Ammonium ionenes are polycations that have quaternary nitrogens in their macromolecular backbone and are synthesized via step-growth polymerization technique. They offer interesting coulombic properties, and the synthetic design provides control over charge density. Non-covalent interactions including nucleobase hydrogen bonding and electrostatics were studied in ammonium ionenes. The non-covalent interactions are expected to increase the effective molecular weight of polymeric precursors and induce microphase separation due to intermolecular associations. The influence of non-covalent interactions on structure-property relationships of ammonium ionenes were studied regarding mechanical (tensile, DMA), thermal (DSC, TGA), and morphological (AFM, SAXS) properties. Hydrogen bonding interaction (10-40 kJ/mol) was introduced using DNA nucleobase pairs such as adenine and thymine. Novel adenine and thymine functionalized segmented and non-segmented ammonium ionenes were successfully synthesized using Michael addition chemistry. In non-segmented systems, we investigated the influence of spacer length on homoassociation and heteroassociation of complementary nucleobase-containing ionenes. Based on DSC analyses, complementary non-segmented ionenes made miscible blends. The Tgs of ionene blends with shorter spacer length (4 bonds between the nucleobase and secondary amine in the polymer backbone) followed the Fox equation, which indicated no intermolecular interactions. The longer alkyl spacer (9 bonds between nucleobase and secondary amine in the polymer backbone) provided efficient flexibility for the self-assembly process to occur. Thus, increasing the spacer length from 4-bonds to 9-bonds, the Tgs of the blends deviated from both Fox and Gordon-Taylor equations and demonstrated the presence of hydrogen bonding interactions. In segmented systems, we investigated the association between nucleobase-containing ionenes and their complementary guest molecules. Job's method revealed a 1:1 stoichiometry for the hydrogen-bonded complexes. These association constants for the 1:1 complexes, based on the Benesi-Hildebrand model were 94 and 130 M-1 respectively, which were in agreement with literature values for adenine and thymine nucleobase pairs (10-100 M-1). DSC thermograms confirmed no macrophase separation for 1:1 [ionene-A/T]:[guest molecule] complexes based on the disappearance of the melting peak of the guest molecule. Morphological studies including atomic force microscopy (AFM) demonstrated a reduced degree of microphase separation for the 1:1 complexes due to the disruption of adenine-adenine or thymine-thymine interactions. Poly(dimethyl siloxane)-based ammonium ionenes having various hard segment contents were synthesized. The charge density or hard segment content was tuned for appropriate application using low molecular weight monomer. The change in hard segment content had a profound effect on thermal, mechanical, rheological, and gas permeability. Microphase separation was confirmed using DSC and DMA in these systems. DMA showed that the rubbery plateau modulus extended to higher temperatures with increasing hard segment content. Tensile analysis demonstrated systematic increase in modulus of PDMS-ionenes with increasing hard segment content. Oxygen transmission rates decreased linearly as the wt% hard segment increased. / Ph. D.

