Several new families of organic acceptors that are candidates as building blocks of molecule-based ferrimagnets were synthesized and characterized. These families include fluorodicyanostilbenes, a tetrachlorodicyanostilbene, naphthyltricyanoethylenes, bromophenyltricyanoethylenes, and an anthryltricyanoethylene. The magnetic networks were synthesized by reacting each acceptor with V(CO)6. The magnets synthesized in this study were characterized using a SQUID magnetometer, elemental analysis, and infrared spectroscopy. Although some combinations failed to yield magnetically ordered materials, others exhibited ordering temperatures in the range of 95 K – 260 K. The ordering temperatures and saturation magnetizations were compared among families of acceptors and correlated with individual properties of the acceptors such as reduction potential and structure. / Doctor of Philosophy / Several new families of organic molecules have been created and examined for use as building blocks of molecule-based magnets. These families include fluorodicyanostilbenes, a tetrachlorodicyanostilbene, naphthyltricyanoethylenes, bromophenyltricyanoethylenes, and an anthryltricyanoethylene. The 3-D magnetic scaffoldings were created by combining an individual organic molecule in one of the families listed above with vanadium. The magnets created in this study were examined using a SQUID magnetometer, elemental analysis, and infrared spectroscopy. Some of the combinations of the organic molecules with vanadium failed to result in a 3-D magnetic scaffolding and showed no magnetic properties. Others showed magnetic properties in the below certain temperatures in the range of 95 K – 260 K. The magnetic properties were compared among families of molecules and correlated with individual properties of each molecule such as electronic effects and structure.

Novel imidazole-containing polyelectrolytes based on poly(1-vinylimidazole) (poly(1VIM)) were functionalized with various hydroxyalkyl-substituents to investigate the influence of charge density and hydrogen bonding on nonviral DNA delivery.  Copolymers with higher charge densities exhibited increased cytotoxicity, whereas increased hydroxyl concentrations remained nontoxic.  DNA binding affinity increased with increased charge densities and increased hydroxyl content.  Dynamic light scattering determined the copolymers which delivered DNA most effectively maintained an intermediate binding affinity between copolymer and DNA.  Copolymers containing higher charge densities or hydroxyl concentrations bound DNA too tightly, preventing its release inside the cell.  Copolymers with lower charge densities failed to protect the DNA from enzymatic degradation.  Tuning hydrogen bonding concentration allowed for a less toxic and more effective alternative to conventional, highly charged polymers for the development of nonviral DNA delivery vehicles.  The synthesis of amine-containing imidazolium copolymers functionalized with low concentrations of folic acid enabled the investigation of additional polymer modifications on nonviral gene delivery.   Functionalization of 1VIM with various hydroxyalkyl and alkyl groups and subsequent conventional free radical polymerization afforded a series of imidazolium-containing polyelectrolytes.  Hydroxyl-containing homopolymers exhibited higher thermal stabilities and lower T_g's compared to the respective alkyl-analog.  X-ray scattering demonstrated the polarity of the hydroxyl group facilitated solvation of the electrostatic interactions disrupting the nanophase-separated morphology observed in the alkylated systems.  Impedance spectroscopy determined hydroxyl-containing imidazolium homopolymers displayed higher ionic conductivities compared to the alkyl-containing analogs which was attributed to increased solvation of electrostatic interactions in the hydroxyl analogs. Beyond functionalizing 1VIM monomers and homopolymers to tailor various properties, the synthesis of novel architectures in a controlled fashion remains difficult due to the radically unstable N-vinyl propagating radical.  The regioisomer 4-vinylimidazole (4VIM) contains two resonance structures affording increased radical stability of the propagating radical.  Nitroxide-mediated polymerization (NMP) and atom transfer radical polymerization (ATRP) failed to control 4VIM homopolymerizations; however, reversible addition-fragmentation chain transfer (RAFT) demonstrated unprecedented control.  Linear pseudo-first order kinetics were observed and successful chain extension with additional 4VIM suggested preservation of the trithiocarbonate functionality. Effectively controlling the polymerization of 4VIM enabled the design of amphoteric block copolymers for emerging applications.  The design of ABA triblock copolymers with 4VIM as a high T_g supporting outer block and di(ethylene glycol) methyl ether methacrylate (DEGMEMA) as a low T_g, inner block, required the development of a new difunctional RAFT chain transfer agent (CTA).  The difunctional CTA successfully mediated the synthesis of the ABA triblock copolymer, poly(4VIM-b-DEGMEMA-b-4VIM), which exhibited microphase separated morphologies.  The amphoteric nature of the imidazole ring required substantially lower concentrations of outer block incorporation compared to traditional triblock copolymers to achieve similar mechanical properties and microphase separated morphologies. / Ph. D.

