Yes / Boron neutron capture therapy (BNCT) has a long history of unfulfilled promises for the treatment of aggressive cancers. In the last two decades, chemists, physicists, and clinical scientists have been coordinating their efforts to overcome practical and scientific challenges needed to unlock its full therapeutic potential. From a chemistry point of view, the two current small-molecule drugs used in the clinic were developed in the 1950s, however, they both lack some of the essential requirements for making BNCT a successful therapeutic modality. Novel strategies are currently used to design new drugs, more selective towards cancer cells and tumours, as well as able to deliver high boron contents to the target. In this context, macromolecules, including polymers, are promising tools to make BNCT an effective, accepted, and front-line therapy against cancer. In this review, we will provide a brief overview of BNCT, and its potential and challenges, and we will discuss the most promising strategies that have been developed so far.

Conventional desalination plant, municipal water supply and wastewater treatment system are among the most electricity-intensive facilities. Microbial Desalination Cell (MDC) has emerged as a promising technique to capture the chemical energy stored in wastewater directly for desalination, which has the potential to solve the high energy consumption issue in desalination industry as well as wastewater treatment system. The MDC is composed of two critical components, the electrodes (anode and cathode), and the ion-exchange membranes separating the two electrodes which drive anions migrate towards the anode, and cations migrate towards the cathode. The multiple components allow us to manipulate the configuration to achieve most efficient desalination performance. By coupling with Donnan Dialysis or Microbial Fuel Cell, the device can effectively achieve boron removal which has been a critical issue in desalination plants. The uncertainty of water quality of the final desalinated water caused by contaminant back diffusion from the wastewater side can be theoretically explained by two mechanisms, Donnan exchange and molecule transport which are controlled by bioelectricity and concentration gradient. Scaling and fouling is also a factor needs to be taken into consideration when operating the MDC system in real world. With mathematical modeling, we can provide insight to bridge the gap between lab-scale experiments and industrial applications. This study is expected to provide guidance to enhance the efficiency as well as the reliability and controllability of MDC for desalination. / Ph. D. / Water and energy are the world’s most valuable resources. The recent emerging technology, Microbial Desalination Cell (MDC), however, can achieve wastewater treatment, desalination for fresh water production, and energy generation simultaneously. Owing to the anodophilic microorganisms working as organic matter consumer and electron generator, the wastewater can be cleaned and the device can generate electricity through electron flow to drive ion separation for salt removal in the solution. The MDC can be constructed in versatile configurations. Decoupled configuration of anode and cathode allows flexibility of operation and maintenance. Although the MDC has wastewater adjacent to seawater which are separated by a piece of anion exchange membrane, the microorganisms and viruses are effectively blocked by the membrane which has tiny pore size around 1 nm. Back diffusion of contaminants in wastewater into the desalinated water is minimal under bioelectricity generation condition. The MDC has proved to successfully remove various inorganic ions by itself as well as remove non-dissociable boron when coupled to other devices, such as Donnan Dialysis or Microbial Fuel Cell. The water product quality can meet irrigation guideline. Through mathematical modeling tools, we can better understand the MDC process, analyze it, and make informative predictions.

