Rozprawy doktorskie na temat „Hydrogen donors”

The results of combined IR absorption and photoconductivity studies on hydrogen donors in ZnO and TiO2 are presented. It is shown that hydrogen donors in ZnO and rutile TiO2 can be detected as Fano resonances in the photoconductivity spectra at the frequencies corresponding to the vibrational modes of these defects. In the case of anatase TiO2 IR absorption lines at 3412 and 3417 cm-1 are assigned to the stretching local vibrational modes of a donor in the neutral and the positive charge states, respectively. Interstitial hydrogen is suggested as a tentative model for the defect giving rise to these vibrational modes.

Anions are important in many biological and chemical processes, therefore the development of receptors for binding, sensing and extraction is necessary for a range of potential applications, including in medicine and the environment. This thesis details both the development of novel dual hydrogen bonding receptors for anions, and work towards anion sensing and extraction using dual hydrogen bonding motifs. Chapter 2 describes the synthesis and anion binding investigations into the dual hydrogen bond donating motifs diaminomethylenemalononitriles and diaminomethyleneindanediones. Two novel series of compounds were synthesised and anion affinity and selectivity determined in organic solvent via 1H NMR titrations, crystallographic and computational analysis. Anion binding properties are compared to the widely researched thiourea motif. In Chapter 3, the powerful dual H-bond donating squaramide moiety is appended with fluorophores either directly or through a methylene spacer to produce a library of novel fluorogenic squaramide receptors. The acidity of these squaramides substituents was determined experimentally in order to understand their behaviour in DMSO. UV-Vis and fluorescence anion screens and titrations were performed, which indicate that ratiometric anion sensing can take place in DMSO, induced by aggregation/disaggregation mechanisms upon interaction with anions. Selectivity was observed for interaction with sulfate, acetate and dihydrogen phosphate, with interaction with sulfate resulting in the greatest fluorescence response for all receptors. Chapter 4 describes the development of squaramide-functionalised polymers for anion sensing and extraction. Water soluble polyethylene glycol methyl methacrylate based polymers were functionalised with squaramides and anion binding investigated by UV-Vis and fluorescence screens, and by 1H NMR titration. When dissolved in water, the squaramide appended polymer undergoes a phase transition upon heating. This is exploited to lead to anion extraction that offers selectivity for sulfate and dihydrogen phosphate over anions that are bound less strongly by the squaramide moiety.

Quantum computers have been the dream of many scientists for over thirty years but the fact such devices still consist of only a handful of quantum bits (qubits) highlights the fact that this is not a trivial concept. However the potential of powerful parallelisation, which could out perform classical computers remains a huge incentive for researchers. Interest in donors in silicon has grown since being put forward as a possible candidate for a qubit in 1998 by Kane. Group V atoms, such as phosphorus, substitute into the silicon lattice but possess an extra outer shell electron compared to the neighbouring silicon atoms. This electron orbits the donor much like a hydrogen atom trapped in a silicon crystal. Despite overlapping with thousands of silicon atom, the donor electron experiences very little interaction with its surroundings leading to long spin lifetimes and coherence times. In this thesis the orbital state of donor electrons is explored. Electrical detection is used as a method of reading out coherent and incoherent manipulations of donor orbits. This is due to the high sensitivity achievable with electrical measurements. This work looked the detection mechanism in low and high intensity regimes as well as exploring the dynamics of the electron donor system in the time domain. Such experiments are use to measure the saturation of absorption and the electron-ion recombination rate (a quantity for which a range of values have previously been reported). Finally, the first electrical detection of coherent control of orbital states in silicon donors is presented, with T.J. found to be 30 - SOps.

Hydrogen sulfide (H2S) has been identified to be produced in small quantities in plants and animals. H2S has been shown to have numerous benefits including improving the tolerance of plants to a variety of stressors and improving the harvest yields of plants. Because of the ever-increasing population of the planet, it is necessary to grow more food and increasing the yield of a harvest is essential to do that. GYY-4137, a H2S donor, releases H2S very slowly in water but released it much faster with organic solvents and soil. The long-term growth of plants with GYY-4137 was investigated for 6 weeks with radishes, peas, and lettuce. Dithiophosphosphates were investigated as H2S donors to be used to improve the growth of crops. These donors were studied to determine their degradation rates in water and organic solvents. Rates of H2S release were compared at various concentrations in water and contrasted with the release of H2S from GYY-4137. Dialkyldithiophosphates have not been used in prior work as H2S donors to improve crop yields. Maize was grown for 4 weeks with dibutyldithiophosphate ammonium salt and the plants showed up to 38% increase in weight. These results show that dibutyldithiophosphate releases H2S at a similar rate to that of GYY-4137 and can have a significant benefit to increase the weight of maize.

The research described here explores the ability of dual H-bond donor catalysts to induce asymmetry in a variety of synthetically useful transformations that proceed via diverse reactive intermediates. In Chapters 1-3, we investigate ureas and thioureas as anion-binding catalysts for asymmetric reactions that proceeed via cationic intermediates with little precedent as electrophiles in asymmetric catalysis. Chapter 4 details our application of H-bond donor catalysis to the Cope-type hydroamination. Chapter 1 describes the development of an asymmetric aldehyde alkylation catalyzed by a bifunctional primary aminothiourea. A variety of 2-aryl propionaldehydes are alkylated with benzhydryl bromides in moderate to good yields and good enantioselectivities. Catalyst structure-activity relationship studies of the alkylation pointed towards electrophile activation by the dual H-bond donor moiety. Experiments aimed at gaining a better understanding of the electophile activation mode and characterizing the activated electrophilic intermediate in the alkylation reaction are described in Chapter 2. The development of an enantioselective cyanide addition to N,N-dialkyliminium intermediates is the subject of Chapter 3. A variety of strategies for accessing N,N- dialkyliminium ions are established, and chiral thioureas are shown to promote the addition of cyanide to such intermediates with moderate enantioselectivities. Chapter 4 details our discovery that thioureas bearing polarizable and conformationally constrained aromatic groups catalyze highly enantioselective Cope-type hydroaminations. This powerful transformation provides a variety of chiral pyrrolidine products under mild reaction conditions.
Chemistry and Chemical Biology