Developing a fundamental understanding of the interactions of chemical warfare agents (CWAs) with surfaces is essential for the rational design of new sorbents, sensors, and decontamination strategies. The interactions of chemical warfare agent simulants, molecules which retain many of the same chemical or physical properties of the agent without the toxic effects, with amorphous silica were conducted to investigate how small changes in chemical structure affect the overall chemistry. Experiments investigating the surface chemistry of two classes of CWAs, nerve and blister agents, were performed in ultrahigh vacuum to provide a well-characterized system in the absence of background gases. Transmission infrared spectroscopy and temperature-programmed desorption techniques were used to learn about the adsorption mechanism and to measure the activation energy for desorption for each of the simulant studied. In the organophosphate series, the simulants diisopropyl methylphosphonate (DIMP), dimethyl methylphosphonate (DMMP), trimethyl phosphate (TMP), dimethyl chlorophosphate (DMCP), and methyl dichlorophosphate (MDCP) were all observed to interact with the silica surface through the formation of a hydrogen bond between the phosphoryl oxygen of the simulant and an isolated hydroxyl group on the surface. In the limit of zero coverage, and after defect effects were excluded, the activation energies for desorption were measured to be 57.9 ± 1, 54.5 ± 0.3, 52.4 ± 0.6, 48.4 ± 1, and 43.0 ± 0.8 kJ/mol for DIMP. DMMP, TMP, DMCP, and MDCP respectively. The adsorption strength was linearly correlated to the magnitude of the frequency shift of the ν(SiO-H) mode upon simulant adsorption. The interaction strength was also linearly correlated to the calculated negative charge on the phosphoryl oxygen, which is affected by the combined inductive effects of the simulants' different substituents. From the structure-function relationship provided by the simulant studies, the CWA, Sarin is predicted to adsorb to isolated hydroxyl groups of the silica surface via the phosphoryl oxygen with a strength of 53 kJ/mol. The interactions of two common mustard simulants, 2-chloroethyl ethyl sulfide (2-CEES) and methyl salicylate (MeS), with amorphous silica were also studied. 2-CEES was observed to adsorb to form two different types of hydrogen bonds with isolated hydroxyl groups, one via the S moiety and another via the Cl moiety. The desorption energy depends strongly on the simulant coverage, suggesting that each 2-CEES adsorbate forms two hydrogen bonds. MeS interacts with the surface via a single hydrogen bond through either its hydroxyl or carbonyl functionality. While the simulant work has allowed us to make predictions agent-surface interactions, actual experiments with the live agents need to be conducted to fully understand this chemistry. To this end, a new surface science instrument specifically designed for agent-surface experiments has been developed, constructed, and tested. The instrument, located at Edgewood Chemical Biological Center, now makes it possible to make direct comparisons between simulants and agents that will aid in choosing which simulants best model live agent chemistry for a given system. These fundamental studies will also contribute to the development of new agent detection and decontamination strategies. / Ph. D.

With its unrivaled versatility and atom economy, olefin metathesis is arguably the most powerful catalyst methodology now known for the construction of carbon-carbon bonds. When compared to palladium-catalyzed cross-coupling methodologies, however, catalyst productivity lags far behind, even for the “robust” ruthenium metathesis catalysts. Unexpected limitations to the robustness of these catalysts were first widely publicized by reports describing the implementation of metathesis in pharmaceutical manufacturing. Recurring discussion centered on low catalyst productivity resulting from decomposition of the Ru catalysts by impurities, including ppm-level contaminants in the technical-grade solvent. Over the past 7 years, a series of mechanistic studies from the Fogg group has uncovered the pathways by which common contaminants (or indeed reagents) trigger catalyst decomposition. Two principal pathways were identified: abstraction of the alkylidene or methylidene ligand by nucleophiles, and deprotonation of the metallacyclobutane intermediate by Bronsted base. Emerging applications, however, notably in chemical biology, highlight new challenges to catalyst productivity. The first part of this thesis emphasizes the need for informed mechanistic insight as a guide to catalyst redesign. The widespread observation of a cyclometallated N-heterocyclic carbene (NHC) motif in crystal structures of catalyst decomposition products led to the presumption that activation of a C-H bond in the NHC ligand initiates catalyst decomposition. Reducing NHC bulk has therefore been proposed as critical to catalyst redesign. In experiments designed to probe the viability of this solution, the small NHC ligand IMe4 (tetramethylimidazol-2-ylidene) was added to the resting-state methylidene complexes formed in metathesis by the first- and second-generation Grubbs catalysts (RuCl2(PCy3)2(=CH2) GIm or RuCl2(H2IMes)(PCy3)(=CH2) GIIm, respectively). The intended product, a resting-state methylidene species bearing a truncated NHC, was not formed, owing to immediate loss of the methylidene ligand. Methylidene loss is now shown to result from nucleophilic attack by the NHC – a small, highly potent nucleophile – on the methylidene. Density functional calculations indicate that IMe4 abstracts the methylidene, generating the N-heterocyclic olefin H2C=IMe4. The latter is an even more potent nucleophile, which attacks a second methylidene, resulting in liberation of [EtIMe4]Cl. These findings report indirectly on the original question concerning the impact of ligand truncation. The ease with which a small, potent nucleophile can abstract the key methylidene ligand from GIm and GIIm underscores the importance of increasing steric protection at the [Ru]=CH2 site. This chemistry also suggests intriguing possibilities for efficient, selective, controlled methylidene abstraction to terminate metathesis activity while leaving the “RuCl2(H2IMes)(PCy3)” core intact. This could prove an enabling strategy for tandem catalysis applications in which metathesis is the first step. The second part of this thesis, inspired by the potential of olefin metathesis in chemical biology, focuses on the impact of hydroxide ion and water on the productivity of phosphine-free metathesis catalysts. In reactions with the important second-generation Hoveyda catalyst HII, hydroxide anion is found to engage in salt metathesis with the chloride ligands, rather than nucleophilic attack. The resulting Ru-hydroxide complex is unreactive toward any olefins larger than ethylene, while ethylene itself causes rapid decomposition. Proposed as the decomposition pathway is bimolecular coupling promoted by the strong H-bonding character of the hydroxide ligands. Lastly, the impact of the water on Ru-catalyzed olefin metathesis is examined. In a survey of normally facile metathesis reactions using state-of-the-art catalysts, even trace water (0.1% v/v) is found to be highly detrimental. The impact of water is shown to be greater at room temperature than previously established at 60 °C. Preliminary evidence strongly suggests that the mechanism by which water induces decomposition is temperature-dependent. Thus, at high temperature, decomposition of the metallacyclobutane intermediate appears to dominate, but this pathway is ruled out at ambient temperatures. Instead, water is proposed to promote bimolecular decomposition. Polyphenol resin, which can sequester water by H-bonding, is shown to offer an interim solution to the presence of trace water in organic media. These findings suggest that major avenues of investigation aimed at reducing intrinsic catalyst decomposition may likewise be relevant to the development of water-tolerant catalysts.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18518号 / 工博第3910号 / 新制||工||1600(附属図書館) / 31404 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 澤本 光男, 教授 伊藤 紳三郎, 教授 中條 善樹 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