Thesis advisor: James P. Morken / Thesis advisor: Peter X. Zhang / This dissertation presents research on novel synthetic methodologies and mechanistic studies focused on boron chemistry in organic synthesis. Chapter one introduces the “sam” auxiliary, a chiral ligand designed to enhance stereoselectivity in cycloaddition reactions. The auxiliary's synthesis, installation on alkenyl boron species, and applications in cycloadditions with nitrones, glycine imine ylides, and radicals are discussed, demonstrating high-yielding and stereoselective results. Chapter two introduces a catalytic enantioselective Suzuki-Miyaura cross-coupling reaction for desymmetrizing vicinal bis(boronic) esters, synthesizing enantiomerically enriched substituted carbocycles and heterocycles while retaining a boronic ester. Mechanistic studies highlighted the cooperative effect of vicinal boronic esters, and practical applications were demonstrated through the synthesis of bioactive molecules. Chapter three discusses the catalytic enantioselective synthesis of disubstituted nortricyclanes as meta benzene isosteres and the acid-catalyzed rearrangement of borylated norbornenes. Boron moieties were crucial for enhancing reactivity and selectivity. Overall, this dissertation demonstrates the potential of boron chemistry in developing new synthetic methodologies, offering valuable insights for advancing organic synthesis and medicinal chemistry. / Thesis (PhD) — Boston College, 2024. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Master of Science / Department of Chemical Engineering / James H. Edgar / Pure boron exists in two main polymorphs, the common β-rhombohedral boron and the relatively rare α-rhombohedral boron. α-rhombohedral boron (α-B) possesses several extraordinary properties: self-healing from radiation damage and a high hole mobility. In addition, the [superscript]10B isotope has a large thermal neutron capture cross section. Such properties make it an excellent candidate for novel electronic device, such as direct energy conversion devices (alphacells and betacells) and neutron detectors. However, research on the properties and applications of α-B has been limited due to the difficulty to produce high quality α-B crystals of significant size. The preparation of α-rhombohedral boron is challenging for several reasons: first, α-rhombohedral boron has a low thermodynamic stability; it is only stable below 1100°C, at higher temperature β-rhombohedral boron is the stable polymorph. In addition, at elevated temperatures, boron is highly reactive, which make it is difficult to produce pure boron crystals. The primary goal of this research was to produce high quality α-B crystals of significant size. The main focus of this study was to explore the feasibility of producing α-B from a copper flux. Copper is a promising solvent for α-B crystal growth: the eutectic temperature of copper-boron is low, 996°C, and the phase diagram of copper-boron is relatively simple, and there are not many intermediate boride-copper compounds. In addition, copper is easily removed from crystals by etching with concentrated nitric acid. Last but not least, copper is less expensive than other metal solvents such as platinum. Boron crystal growth from a platinum solvent and vapor-liquid-solid growth by chemical vapor deposition were also performed for comparison. A series of crystals were grown over a range of initial boron concentrations (9.9 to 27.7 mole %) and cooling rates. Small irregular-shaped black crystals (>100μm) and well-faceted red crystals in various shapes, as large as 500 microns were produced. The crystals were characterized by optical microscopy, scanning electron microscopy, energy dispersive spectroscopy, x-ray diffraction analysis, and Raman spectroscopy. The correlation between experiment results and experimental parameters (source materials, the purity of growth atmosphere, and crucible materials, etc.) are reported. Suggestions about further investigation for α-B crystal growth are proposed.

This thesis is a theoretical study of configurational disorder in icosahedral boron-rich solids, in particular boron carbide, including also the development of a methodological framework for treating configurational disorder in such materials, namely superatom-special quasirandom structure (SA-SQS). In terms of its practical implementations, the SA-SQS method is demonstrated to be capable of efficiently modeling configurational disorder in icosahedral boron-rich solids, whiles the thermodynamic stability as well as the properties of the configurationally disordered icosahedral boron-rich solids, modeled from the SA-SQS method, can be directly investigated, using the density functional theory (DFT). In case of boron carbide, especially B4C and B13C2 compositions, the SA-SQS method is used for modeling configurational disorder, arising from a high concentration of low-energy B/C substitutional defects. The results, obtained from the DFT-based calculations, demonstrate that configurational disorder of B and C atoms in boron carbide is not only thermodynamically favored at high temperature, but it also plays an important role in altering the properties of boron carbide − for example, restoration of higher rhombohedral symmetry of B4C, a metal-to-nonmetal transition and a drastic increase in the elastic moduli of B13C2. The configurational disorder can also explain large discrepancies, regarding the proper- ties of boron carbide, between experiments and previous theoretical calculations, having been a long standing controversial issue in the field of icosahedral boron- rich solids, as the calculated properties of the disordered boron carbides are found to be in qualitatively good agreement with those, observed in experiments. In order to investigate the configurational evolution of B4C as a function of temperature, beyond the SA-SQS level, a brute-force cluster-expansion method in combination with Monte Carlo simulations is implemented. The results demonstrate that configurational disorder in B4C indeed essentially takes place within the icosahedra in a way that justifies the focus on lowenergy defect patterns of the superatom picture. The investigation of the thermodynamic stability of icosahedral carbon-rich boron carbides beyond the believed solubility limit of carbon (20 at.% C) demonstrates that, apart from B4C generally addressed in the literature, B2.5C represented by B10Cp2(CC) is predicted to be thermodynamically stable with respect to B4C as well as pure boron and carbon under high pressure, ranging between 40 and 67 GPa, and also at elevated temperature. B2.5C is expected to be metastable at ambient pressure, as indicated by its dynamical and mechanical stabilities at 0 GPa. A possible synthesis route of B2.5C and a fingerprint for its characterization from the simulations of x-ray powder diffraction pattern are suggested. Besides modeling configurational disorder in boron carbide, the SA-SQS method also opens up for theoretical studies of new alloys between different icosahedral boron-rich solids − for example, (B6O)1−x(B13C2)x and B12(As1−xPx)2. As for the pseudo-binary (B6O)1−x(B13C2)x alloy, it is predicted to display a miscibility gap resulting in B6O-rich and either ordered or disordered B13C2-rich domains for intermediate global compositions at all temperatures up to melting points of the materials. However, some intermixing of B6O and B13C2 to form solid solutions is also predicted at high temperature. A noticeable mutual solubility of icosahedral B12As2 and B12P2 in each other to form B12(As1−xPx)2 disordered alloy is predicted even at room temperature, and a complete closure of a pseudo-binary miscibility gap is achieved at around 900 K. Apart from B12(As1−xPx)2, the thermodynamic stability of other compounds and alloys in the ternary B-As-P system is also investigated. For the binary B-As system, zincblende BAs is found to be thermodynamically unstable with respect to icosahedral B12As2 and gray arsenic at 0 K and increasingly so at higher temperature, indicating that BAs may merely exist as a metastable phase. This is in contrast to the binary B-P system, in which zinc-blende BP and icosahedral B12P2 are both predicted to be stable. Owing to the instability of BAs with respect to B12As2 and gray arsenic, only a tiny amount of BAs is predicted to be able to dissolve in BP to form BAs1−xPx disordered alloy at elevated temperature. For example, less than 5% BAs can dissolve in BP at 1000 K. As for the binary As-P system, As1−xPx disordered alloys are predicted at elevated temperature − for example, a disordered solid solution of up to ∼75% As in black phosphorus as well as a small solubility of ∼1% P in gray arsenic at 750 K, together with the presence of miscibility gaps. The thermodynamic stability of three different compositions of α-rhombohedral boron-like boron subnitride, having been proposed so far in the literature, is investigated. Those are, B6N, B13N2, and B38N6, represented respectively by B12(N-N), B12(NBN), and [B12(N-N)]0.33[B12(NBN)]0.67. It is found that, out of these sub- nitrides, only B38N6 is thermodynamically stable from 0 GPa up to ∼7.5 GPa, depending on the temperature, and is thus concluded as a stable composition of α-rhombohedral boron-like boron subnitride.