The infrared spectra of mixtures of HC1 and the following have been recorded in the gas phase and low temperature matrices: argon, ethene, ethyne, de-benzene, fluorobenzene, CO, CO 2 , SOz, CC1*, CHCls, de-acetone, ethanal, HCN and acrylonitrile. The features which have been measured are: firstly the changes in the integrated intensity of lines in the rotation-vibration spectrum of the fundamental HC1 band as a function of interactions with other components of the mixture, and secondly bands associated with specific interactions forming hydrogen-bonded complexes. The enhancement of HC1 is generally found to vary linearly with the pressure of added gas over a limited pressure range. Assuming that line enhancement is caused by collisionally-induced rotation-translation energy exchange to or from the HC1 molecule, a combination of expressions derived from Ehrenfest's Adiabatic Principle and the "rigid rotor" approximation leads to a model which qualitatively predicts the enhancements observed. The model also rationalises the enhancement of HCN and SOa absorptions by HC1. Examination of the experimentally determined data leads to the conclusion that the total intermolecular force between the monomer base and HC1 controls the degree of enhancement but it is concluded that there is no general connection between the degree of HC1 enhancement and hydrogen-bond strength. Hydrogen-bonded complexes were examined in the gas and argon matrix phases and the shifts in the modified hydrogen chloride stretch compared for various bases. The spectra of pi-complexes formed between HC1 and ethene, ethyne and benzene were found to be detectable by low-resolution infrared spectroscopy at room temperature. Complexation of HCN, he-acetone and de-acetone with HC1 caused CN and C=O band shifts. The Chem-X molecular modelling program was evaluated by using it to predict the geometry of simple complexes for which experimental data is already available. It is concluded that the program requires more development before it can be confidently used as a theoretical aid with which to study hydrogen-bonded dimers.

Quinones are organic oxidants that play important roles in biological contexts and find wide application in organic synthesis. They are known to be activated toward electron transfer through hydrogen bonding, which has largely been observed for Lewis basic, weakly oxidizing quinones. Comparable activation through H-bonding is more difficult to achieve when more reactive, electron-deficient quinones are used, as these intrinsically weaker Lewis bases are less prone to engage in H-bonding interactions. Herein, we describe the successful application of HBD-coupled electron transfer as a strategy to activate electron-deficient quinones. A systematic investigation of several small-molecule HBDs allowed examination of the effects of H-bonding on electron transfer to o-chloranil, an electron-deficient quinone that lacks the intrinsic reactivity necessary to oxidize many organic substrates of synthetic interest. This study has led to the discovery that dicationic HBDs have an exceptionally large effect on the rate and thermodynamics of these electron transfer reactions. Favorable modulation of the thermodynamics occurs as a result of the stabilization provided to the reduced quinone (Q•–) by the HBD. Electrochemical experiments have allowed quantification of the binding affinity for Q•– to each of the HBDs, as well as elucidation of the binding stoichiometry of the resulting ground-state complex. Monocationic HBDs bind to Q•– with 2:1 stoichiometry, whereas dicationic HBDs bind in a 1:1 complex. Dicationic bis-amidinium salts exhibit significantly improved binding to Q•–, offering more thermodynamic stabilization to this reduced state. The effects of HBDs on the kinetics of electron transfer have also been evaluated under homogenous conditions. Reactions between o-chloranil and ferrocene derivatives exhibit pronounced HBD-dependent rate enhancements, with dicationic HBDs displaying the greatest effect. Relative to neutral dual HBDs, the bis-amidinium salts accelerate the rate of electron transfer by > 1012. Binding stoichiometries within the rate-limiting transition states corroborate the results determined electrochemically, and binding affinity correlates with rate enhancement was observed across the series of HBDs evaluated. Application of HBD-coupled electron transfer in an oxidative lactonization illustrates that this strategy is applicable to catalysis of organic reactions. A dicationic HBD catalyst affords the lactone product in nearly quantitative yield within 24 h, whereas o-chloranil alone was ineffective (< 5% yield). The rates of lactonization with several HBD catalysts correlate well with the thermodynamic and kinetic trends described above. This trend indicates that the rate of the oxidative lactonization is related to the ability of the HBD to promote an electron transfer step. Potential strategies for application in enantioselective transformations and possibilities for future mechanistic investigation are presented.
Chemistry and Chemical Biology