Ultrasound can be used to create free radicals by growth and collapse of cavitation bubbles. These free radicals have potential use in various fields. The formation of free radicals can be monitored by decrease in T1 during NMR experiments due to paramagnetic effects. Our goal is to develop a method in which ultrasound is used to enhance NMR. By irradiating the sample during analytical measurements, we can decrease T1 which can be used as a non-toxic contrast agent1 producing hydroxyl radicals from the water in the body, invoke NMR enhancement using dynamic nuclear polarization2, control and understand polymer reactions3,4, and study the formation of radicals in chemical systems with EPR5. The experiments conducted indicated a decrease in T1 when ultrasound was applied. A maximum decrease was observed when 104 W of ultrasound power was applied and with higher concentrations of radical producing species. Through the experiments it was evident that the sample temperature increased during sonication. To counter this, gated sonication was used to minimize temperature increase. During sonication, the sample was vigorously mixed. Experiments where the sample was mixed through alternate means and theoretical simulations indicate that sample mixing gives an apparent decrease in T1. In situ sonication to decrease T1 shows promise. The question remains if the decrease is due to a combination of radical production and mixing or just an artifact of sample mixing. This is a difficult parameter to determine but future experiments will attempt to supply further conclusions. / Master of Science

Many pathogenic bacteria can enter phagocytic cells and replicate in them, and these intracellular bacteria are difficult to treat because the recommended antibiotics do not transport into the cells efficiently. Examples include food-borne bacteria such as Salmonella and Listeria as well as more toxic bacteria such as Brucella and the Mycobacteria that lead to tuberculosis. Current treatments utilize aminoglycoside antibiotics that are polar and positively charged and such drugs do not enter the cells in sufficient concentrations to eradicate the intracellular infections. We have developed core-shell polymeric drug delivery vehicles containing gentamicin to potentially overcome this challenge. Pentablock and diblock copolymers comprised of amphiphilic nonionic polyether blocks and anionic poly(sodium acrylate) blocks have been complexed with the cationic aminoglycoside gentamicin. The electrostatic interaction between the anionic polyacrylates and the cationic aminoglycosides form the cores of the nanoplexes, while the amphiphilic nature of the polyethers stabilize their dispersion in physiological media. The amphiphilic nature of the polyethers in the outer shell aid in interaction of the nanoplexes with extra- and intra-cellular components and help to protect the electrostatic core from any physiological media. This thesis investigates the electrostatic cooperativity between the anionic polyacrylates and cationic aminoglycosides and evaluated the release rates of gentamicin as a function of pH. / Master of Science

Thesis advisor: X. Peter Zhang / Chapter 1. Co(II)-Based Metalloradical Catalysis for Stereoselective Radical Cyclopropanation of Alkenes This Account summarizes our group’s recent efforts in developing metalloradical catalysis as a one-electron approach for catalytic radical cyclopropanation of alkenes with diazo compounds. Chapter 2. Asymmetric Radical Process for General Synthesis of Chiral Heteroaryl Cyclopropanes We have developed a Co(II)-based metalloradical system that is highly effective for asymmetric radical cyclopropanation of alkenes with in situ-generated heteroaryldiazomethanes. Through fine-tuning the cavity-like environments of newly developed D2-symmetric chiral amidoporphyrins as the supporting ligand, the optimized Co(II)-based metalloradical system is broadly applicable to pyridyl and other heteroaryldiazomethanes for asymmetric cyclopropanation of a wide range of alkenes, providing general access to valuable chiral heteroaryl cyclopropanes in high yields with excellent diastereoselectivities and enantioselectivities. Chapter 3. Enantioselective Metalloradical 1,6-C–H Alkylation of In Situ-Generated Alkyldiazomethanes for Synthesis of Chiral Piperidines We have disclosed an effective Co(II)-based metalloradical system as a fundamentally different approach to harness the potential of 1,6-HAA radical process, enabling asymmetric 1,6-C–H alkylation of in situ-generated alkyldiazomethanes to construct chiral piperidines. Supported by an optimal D2-symmetric chiral amidoporphyrin ligand, the Co(II)-catalyzed alkylation system is capable of activating a wide array of alkyldiazomethanes containing C(sp3)–H bonds with varied steric and electronic properties, providing access to chiral piperidines in good to high yields with high enantioselectivities from readily accessible 4-aminobutanal derivatives. In addition to practical attributes, such as operational simplicity and mild conditions, the metalloradical system is highlighted by its tolerance to different functional groups as well as compatibility with heteroaryl units. Chapter 4. Design and Synthesis of A Novel D2-Symmetric Chiral Porphyrin for Co(II)-Based Metalloradical Catalysis A novel D2-symmetric chiral amidoporphyrin derived from chiral cyclopropanecarboxamide containing diphenyl units has been effectively constructed based on Co(II)-catalyzed asymmetric cyclopropanation of alkenes. / Thesis (PhD) — Boston College, 2022. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Ultraviolet light damages genomic material by inducing the formation of covalent bonds between adjacent pyrimidines. Cis-syn cyclobutane pyrimidine dimers (CPD)constitute the most abundant primary lesion in DNA. Photolyase, a light-activated enzyme, catalytically repairs these lesions. Although many steps in the photolyase-mediated repair process have been mapped, details of the mechanism remain cryptic. Difference FT-IR spectroscopy was employed to obtain new mechanistic information about photorepair. Purified oligonucleotides, containing a central diuracil, dithymidine, or cyclobutane thymidine dimer, were monitored using vibrational methods. Construction of difference infrared data between undamaged and damaged DNA permitted examination of nucleic acid changes upon formation of the CPD lesion; these experiments indicated that C=O and C-H frequencies can be used as markers for DNA damage. Furthermore, in purified photolyase containing isotopically-labeled aromatic amino acids, we observed that tryptophan residues in photolyase underwent structural changes during photorepair. These data indicate that electron transfer during DNA repair occurs through-bond, and that redox-active, aromatic residues form the pathway for electron transfer. / Master of Science