<p>In vapour phase deposition, the knowledge and control of homogeneous and heterogeneous reactions in connection to precursor design may lead to the deposition of the desired material; structure or phase. This thesis is a document attempting to increase the knowledge of film growth in the B-N system.</p><p>In the present work, surface processes like adsorption, abstraction, migration and nucleation have been modelled on an atomic scale using density functional theory (DFT). The systems studied are mainly cubic and hexagonal boron nitride surfaces ((c-BN) vs. (h-BN)), but also the α-boron (001) surface.</p><p>It has been shown that DFT and a cluster approach is a reliable tool in modelling boron nitride surfaces and surface processes, provided that certain functionals, basis sets and geometrical constraints are used.</p><p>By using surface stabilisers such as H species in an electron- or radical-rich environment, it has been shown that <i>i)</i> the structure of cubic boron nitride surfaces can be sustained, and <i>ii)</i> c-BN may nucleate on the h-BN (001) basal plane. Furthermore, the nucleation of c-BN from arbitrary and experimental growth species is energetically preferable over a continuous growth of h-BN on the h-BN (001) edges.</p><p>An atomic layer deposition (ALD) process for boron nitride was developed. It resulted in turbostratic (t-BN), transparent, well-adherent and almost atomically smooth BN films. However, with the cubic phase of boron nitride absent in the ALD films, more effort needs to be put into both the theoretical and the experimental branches of this field of science.</p>

In vapour phase deposition, the knowledge and control of homogeneous and heterogeneous reactions in connection to precursor design may lead to the deposition of the desired material; structure or phase. This thesis is a document attempting to increase the knowledge of film growth in the B-N system. In the present work, surface processes like adsorption, abstraction, migration and nucleation have been modelled on an atomic scale using density functional theory (DFT). The systems studied are mainly cubic and hexagonal boron nitride surfaces ((c-BN) vs. (h-BN)), but also the α-boron (001) surface. It has been shown that DFT and a cluster approach is a reliable tool in modelling boron nitride surfaces and surface processes, provided that certain functionals, basis sets and geometrical constraints are used. By using surface stabilisers such as H species in an electron- or radical-rich environment, it has been shown that i) the structure of cubic boron nitride surfaces can be sustained, and ii) c-BN may nucleate on the h-BN (001) basal plane. Furthermore, the nucleation of c-BN from arbitrary and experimental growth species is energetically preferable over a continuous growth of h-BN on the h-BN (001) edges. An atomic layer deposition (ALD) process for boron nitride was developed. It resulted in turbostratic (t-BN), transparent, well-adherent and almost atomically smooth BN films. However, with the cubic phase of boron nitride absent in the ALD films, more effort needs to be put into both the theoretical and the experimental branches of this field of science.