One of the challenges in natural product discovery is the re-isolation and identification of known compounds. Dereplication is the process of identifying known compounds, allowing time and effort involved in their isolation and structure elucidation to be saved, thus enabling focus to be directed solely on new compounds. While dereplication is mainly MS-based, the main tool for structure elucidation of natural products is NMR. These techniques are very different to each other, with the only current approach in which they can be correlated is by hyphenated techniques such as LC-NMR-MS, requiring specialist and expensive hardware that is not available in every lab. In this thesis we develop structure and molecular size based NMR methodology for analysis of complex mixtures, such as those encountered in natural product research. We have used Diffusion Ordered Spectroscopy (DOSY), an NMR technique that enables components of a mixture to be distinguished by their diffusion coefficients (D), corresponding to hydrodynamic size. Since DOSY has mostly been used for organometallic and polymer analysis, we have established a calibration curve consisting mostly of natural products that provides a correlation between D to molecular weight (MW), allowing MW prediction from experimental D. Since physicochemical properties such as hydrogen bonding, molar density and molecular shape have been shown to affect D and therefore MW prediction, we have generated two new MW prediction models. The first model takes hydrogen bonding into account by the chemical shift of the most acidic hydrogen bond donor (HBD), and the second model provides a more accurate MW prediction for RP HPLC fractions based on the percentage MeOH the compound elutes it. We have generated predicted D based on structural and chemical properties for a database of 220,817 natural products, allowing dereplication by use of a D filter based on the experimental D in conjunction with structural filters based on NMR data. These models have been validated by the dereplication of a mixture of two sesquiterpenes from the plant Tasmannia xerophila, and the dereplication of three known tropane alkaloids in a complex mixture from Darlingia ferruginea. 3D DOSY methodology was undertaken for the analysis of the D. ferruginea complex mixture, allowing molecular fragments to be constructed from DOSY-COSY data. We have also projected diffusion data derived from DOSY-HSQC data onto an HMBC spectrum to generate complex fragments containing non protonated carbons, and this has provided a powerful tool for dereplication. These molecular fragments allowed dereplication and the annotation of three new tropane alkaloids in a complex mixture. These new compounds, together with other known alkaloids were subsequently isolated, and extensive 2D NMR and ECD data allowed their total absolute structures to be assigned to the three new compounds and the structure revision of two of the known compounds, one previously reported as it is diastereomer and both originally wrongly assigned as their opposite enantiomers. In this thesis we report the chemical investigation of two bryozoan species, members of a marine invertebrate phylum that is one of the most understudied. These species were selected for investigation after their extracts were identified as possessing potent bioactivity during an antiplasmodial screening of 486 marine invertebrate crude extracts collected in Australia as active toward the Plasmodium falciparum parasite, the causative agent of the malaria disease. The bryozoan Orthoscuticella ventricosa has afforded five new β-carboline alkaloids, two of which contained were bis-β-carboline containing an uncommon 1,2-disubstituted cyclobutane moiety. These compounds displayed weak antiplasmodial activity against the chloroquine-sensitive strain (3D7) of the P. falciparum. The bryozoan Amathia lamourouxi has afforded six new brominated alkaloids. Two of these displayed sub-micromolar antiplasmodial activity against both chloroquine-sensitive (3D7) and chloroquine-resistant (Dd2) P. falciparum strains and good selectivity relative to the human cell line, marking these compounds as validated antimalarial hits.
Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
School of Environment and Sc
Science, Environment, Engineering and Technology
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In-situ upgrading of oil using hydrogen donors is a new process. In particular, very little research has been conducted with respect to in-situ oil upgrading using hydrogen donor under in-situ combustion. Several papers describe the use of metal additives mixed with oil and their influence on oil properties such as viscosity and API gravity. The main objective of my research is to determine if a catalyst mixed with a hydrogen donor (tetralin) is going to affect the Jobo crude oil properties while undergoing in-situ combustion. Six runs were performed with Jobo crude oil (9-11ºAPI) from the Orinoco Belt in Venezuela. Four of the runs were successful. Two of them are base runs; the remaining ones are with tetralin with concentration of 5 wt% (of oil) and catalyst with concentration of 750 ppm. For all runs, the following were kept constant: the air injection rate (3 std. L/min) and production (combustion tube outlet) pressure, 300 psig. Concentration by weight of oil, water, and sand in the samples were approximately 4.8%, 4.2%, and 91% respectively. Oil viscosity at the end of combustion at 40°C decreased from 42.3 and 73.6 to 16.6 and 25.2; API gravity at the end of combustion increased from 18.4 and 16.8 to 20 and 18.8. Oil recovery is higher; combustion front velocity is faster in the case of additives, water production decreased. Since oil viscosity decreased and API gravity increased oil moves faster and consequently combustion time is lower.

Ce travail est consacré à la synthèse de nouveaux polymères donneurs de liaison Hydrogène et à leur utilisation comme partenaire dans la construction de nouveaux films multicouches préparés par le procédé d’élaboration en couche-par-couche (LbL). Plus particulièrement, une nouvelle réaction impliquant des mercaptoalcools non protégés et le poly(2,3,4,5,6-pentafluorostyrène) (PPFS) a été développé et appliquée à la synthèse de nouveaux polymères donneurs de liaisons H. Ce couplage régiosélectif et chimiosélectif de type « click » avec un thiol hétérofonctionnel peut être utilisée pour préparer une bibliothèque de polymères qui diffèrent de par leur degré de substitution (DS) et/ou leur fonctionnalité en groupements associatifs. Le contrôle de ces paramètres structuraux permet de moduler leur force d’interactions avec des partenaires accepteurs de liaison H variés, comme la poly(4-vinyl pyridine) (P4VP), le poly(acrylate de n-butyle) (PBA) et le poly(oxyde d'éthylène) (PEO), de telle façon que tous les types de mélanges binaires (mélange non miscible, partiellement ou totalement miscible, ou complexe interpolymère) peuvent être obtenus. Ensuite, les dérivés de PPFS donneurs de liaisons H ont été utilisés en partenariat avec le P4VP pour élaborer avec succès de nouveaux films multicouche dont la force motrice est l’établissement de liaisons H. L'influence de nombreux paramètres relatifs à la structure des polymères donneurs (DS, structure chimique du groupement associatif), au type de modification chimique subie par le substrat sur lequel est élaboré le film multicouche (monocouche auto-assemblée vs. polymère greffée en conformation de type brosse) ou encore des paramètres expérimentaux liés aux conditions de dépôt (concentration des solutions de dépôt, nature du partenaire adsorbé en premier) a été étudiée. Plus particulièrement, le mécanisme de croissance ainsi que les caractéristiques de surface du film ont été évalués
This work deals with the design of novel hydrogen-bond donor polymers and their use as partner in new tailor-made multilayered films prepared by the layer-by-layer (LbL) process. In this context, a novel regioselective and chemoselective “click-type” reaction of unprotected mercaptoalcohols onto poly(2,3,4,5,6-pentafluoro-styrene) (PPFS) has been developed, and applied to the synthesis of new hydroxylated H-bond donor polymers. This coupling with heterofunctional thiol is used to prepare a library of polymers differing in the degree of substitution (DS) and/or functionality. The fine control of these parameters makes it possible to tune their interaction ability with various acceptor polymers such as poly(4-vinyl pyridine) (P4VP), poly(n-butyl acrylate) (PBA) and poly(ethylene oxide) (PEO), such that all possible scenarios (immiscible blend, partially or totally miscible blend or interpolymer complex) can be achieved. Subsequently, the resulting H-bond donor polymers (PPFS derivatives) were used to successfully build-up multilayered films with using P4VP as partner via layer-by-layer (LbL) through the dip deposition process. The influence of various parameters related to structure of the partners (DS, nature of the PPFS derivatives), the chemical structure of the surface onto which the film is built-up (self-assembled monolayer vs. polymer brush) and the deposition process (concentration of deposition solutions, nature of the first deposited partner) was in-depth evaluated, on both the growth mechanism and on the surface features of the multilayered films