付記する学位プログラム名: 充実した健康長寿社会を築く総合医療開発リーダー育成プログラム / 京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21798号 / 工博第4615号 / 新制||工||1719(附属図書館) / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 松田 建児, 教授 杉野目 道紀, 教授 浜地 格 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

No description available.

Flavonols are hydroxyl-substituted flavonoids and naturally occur as secondary metabolites in plants. Several studies have discovered extensive medicinal properties of flavonols. The present work reports on structural and functional investigation of the B ring substituted flavonols based on spectroscopic and electrochemical techniques. The purpose of this study is to determine the influence of the B ring substitutions on the hydrogen bonding interactions, the electronic effects in ruthenium complexes and the Al3+ chelation of B ring substituted flavonols. The electronic effects of the B rings were changed by introducing methyl, methoxy and nitro groups at position 4ʹ on the B ring. The 3ʹ-methyl substitution was performed in order to increase the electronic density of the B ring via inductive effects. The 2ʹ-methyl and 2ʹ, 6ʹ-dimethyl substitutions increased the steric effects around the inter-ring bond between the B and the C rings, and the B ring was highly deconjugated from the AC rings. The intramolecular hydrogen bonding distances at 3-hydroxy-4-carbonyl units of the B ring substituted flavonols were elongated while the dihedral angles between the B and AC increased. Strong intermolecular hydrogen bonding interactions were also observed in the crystal structures of 4ʹ-methylflavonol, 4ʹ-methoxyflavonol, 4ʹ-nitroflavonol and 2ʹ,6ʹ-dimethylflavonol. Furthermore, several crystal packing patterns were observed, and it is postulated that dihedral angles and intramolecular hydrogen bonding distances are both affected by the intermolecular hydrogen bonding interactions and the crystal packing forces. In addition, the ruthenium complexes of B ring substituted flavonols were synthesized and characterized by spectroscopic and electrochemical techniques. B ring substitution effects were minimal in IR spectroscopy and X-ray crystallography. The levels of the conjugation of the rutheniumlavonolate complexes were demonstrated by electronic absorption spectra recorded in methanol at room temperature. The most positive oxidation potential was obtained with the electron withdrawing nitro group substitution, and the electron donating substitutions resulted in more negative oxidation potentials. The spectroscopic investigation of the complex formation of Al(III) with flavonols and 3-hydroxychromone is described. The stoichiometric composition and stability constants are also given. The comparison of the results obtained from Al(III) chelation shows significant effects of the B ring substitutions.