In many regards, the Black church has been incapable of reaching its fullest potential given its embrace of sexist and heterosexist theologies that marginalize and demonize women and our LGBTQ siblings. This project examines the source of these pernicious theologies and presents an inclusive alternative rooted in the radical love ethic best demonstrated through the life and ministry of Jesus Christ. Appropriating Thomas Groome’s Shared Christian Praxis pedagogy, this project sets forth a path for critically evaluating existing theologies within the Black church; and establishes practices for reconstructing inclusive theologies, in community. By establishing theological foundations that reject the perpetuation of oppression, the Black church can more fully live into its Christian witness, more faithfully engage the work of liberation and more genuinely resemble the Christ whom we seek to serve.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24813号 / 工博第5156号 / 新制||工||1985(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 山子 茂, 教授 辻井 敬亘, 教授 大内 誠 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

The aim of this study is to explore whether Fratelli d’Italia can be classified as a populist radical right party based on their 2022 electoral manifesto. This thesis puts much emphasis on reviewing the existing literature on the understanding and definition of the populist radical right and the radical right. This is since the concept itself has been written extensively on with many different definitions and terminology existing in the scholarly field. Due to this confusion in how to define the concept this study will explain the chosen definition of the populist radical right applied in this thesis in depth.  This thesis will apply Mudde’s (2007) definition of the populist radical with the main ideological attributes being: authoritarianism, nativism and, populism.  The selected method for this study is qualitative content analysis (QCA) which will operationalize the ideological attributes of the populist radical right into main – and subcategories that will guide the analysis of FdI’s 2022 manifesto. The findings from analysing the party’s 2022 manifesto will show that the party can still be assigned to the populist radical right, although, with a revised tone compared to previous manifestos issued from FdI. The result of this study contributes to existing research on contemporary Italian politics and to the study of ideologies.

Polyrotaxanes are molecular composites consisting of three components: linear polymers, bulky stoppers at the ends of polymer chains and macrocycles threaded by the polymers. A series of tetraarylmethyl derivatives as blocking groups were synthesized. Using tris(p-ten-butylphenyl)( 4-hydroxyphenyl)methane a new blocking groupfmitiator (BO(mit) was synthesized. The BG(mit's ability of blockingfmitiation in free radical polymerizations was established by polymerization of styrene. As cyclic components, aliphatic crown ethers (30-crown-lO, "42-crown-14" and "6O-crown-20") were synthesized by multi-piece combination methods. The purification of the crown ethers was achieved by treatment with poly(methacryloyl chloride), column chromatography and recrystallization; by NMR in DMSO-<i>d₆</i> the purity of the products was demonstrated. The 42-crown-based [2]catenane was isolated while synthesizing "42- crown-14" and characterized in terms of its physically interlocked structure. Two new hydrocarbon-based macrocycles were prepared by two-piece combination method. / Ph. D.