The first part of this work reports a comparative study on electrochromic properties of two Donor-Acceptor-Donor (DAD) type polymers, namely poly(2-heptyl-4,7-di(thiophen-2-yl)-1H-benzo[d]imidazole) (BImTh) and poly(4,7-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2-heptyl-1H-benzo[d]imidazole) (BImEd). DAD type polymers are designed to bear the same acceptor unit, benzimidazole and two different donor units, thiophene and 3,4-ethylenedioxy thiophene (EDOT) to make a comparison based on the donor unit effect. The resulting polymers are both multichromic and have low band gap values (1.93 eV for PBImTh and 1.74 eV for PBImEd). In the second part, 4,7-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)-2-phenyl-1H-benzo[d]imidazole (BImBEd) is synthesized. In order to figure out the presence of an intramolecular hydrogen bonding between the amine bond of the imidazole ring and the oxygen of the EDOT molecule, different amounts of trifluoroacetic acid (TFA) and concentrated sodium hydroxide (NaOH) solutions were added during electrochemical polymerization. These treatments caused protonation of the imine and deprotonation of the amine bonds respectively. In order to prove the changes in the optical properties of the polymers due to different number of protonated and deprotonated imine and amine bonds, 1,4-bis(2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)benzene (BEDOT-B) was also synthesized and treated with the same procedures. Results showed that it is possible to control the main chain conformation of even an insoluble polymer via acid and base treatments during in situ polymerization.

Experiments were conducted to investigate the feasibility of in situ upgrading of heavy oil by the use of an orgametallic catalyst and a hydrogen donor (tetralin). The experiments used a vertical injection cell into which a mixture of sand, water, and Jobo oil was thoroughly mixed and packed. Two types of runs were conducted: a run where the tetralin and catalyst were mixed within the mixture before packing into the cell, and the other was conducted by injecting a slug of the tetralin-catalyst solution before commencing with the steam injection. The Jobo oil used had an oil gravity of 12.4° API and a viscosity of 7800 cp at 30°C. The injection cell was placed in a vacuum jacket and set to a reservoir temperature of 50°C. Superheated steam at 273°C was then injected into the injection cell at a rate of 5.5 cc/min (cold water equivalent). The cell outlet pressure was maintained at 500 psig. Produced liquid samples were collected periodically through a series of separators. The produced oil was divided into two halves and several measurements and analyses were carried out on them. These included viscosity, density, elemental analysis and liquid composition. Experimental results indicated that tetralin alone was a worthy additive and increased recovery by 15% compared to that of pure steam. The premixed tetralincatalyst run showed improved recovery to that of pure steam by 20%. Experiments also showed that, when the tetralin-catalyst solution was injected rather than mixed, the results were equivalent to tetralin injection runs. Oil production acceleration was displayed by all the runs with tetralin and tetralin-catalyst but was more pronounced with the availability of catalyst.

