BNNTs exhibited Type II isotherms with a Type B hysteresis. A decrease in the surface area of the synthesized BNNTs was observed with an increase in temperature. The highest surface area was 147.6 m2/g. Average pore diameter of BNNTs synthesized at different temperatures was around 38 &Aring / . Deposition rate of boron nitride increased with an increase in temperature. After a certain temperature, deposition rate decreased with temperature due to the sintering effect. The highest deposition rate was observed when BNNTs were synthesized with the B/Fe weight ratio of 15/1 at 1300 &deg / C.

This thesis is based on the development of novel catalytic reactions for the synthesis and application of organometallic reagents. The main focus is directed towards organoboronate derivatives. We developed an efficient procedure for converting allylic alcohols to the corresponding allylboronates using palladium pincer complexes as catalysts. The reactions were performed under mild conditions with high selectivity, allowing further one-pot transformations. Using this approach, a variety of stereodefined homoallylic alcohols and amino acid derivatives were synthesized via trapping of the in situ generated allylboronate derivatives with an appropriate electrophile. The synthetic scope of these types of multi-component reactions is broad as many different substrate allylic alcohols may be used together with various electrophiles. Several aspects of these reactions were studied, including different reagents, catalysts and electrophiles. Furthermore, we studied the possibility to use oxidizing reagents as an essential component in the functionalization of olefins. Two main strategies were utilized for these catalytic methods using palladium pincer complexes. The functional group was either transferred from the oxidizing reagent, or introduced via an oxidation-transmetallation route. We propose that both methods involve palladium(IV) intermediates thus expanding both the coordination sphere of palladium and the synthetic scope of pincer complex catalysis. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 11: In press.

Current body armor technologies need further improvements in their design to help reduce combat injuries of military and law enforcement personnel. Kevlar-based body armor systems have good ballistic resistance up to a certain ballistic threat level due to limitations such as decreased mobility and increased weight [1,2]. Kevlar fibers have been modified in this work using a nano-scale boron carbide coating and a marked increase in the puncture resistance has been experimentally observed. It is hypothesized that this improvement is due to the enhancement of the mechanical properties of the individual Kevlar fibers due to the nano-scale coatings. This study presents a comprehensive experimental investigation of individual Kevlar fibers based on nanoindentation to quantify the cause of the enhanced puncture resistance. The experimental setup was validated using copper wires with a diameter size in the same order of magnitude as Kevlar fibers. Results from nanoindentation did not show significant changes in the modulus or hardness of the Kevlar fibers. Scanning Electron Microscopy revealed that the coated fibers had a marked change in their surface morphology. The main finding of this work is that the boron carbide coating did not affect the properties of the individual fibers due to poor adhesion and non-uniformity. This implies that the observed enhancement in puncture resistance originates from the interaction between fibers due to the increase in roughness. The results are important in identifying further ways to enhance Kevlar puncture resistance by modifying the surface properties of fibers.

c-BN has been in focus for several years due to its interesting properties. The possibility for large area CVD is a requirement for the realization of these different properties in various applications. Unfortunately, there are at present severe problems in the CVD growth of c-BN. The purpose with this research project has been to theoretically investigate, using DFT calculations, the possibility for a layer-by-layer CVD growth of c-BN. It could be established that, PEALD, using a BF3-H2-NH3-F2 pulse cycle and a diamond substrate, is a promising method for deposition of c-BN films. The gaseous species will decompose in the plasma and form BFx, H, NHx, and F species (x = 0, 1, 2, 3). The H and F radicals will uphold the cubic structure by completely hydrogenate, or fluorinate, the growing surface. However, surface radical sites will appear during the growth process as a result of atomic H, or F, abstraction reactions. The addition of NHx growth species (x = 0, 1, 2) to B radical sites, and BFx growth species (x = 0, 1, 2) to N radical sites, will then result in a continuous growth of c-BN.

The results of a solid-state 11B NMR study of a series of boronic acids, boronic esters, and boronic acid catechol cyclic esters with aromatic substituents are reported in this thesis. Boron-11 electric field gradient (EFG) and chemical shift (CS) tensors obtained from analyses of spectra acquired in magnetic fields of 9.4 T and 21.1 T are demonstrated to be useful for gaining insight into the molecular and electronic structure about the boron nucleus. It can be concluded that when adequate electronic variation is present in the compounds being studied, Ω is generally the most characteristic boron NMR parameter of the molecular and electronic environment for boronic acids and esters. Importantly, these data are only reliably accessible in ultrahigh magnetic fields. The experimental span values result from a delicate interplay of several competing factors, including hydrogen bonding, the value of the dihedral angle, and the type of aromatic ring system present.

Gold(I) and copper(I) imidazolium complexes were synthesized and probed for use as bulky Lewis acids in frustrated Lewis pairs (FLPs) with bulky phosphines and amines. Their reactivity with small molecules was investigated and the compounds were fully characterized by multinuclear NMR spectroscopy, elemental analysis and X-ray crystallography. Secondly, a new methylene-linked boron-sulfur Lewis acid was synthesized. Its thermodynamic properties were determined and its reactivity with terminal and internal alkynes was demonstrated. Adducts and heterocycles of this boron-sulfur system were fully characterized by multinuclear NMR spectroscopy, elemental analysis and X-ray crystallography. The application of these new systems for the activation of small molecules is described in this thesis.