The purpose of this dissertation is to investigate the thermochemical properties of nonelectrolyte solutes dissolved in ternary solvent mixtures, and to develop mathematical expressions for predicting and describing behavior in the solvent mixtures. Forty-five ternary solvent systems were studied containing an ether (Methyl tert-butyl ether, Dibutyl ether, or 1,4-Dioxane), an alcohol (1-Propanol, 2-Propanol, 1-Butanol, 2-Butanol, or 2-Methyl-1-propanol), and an alkane (Cyclohexane, Heptane, or 2,2,4-Trimethylpentane) cosolvents. The Combined NIBS (Nearly Ideal Binary Solvent)/Redlich-Kister equation was used to assess the experimental data. The average percent deviation between predicted and observed values was less than ± 2 per cent error, documenting that this model provides a fairly accurate description of the observed solubility behavior. In addition, Mobile Order theory, the Kretschmer-Wiebe model, and the Mecke-Kempter model were extended to ternary solvent mixtures containing an alcohol (or an alkoxyalcohol) and alkane cosolvents. Expressions derived from Mobile Order theory predicted the experimental mole fraction solubility of anthracene in ternary alcohol + alkane + alkane mixtures to within ± 5.8%, in ternary alcohol + alcohol + alkane mixtures to within ± 4.0%, and in ternary alcohol + alcohol + alcohol mixtures to within ± 3.6%. In comparison, expressions derived from the Kretschmer-Wiebe model and the Mecke-Kempter model predicted the anthracene solubility in ternary alcohol + alkane + alkane mixtures to within ± 8.2% and ± 8.8%, respectively. The Kretschmer-Wiebe model and the Mecke-Kempter model could not be extended easily to systems containing two or more alcohol cosolvents.

No description available.

We have modelled structures and dynamics of hydrogen bond networks that form from imidazoles tethered to oligomeric aliphatic backbones in crystalline and glassy phases. We have studied the behavior of oligomers containing 5 or 10 imidazole groups. These systems have been simulated over the range 100-900 K with constantpressure molecular dynamics using the AMBER 94 force field, which was found to show good agreement with ab initio calculations on hydrogen bond strengths and imidazole rotational barriers. Hypothetical crystalline solids formed from packed 5-mers and 10-mers melt above 600 K, then form glassy solids upon cooling. Viewing hydrogen bond networks as clusters, we gathered statistics on cluster sizes and percolating pathways as a function of temperature, for comparison with the same quantities extracted from neat imidazole liquid. We have found that, at a given temperature, the glass composed of imidazole 5-mers shows the same hydrogen bond mean cluster size as that from the 10-mer glass, and that this size is consistently larger than that in liquid imidazole. Hydrogen bond clusters were found to percolate across the simulation cell for all glassy and crystalline solids, but not for any imidazole liquid. The apparent activation energy associated with hydrogen bond lifetimes in these glasses (9.3 kJ/mol) is close to that for the liquid (8.7 kJ/mol), but is substantially less than that in the crystalline solid (13.3 kJ/mol). These results indicate that glassy oligomeric solids show a promising mixture of extended hydrogen bond clusters and liquid-like dynamics. This study prompted a continued look at smaller oligomers (monomers, dimers, trimers, and pentamers). Using many of the above statistics we found that decreased chain length decreased the tendency to form global hydrogen bonding networks (percolation pathways). We also developed an reorientational correlation for the imidazole ring which allowed us to extract a timescale for reorientation. Smaller chains produce faster reorientation timescales and thus there is a trade off between faster reorientation dynamics and long global hydrogen bonding networks. Moreover we showed that homogeneity of chain length has no effect on hydrogen bonding statistics. Initial development on a multi-state empirical valence bond model has been to study proton transfer in liquid imidazole. We have shown that GAFF produces very large proton transfer barriers created by a highly repulsive N· · ·H VDW interaction at the transition point. In order to produce an acceptable fit to the potential energy surface while still producing stable dynamics this interaction must be turned off. This is in contrary to what is reported in the literature [14]. Using our model we have produced simulations with acceptable drift in the total energy (3.2 kcal/mol per ns) and negligible drift in the temperature (.12 K/ns).