Les mescles de baix punt de fusió o mescles eutèctiques denominades DES per les sigles en anglès (Deep Eutectic Solvents), són bàsicament preparades a partir de compostos acceptors de ponts de hidrogen, els anomenats HBA, (en general una sal d'amoni quaternària), i donadors de ponts d'hidrogen (HBD) com són alcohols, àcids, amines i carbohidrats; que formen sistemes que contenen una àmplia varietat d'espècies catiòniques i / o aniòniques regides per interaccions de pont d'hidrogen que presenten una baixa energia d'enllaç, causant dels baixos punts de fusió que aquestes presenten. Aquesta és una de les característiques importants a l'hora d'emprar els diferents tipus de DES, pel que fa a el tipus de reacció i / o procés sintètic; per exemple, aquests dissolvents eutèctics han estat àmpliament utilitzats i estudiats en processos d'extracció de biomassa, síntesi de polímers, catàlisi, electroquímica, síntesi de nano partícules, entre d'altres. En el present treball, es presenta la preparació de nous solvents eutèctics de base biològica a partir de glicerol (Gly), el qual va ser obtingut mitjançant la hidròlisi de greixos animals no comestibles i després emprat per sintetitzar l'alcohol 3- cloro-1,2-propanodiol, que és el precursor del compost racèmic: clorur de rac-2,3-dihidroxipropiltrietilamonio: [Et3N+CH2CH(OH)CH2OH]Cl- (DPTAC). Dit compost es va sintetitzar emprant el 3- cloro-1,2-propanodiol, trietilamina i metanol. El compost (DPTAC), que inicialment va ser obtingut en forma de barreja racèmica, va ser transformat en un compost enantiomèricament enriquit mitjançant un procés d'acetilació quimioenzimàtica i d'acetilació directa emprant acetat d’isopropilè, per tal de separar la mescla racèmica. De la mateixa manera, es va obtenir el clorur de S - (-) 2,3-dihidroxipropiltrietilamoni, partint de l'alcohol precursor òpticament pur (2a). Totes aquestes sals van ser acetilades directament amb anhídrid acètic. Tots ells van ser emprats com HBA per preparar diferents mescles eutèctiques (DES). Així, es van emprar tres compostos de base biològica: glicerol (Gly), àcid làctic (LA) i urea com HBD per formar cadascuna de les mescles. Finalment, l'etilenglicol (7) va ser també utilitzat per formar un DES concret. És important destacar que el disseny d'aquests dissolvents es va dur a terme utilitzant l'estratègia de "disseny modular" en què cada DES conté un HBA de diferent naturalesa i propietats. Inicialment, es presenta l'estudi de les propietats físiques (viscositat, densitat, relació estequiomètrica, entre d'altres) de cada DES. Posteriorment, s'estudia la seva funció com a dissolvents en diferents processos químics. Els DES preparats van ser utilitzats com a dissolvents en el procés de fraccionament i extracció de material ligno-cel·lulòsic en diferents mostres de biomassa de fusta dura, com són la sansa, i la poda de branques (de tipus llenyós) d'arbres fruiters. Els resultats van mostrar que es pot extreure lignina tipus Klasson i es recuperen fraccions riques en holocel·lulosa utilitzant cada un dels DES. Els DES preparats van ser també utilitzats per estudiar la seva influència sobre la formació dels adductes endo:exo, en reaccions típiques de ciclació [4π + 2π] tipus Diels-Alder, entre el ciclopentadiè i acrilat d'etil o acrilat de butil. D'altra banda, amb base en els requeriments del procés, van ser seleccionats els DES adequats per ser utilitzats com a mitjans de reacció en la reacció d'obtenció d'alcohols quirals secundaris mitjançant la reducció de cetones pro-quirals en presència de NaBH4. La riquesa enantiomèrica dels alcohols produïts es va estudiar emprant un reactiu de derivatització quiral (reactiu de Mosher). D'aquesta manera es va estudiar la configuració absoluta de l'alcohol: 1-feniletanol (12) (obtingut com a producte de la reacció anterior). A més, van ser realitzats assajos preliminars per valorar la possibilitat de reciclar els DES obtinguts. Per a això, els DES inicials, preparats entre el compost racèmic (DPTAC) amb els quatre compostos HBD van ser fraccionats, fent ús d'una resina de bescanvi catiònic fort, per tal de comprovar que la facilitat amb què aquests són separables; a més de ser reusables i reciclables. Condicions que ha de complir un solvent perquè pugui ser considerat dins de la categoria "Green Solvents"; tenint en compte que els materials de partida per a la formació de les mescles eutèctiques gairebé són íntegrament compostos de base biològica. Tots els compostos precursors i els DES preparats van ser caracteritzades per FT-IR i tècniques d'espectroscòpia de 1H i 13C RMN; el compost racèmic va ser analitzat mitjançant espectrometria de masses; la proporció entre els adductes formats en les reaccions de Diels-Alder, va ser estudiada utilitzant cromatografia de gasos GC-FID (230 ° C i 270 ° C). L'activitat òptica i l'angle de rotació específica van ser mesurats en els compostos enantiomèricament enriquits i òpticament purs. Finalment, la separació de cada DES, realitzada mitjançant columnes de bescanvi catiònic, va ser seguida per FT-IR i 1H RMN.
Las mezclas de bajo punto de fusión o mezclas eutécticas denominadas DES por sus siglas en inglés (Deep Eutectic Solvents), son básicamente mezclas preparadas a partir de compuestos aceptores de puentes de hidrógeno llamados HBA, (generalmente sales de amonio cuaternarias) y donantes de puentes de hidrógeno de diferente naturaleza (HBD), por ejemplo, alcoholes, ácidos, aminas y carbohidratos; que forman sistemas que contienen una amplia variedad de especies catiónicas y/o aniónicas regidas por interacciones, principalmente de puentes de hidrógeno, que presentan una baja energía de enlace que causan los bajos puntos de fusión que estas presentan. Precisamente, esta es una de las características importantes a la hora de emplear los diferentes tipos de DES, dependiendo del tipo de reacción y/o proceso sintético. Por ejemplo, estos disolventes eutécticos han sido ampliamente utilizados y estudiados en procesos de extracción de biomasa, síntesis de polímeros, catálisis, electroquímica, síntesis de nanopartículas, entre otros. En el presente trabajo se presenta la preparación de diferentes novedosos disolventes eutécticos de base biológica, a partir de glicerol (Gly). Este glicerol fue obtenido mediante la hidrólisis y trans-esterificación de grasas animales no comestibles, y luego empleado para sintetizar el alcohol 3-cloro-1,2-propanodiol, que es el precursor del compuesto racémico de interés: el cloruro de rac-2,3-dihidroxipropiltrietilamonio: [Et3N+CH2CH(OH)CH2OH]Cl-, [C9H22N+O2]Cl- o (DPTAC). Dicho compuesto se sintetizó empleando el cloroalcohol obtenido, trietilamina y metanol. El compuesto (DPTAC) que inicialmente fue obtenido en forma de mezcla racémica, fue transformado en un compuesto enantiomericamente enriquecido mediante un proceso de acetilación quimioenzimática y de acetilación directa empleando acetato de isopropileno, con el fin enriquecer enantiomericamente este compuesto racémico. Además, se obtuvo el cloruro de S-(-)-2,3-dihidroxipropiltrietilamonio (S)-(-)-(DPTAC), partiendo del alcohol precursor ópticamente puro. Estas sales fueron acetiladas directamente con anhídrido acético y empleadas como componente HBA, en presencia de tres compuestos de base biológica: glicerol (Gly), ácido láctico (LA) y urea que actuaron como compuesto HBD en la formación de cada una de las mezclas eutécticas (DES). Además, el etilenglicol (EG) fue también utilizado para formar otro DES concreto. Es importante tener en cuenta que, el diseño de estos disolventes se realizó empleando la estrategia de “diseño modular” para que cada DES contenga un HBA de naturaleza y propiedades diferentes. En este trabajo es presentado el estudio de las propiedades físicas (viscosidad, densidad, relación estequiométrica, entre otras) de cada DES. Posteriormente, se estudió su empleo como disolventes en diferentes procesos químicos; donde, los DES preparados fueron utilizados como disolventes en el proceso de fraccionamiento y extracción de material ligno-celulósico en diferentes muestras de biomasa de madera dura como son: el orujo de oliva, y la poda de ramas (de tipo leñoso) de árboles frutales. Los resultados mostraron la obtención de lignina tipo Klasson y de fracciones ricas en holocelulosa utilizando cada uno de los DES. Asimismo, los DES preparados fueron utilizados para estudiar su influencia sobre la formación de los aductos endo:exo, en reacciones típicas de ciclación [4π+2π] tipo Diels-Alder, entre el ciclopentadieno con acrilato de etilo y acrilato de butilo. Por otra parte, con base en los requerimientos del proceso, fueron seleccionados los DES adecuados para ser utilizados como medios de reacción, en la obtención de alcoholes quirales secundarios mediante la reducción de cetonas pro-quirales en presencia de NaBH4. La riqueza enantiomérica de los alcoholes producidos se estudió empleando un reactivo de derivatización quiral (reactivo de Mosher). De esta manera se estudió la configuración absoluta del alcohol: 1-feniletanol (12) (obtenido como producto de la reacción anterior).
Low melting mixtures or Deep eutectic mixtures called DES (Deep Eutectic Solvents) are prepared from hydrogen bond acceptors called HBA, (usually a quaternary ammonium salt), and different hydrogen bond donors (HBD) for example alcohols, acid amines, and carbohydrates; form systems that contain a wide variety of cationic and/or anionic species governed by hydrogen bonding interactions that present low binding energy, causing their low melting points. This is one of the important characteristics when using the different types of DES, in terms of the type of reaction and/or synthetic process; for example, these eutectic solvents have been widely used and studied in biomass extraction processes, polymer synthesis, catalysis, electrochemistry, nanoparticle synthesis, among others. This work presents the preparation of several novel bio-based eutectic solvents from glycerol (Gly), which was obtained by hydrolysis and trans-esterification of inedible animal fats and then used to synthesize alcohol 3-chloro-1,2-propanediol, which is the precursor of the racemic compound: rac-2,3-dihydroxypropyltriethylammonium chloride: [Et3N+CH2CH(OH)CH2OH]Cl- (DPTAC). This compound was synthesized using the mentioned chloro-alcohol, triethylamine, and methanol. Compound (DPTAC) that was initially obtained as a racemic mixture, was transformed into an enantiomerically enriched compound employing chemoenzymatic acetylation and direct acetylation process using isopropylene acetate to separate the racemic mixture. Similarly, S-(-)-2,3-dihydroxypropyltriethylammonium chloride was obtained starting from the optically pure precursor alcohol. All these salts were acetylated directly with acetic anhydride. All of them were used as HBA to prepare different eutectic mixtures (DES). Thus, three bio-based compounds were used: glycerol (Gly), lactic acid (LA), and urea as HBD to form each of the mixtures. Finally, ethylene glycol (7) was also used to form a specific DES. It is important to note that the design of these solvents was carried out using the strategy of "modular design" in which each DES contains an HBA of different nature and properties. Initially, the study of the physical properties (viscosity, density, stoichiometric ratio, among others) of each DES is presented. Subsequently, their use as solvents in different chemical processes is also studied, the DES prepared were used as solvents in the process of fractionation and extraction of lignocellulosic material in different samples of hardwood biomass, such as olive pomace, and pruning of branches (woody type) of fruit trees. Results showed the obtaining of Klasson-type lignin and fractions rich in holocellulose using each of the DES. DES prepared were used to study their influence on the formation of endo: exo adducts, in a typical [4π + 2π] Diels-Alder type cyclization reactions, between cyclopentadiene with ethyl acrylate and butyl acrylate. On the other hand, based on the process requirements, suitable DES were selected to be used as reaction media to obtain chiral secondary alcohols by reducing pro-chiral ketones in the presence of NaBH4. The enantiomeric richness of the alcohols produced was studied using a chiral derivatization reagent (Mosher's reagent). In this way, the absolute configuration of the alcohol was studied: 1-phenylethanol (12) (obtained as a product of the previous reaction). In addition, preliminary tests were carried out to assess the possibility of recycling the DES obtained. For this reason, the initial DES prepared between the racemic compound (DPTAC) with the four HBD compounds were fractionated using a strong cation exchange resin to verify the ease with which they are separable; besides, being reusable and recyclable. Conditions that a solvent must meet to be considered within the “Green Solvents” category. Taking into account that the starting materials for the formation of eutectic mixtures are almost entirely bio-based compounds. All the precursor compounds and DES prepared were characterized by FT-IR and 1H and 13C NMR spectroscopy techniques; the racemic compound was analyzed by mass spectrometry; the proportion between the adducts formed in the Diels – Alder reactions was studied using GC-FID gas chromatography (230 ° C and 270 ° C); Optical activity and specific angle of rotation were measured on enantiomerically enriched and optically pure compounds. Finally, the separation of each DES, carried out using cation exchange columns and followed by FT-IR and 1H RMN.