GaN-based HEMTs are among the most promising candidates for high-power and high-frequency applications; a niche for millimeter-wave technologies. Nitride materials indeed outperform other mainstream III-V materials (InP or GaAs) because of several properties, including wider bandgaps, high peak and saturation velocities, large breakdown voltages, together with good thermal conductivities. Nonetheless, the state-of-the-art of nitrides is not yet industrially mature to exploit the entire millimeter-wave range. A way to push further performance is to develop innovative designs, notably by exploring novel materials. The purpose of this research was therefore to investigate the use of boron-containing III-nitrides in high electron mobility transistors (HEMTs). The study was first conducted theoretically, through solving the Schrodinger-Poisson equation. Key parameters and relevant equations were derived to implement BGaN materials in our simulations. A GaN/ultrathin-BGaN/GaN heterojunction was showed to provide an electrostatic barrier to electrons and to improve the confinement of the two-dimensional electron gas. GaN back-barrier layers happen to limit leakage in the GaN buffer thanks to two effects: (i) a polarization-induced band discontinuity and (ii) a resistive barrier originating from excellent insulation properties of BGaN. The study was then, experimentally, several growth campaigns were carried out that led to the fabrication of devices. First, we confirmed the key characteristics of BGaN materials by electrical and optical measurements. Second, we demonstrated the evidence of a significant enhancement of performance of standard AlGaN/GaN structures by the introduction of a BGaN layer in the buffer layer. Compared to conventional AlGaN/GaN HEMTs, structures grown with BGaN back-barriers showed a significant improvement of static performances, transport properties, and trapping effects involving a limited current collapse in dynamic regime.

Formation of hexagonal boron nitride (h-BN) by carbothermic reduction of B2O3 under nitrogen atmosphere at 1500oC was investigated. Reaction products were subjected to powder X-ray diffraction analysis, chemical analysis and were examined by SEM. B4C was found to exist in the reaction products of the experiments in which h-BN formation was not complete. One of the aims of this study was to investigate the role of B4C in the carbothermic production of h-BN. For this purpose, conversion reaction of B4C into h-BN was studied. B4C used in these experiments was produced in the same conditions that h-BN was formed, but under argon atmosphere. It was found that formation of h-BN from B4C&ndash / B2O3 mixtures was slower than activated C&ndash / B2O3 mixtures. It was concluded that B4C is not a necessary intermediate product in the carbothermic production of h-BN. Some additives are known to catalytically affect the h-BN formation. The second aim of this study was to examine the catalytic effect of some alkaline earth metal oxides and carbonates, some transition metal oxides and cupric nitrate. It was found that addition of 10wt% CaCO3 into the B2O3+C mixture was optimum for increasing the rate and yield of h-BN formation and decreasing the B4C amount in the products and that the reaction was complete in 2 hours. CaCO3 was observed to be effective in increasing the rate and grain size of the formed h-BN. Addition of cupric nitrate together with CaCO3 provided a further increase in the size of the h-BN grains.

Both deficiency and toxicity of the essential micronutrient boron (B) lead to reduced crop yield in agriculture. However, our understanding of the molecular responses of plants under B stresses to tackle the yield loss is limited. Therefore, in the present study, transcriptional alterations in sensitive and tolerant barley cultivars under B deficiency and toxicity were investigated in order to reveal the molecular responses. Transcriptomes were monitored at seedling stage by global expression profiling using oligonucleotide microarrays. In the context of the study, we have determined that response to B toxicity in barley involved jasmonic acid and various components of biotic stress responses. Examination of expression profiles indicated that B toxicity and deficiency resulted in significant global changes in the transcriptomes of leaf and root tissues, respectively. Inter-varietal comparison of sensitive and tolerant genotypes of barley revealed that a combinatorial effect of transcription factors on regulation could alter the gene expression patterns in tolerant cultivar and provide B toxicity tolerance. Furthermore, mechanisms of vacuolar sorting or efflux by transporters and aquaporins might be contributing to the tolerance to B stresses in barley according to the results of this study. Additionally, we have identified and cloned the HvBor1a gene encoding a putative B transporter in barley using candidate gene approach and functionally characterized its roles in the tolerance to B stresses. The full length coding sequence and also the non-coding regions of the gene were identified. It was demonstrated that the protein product of HvBor1a was localized to the plasma membrane and it displayed B transporter activity. High transcript abundances in leaf tissues of barley suggested a role for HvBor1a in re-distribution of B within the plant tissues. Interestingly, examination of last intron of HvBor1a has led to the identification of an alternatively spliced variant in certain cultivars of barley. Furthermore, interval mapping and positional cloning was performed to locate the HvBor1a on 3H B tolerance QTL and a novel CAPS marker was developed to narrow the genetic distances at the locus. As a conclusion, this work presents, for the first time, the transcriptome profiling of a member of Triticeae under B toxicity and deficiency. The data generated should enlighten succeeding studies to unravel molecular mechanisms and signaling networks of tolerance to B stresses especially in crops like barley and wheat. The results of the study will provide novel tools and genes for conventional and biotechnological approaches for the reduction of yield loss due to B toxicity or deficiency.