Les solvants eutectiques profonds (DES) sont récemment apparus comme une nouvelle classe de solvants verts présentant un potentiel élevé pour remplacer les solvants organiques usuels. Bien que découverts récemment, les DES ont fait l'objet de nombreuses recherches au cours des dernières années en raison de leurs propriétés intéressantes. Cependant, il reste encore beaucoup à découvrir étant donné le nombre quasiment illimité de DES potentiels et de leur polyvalence. Notre étude vise à examiner l'effet des DES sur les liposomes, adoptés comme modèles membranaires, et sur les membranes cellulaires. Elle a également cherché à évaluer la capacité de solubilisation des DES envers des composés bioactifs volatils. Ainsi, une sélection de DES ainsi que de nouveaux solvants ont été tout d'abord préparés et caractérisés. Des mesures de densité, de viscosité et de polarité ont été effectuées et ont montrées que les propriétés des DES pouvaient être ajustées en fonction de leur composition. L'organisation des phospholipides et des liposomes au sein des DES a ensuite été étudiée à l'aide de microscopies optique et à force atomique. Les phospholipides s'auto-assemblent en vésicules dans les DES à base de chlorure de choline tandis que les liposomes se convertissent en bicouches lipidiques avant leur reconstitution en vésicules. De plus, des études de cytotoxicité et des examens morphologiques ont été combinés afin d'évaluer l'impact de quelques DES sur MDA-MB-231, une lignée cellulaire de cancer du sein humain. Les résultats ont montrés que l'effet dépendait fortement de la composition du DES. D'autre part, la capacité de solubilisation des DES envers des composés bioactifs volatils a été testée par chromatographie en phase gazeuse couplée à un espace de tête. L'influence de la présence d'eau et de certains systèmes d'encapsulation tels que les liposomes et les cyclodextrines sur la capacité de solubilisation des DES ont été analysés. Enfin, la libération du trans-anéthole à partir des DES a été suivie par extraction multiple de l'espace de tête. Les DES ont été capables de mieux solubiliser les composés bioactifs volatils et de contrôler leur libération par rapport à l'eau. Dans l'ensemble, ces travaux mettent en évidence l'utilisation potentielle des systèmes à base de DES comme véhicules de solubilisation de composés bioactifs
Deep eutectic solvents (DES) recently emerged as a novel class of green solvents with a high potential to replace common organic solvents. Despite their novelty, DES were extensively explored in the past years owing to their remarkably interesting properties. Yet, a lot remains to be uncovered given the limitless number of possible DES and their versatility. The current sudy aimed to examine the effect of DES on liposomes, adopted as model membranes, and on cell membranes. It also sought to evaluate the solubilizing ability of DES toward bbioactive volatile compounds. Therefore, a group of selected DES along with new solvents were first prepared and characterized. Density, viscosity and polarity measurements were mainly carried out and showed that DES' properties can be tuned depending on their composition. The organization of phospholipids and liposomes within the DES was then investigated using optical- and atomical force microscopies. Phospholipids self-assembled into vesicles in choline chloride-based DES while liposomes converted to lipid bilayers before their reconstitution into vesicles. Moreover, cytotoxicity studies and morphological examinations were combined to evaluate the impact of some DES on MDA-MB-231, a human breast cancer cell line. Results showed that the effect is highly dependent on the DES' composition. On the other hand, the solubilizing ability of the DES toward bioactive volatile compounds was tested using static headspace-gas chromatography. The influence of the presence of water and some encapsulation systems such as liposomes and cyclodextrins on the overall DES' solubilization efficiency was further analyzed. At last, the release of trans-anethole from the DES was monitored via multiple headspace extraction. DES were able to greatly solubilize the bioactive volatile compounds and to control their release when compared with water. Altogether, this work highlights the potential use of the DES-based systems as solubilization vehicles for bioactive compounds

Perfluorosulfonate ionomers, such as Nafion® have been shown to demonstrate a profound affinity for large cationic complexes, and the study of polymer-bound cations may provide insight regarding Nafion® morphology by contrasting molecular size with existing models. The trimetallic complex, [{(bpy)2Ru(dpp)}2RhBr2] 5+, is readily absorbed by ion exchange into Na+ -form Nafion® membranes under ambient conditions. The dimensions of three different isomers of the trimetallic complex are estimated to be: 23.6 Å × 13.3 Å × 10.8 Å, 18.9 Å × 18.0 Å × 13.7 Å, and 23.1 Å × 12.0 Å × 11.4 Å, yielding an average molecular volume of 1.2×103 Å3 . At equilibrium, the partition coefficient for the ion-exchange of the trimetallic complex into Nafion® from a DMF solution is 5.7 × 103 . Furthermore, the total cationic charge of the exchanged trimetallic complexes counterbalances 86 ± 2% of the anionic SO3 − sites in Nafion®. The characteristic dimensions of morphological models for the ionic domains in Nafion® are comparable to the molecular dimensions of the large mixedmetal complexes. Surprisingly, SAXS analysis indicates that the complexes absorb into the ionic domains of Nafion® without significantly changing the ionomer morphology. Given the profound affinity for absorption of these large cationic molecules, a more open-channel model for the morphology of perfluorosulfonate ionomers is more reasonable, in agreement with recent experimental findings. In contrast to smaller monometallic complexes, the time- v dependent uptake of the large trimetallic cations is biexponential. This behavior is attributed to a fast initial ion-exchange process on the surface of the membrane, accompanied by a slower, transport-limited ion-exchange for sites in the interior of the ionomer matrix. The development of Nafion®/[{(bpy)2Ru(dpp)}2RhBr2] 5+ modified electrodes is also described for both FTO electrodes and materials made from electrospun carbon mats. The [{(bpy)2Ru(dpp)}2RhBr2] 5+ complexes behave as photocatalytic hydrogen production catalysts in the Nafion® membrane. Furthermore, a second bulk photoelectrolysis experiment with the Nafion®/[{(bpy)2Ru(dpp)}2RhBr2] 5+/FTO electrodes shows an enhancement of catalytic activity compared to the first photoelectrolysis experiment. This enhancement is attributed to halide loss following the first reduction process. Lastly, electrospun carbon nanofiber mats behave as electron donor materials for [{(bpy)2Ru(dpp)}2RhBr2] 5+/Nafion® membranes.
Ph. D.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Biological Engineering, 2009.
Cataloged from PDF version of thesis.
Includes bibliographical references (p. 108-115).
The inability of articular cartilage to heal after damage or disease has motivated investigation of novel cartilage tissue engineering technologies. The objective of this thesis was to advance the use of self-assembling peptide hydrogel scaffolds for cartilage repair by encapsulating bone-marrow-stromal cells (BMSCs) and incorporating chondrogenic cues to stimulate differentiation and neotissue production. To test the hypothesis that self-assembling peptide hydrogels provide cues which enhance the chondrogenic differentiation of BMSCs, a technique for rapid, high-viability BMSC encapsulation was developed. BMSCs were cultured in two peptide hydrogel sequences and compared to agarose hydrogels. BMSCs in all three hydrogels underwent TGF-3 1-mediated chondrogenesis as demonstrated by comparable gene expression and ECM biosynthesis. Cell proliferation occurred only in the peptide hydrogels, not in agarose, resulting in higher sulfated-glycosaminoglycan content and more spatially uniform proteoglycan and type II collagen deposition. These data showed that self-assembling peptide hydrogels enhance chondrogenesis compared to agarose. To evaluate the capacity for BMSCs from young and adult equine donors to produce cartilage-like ECM, neotissue formation was compared to that for animal-matched primary chondrocytes. Young chondrocytes stimulated by TGF-PlI accumulated ECM with higher sulfated-glycosaminoglycan content than adult chondrocytes and BMSCs of either age. BMSCs produced neotissue with higher dynamic stiffness than young chondrocytes. Measurement of aggrecan core-protein and chondroitin-sulfate length by atomic-force microscopy revealed BMSCs produce longer core protein and chondroitin-sulfate, and fewer catabolic-cleavage products than chondrocytes. Therefore, BMSC-produced aggrecan appears to have a younger phenotype than chondrocyte-produced aggrecan. These advantages make BMSCs a potentially superior cell source for peptide-hydrogel-based cartilage repair. To deliver TGF-pl to BMSCs via a bioactive scaffold, BMSCs were encapsulated in peptide hydrogels with both tethered and adsorbed TGF-p1 and cultured in TGF-p 1-free medium. Chondrogenesis was compared to that of unmodified peptide hydrogels with medium-delivered TGF-p1. Adsorbed-TGF-plI peptide hydrogels stimulated chondrogenesis of BMSCs as demonstrated by cell proliferation and cartilage-like ECM accumulation, while tethered TGF-p1 was not different from TGF-pl -free controls. TGF-p1 adsorbed to self-assembling peptide hydrogels can stimulate BMSC chondrogenesis. BMSC-seeded self-assembling peptide hydrogels, modified for controlled delivery of pro-chondrogenic factors, generate cartilage-like neotissue and are compatible with a single-surgery, autologous therapy for cartilage repair.
by Paul Wayne Kopesky.
Ph.D.

Radical cyclizations have become a mainstay of synthetic organic chemistry – useful for the construction of C–C bonds in laboratory-scale applications. However, they are seldom used the industrial scale. In large part, this is because of a reliance on Bu3SnH, widely regarded as the best synthetic equivalent to a hydrogen atom. Transition metal hydrides have emerged as promising alternative hydrogen atom sources. Over the last decade, the Norton group has studied three transition metal systems, with an emphasis on quantifying the M–H bond dissociation energies. Over time, the group has shown that, thermodynamically, first-row transition metal hydrides are good hydrogen atom donors; they often have weak M–H bonds. Modest adjustments to the M–H bond strength result in substantial changes to how a hydride processes a given organic substrate. The Norton group has also studied the kinetics of hydrogen atom transfer, and shown that transition metal hydrides are kinetically competent at transferring hydrogen atoms, both to olefinic substrates and to organic radicals. Some of the transition metal complexes are made catalytic under modest pressures of H2, so they can be used for effecting atom-economical radical reactions. I have leveraged the fundamental kinetic and thermodynamic information that has been gathered by the group to develop new radical reactions – ones that cannot be done by Bu3SnH. Herein are described two cases studies: the first is the generation of α-alkoxy radicals by hydrogen atom transfer to enol ethers (Chapter 2). The second is the development of a radical isomerization and cycloisomerization reactions (Chapter 3). Both of these developments have relied upon an understanding of M–H thermochemistry. Discovering new hydrogen atom donors will lead to discovering new radical reactions. In Chapter 4, I revisit two previously reported transition metal hydrides that are likely to transfer hydrogen atoms: (TMS3tren)CrIV–H and [CpV(CO)3H]–. Although the anionic vanadium hydride was reported as a potent hydrogen atom donor nearly forty years ago, my studies suggest that its M–H bond is actually relatively strong. I have therefore reevaluated the reactivity of [CpV(CO)3H]–, and found that although the 18 electron anionic hydride is not a good hydrogen atom donor, the oxidized 17-electron neutral CpV(CO)3H is an extremely potent one. I have made the reactions with [CpV(CO)3H]– catalytic under H2 (now the reactions are done with an added base). The catalytic reactions that use [CpV(CO)3H]– can enact the exact same transformations that tin does, so I have developed a true catalytic replacement for Bu3SnH.

碩士
國立高雄科技大學
化學工程與材料工程系
107
In this work, we investigated the double bonds conversion efficiencies (DC values) based on different Type II photoinitiator packages through gel fraction method. The formulations are including a trifunctional monomer of trimethylolpropane trimethacrylate (TMPTMA), hydrogen acceptor of Thioxathone (TX) and five amine-type hydrogen donors N-Phenylglycine (NPG), Triethylamine (TEA), Triethanolamine (TEOA), 2,2'-(4-Methylphenylimino)diethanol (p-TDEA), N-Phenyldiethanolamine (n-PDEA), respectively. Among those formulations, the TX/TEOA photoinitiator package showed the best DC values than others. The DC values are in the order of 1:2 wt% > 1.5:1.5wt% > 2:1 wt% for weight ratios investigation of TX/TEOA PI packages. In addition, the DC values are insignificant in either air or nitrogen under TX/TEOA at 1:2 wt%. We also investigated their photochemical and photophysical properties. The hydrogen donors exhibited the absorption band at lower than 300 nm, which followed the trend p-TDEA > n-PDEA > NPG > TEOA > TEA. After mixing TX with various amine-type hydrogen donors, the PL intensity increased in the following order: TX/p-TDEA > TX/n-PDEA > TX/ NPG > TX/TEA > TX/TEOA. Based on the results of photochemical analysis, the measured molar extinction coefficient was TEA> TEOA> p-TDEA> n-PDEA> NPG. Though all the Type II series exhibited good electron transfer ability by cyclic voltammetry (CV) and free energy change ΔGET results. However, steric hindrance and secondary and tertiary of the amines hydrogen donors played the major factor on the rate of photopolymerization.

This research is a study of the in-situ upgrading of Jobo crude oil using steam, tetralin or decalin, and catalyst (Fe(acac)₃) at temperatures of 250 °C, 275 °C and 300 °C for 24 hours, 48 hours and 72 hours using an autoclave. Viscosity, API gravity and compositional changes were investigated. We found that tetralin and decalin alone were good solvents for heavy oil recovery. Tetralin or decalin at concentrations of 9% (weight basis) could reduce the Jobo crude oil viscosity measured at 50 °C by 44±2% and 39±3%. Steam alone had some upgrading effects. It could reduce the oil viscosity by 10% after 48 hours of contact at 300°C. Tetralin, decalin or catalyst showed some upgrading effects when used together with steam and caused 5.4±4%, 4±1% and 19±3% viscosity reduction compared with corresponding pre-upgrading mixture after 48 hours of reaction at 300°C. The combination of hydrogen donor tetralin or decalin and catalyst reduced the viscosity of the mixture the most, by 56±1% and 72±1% compared with pre-upgrading mixture. It meant that hydrogen donors and catalyst had strong synergetic effects on heavy oil upgrading. We also found that 300 °C was an effective temperature for heavy oil upgrading with obvious viscosity reduction in the presence of steam, hydrogen donors and catalyst. Reaction can be considered to have reached almost equilibrium condition after 48 hours. The GC-MS analysis of the gas component showed that light hydrocarbon gases and CO₂ were generated after reaction. The viscosity reduction from decalin use is larger than that of tetralin because decalin has more hydrogen atoms per molecule than tetralin. A mechanism of transferring H (hydrogen atom) from H₂O and hydrogen donors to heavy oil, which can lead to structure and composition changes in heavy oil, is explained. The study has demonstrated that in-situ heavy oil upgrading has great potential applications in heavy and extra heavy oil recovery.

碩士
國立交通大學
材料科學與工程學系
100
In order to study the influence of the structure of siloxane terminal group on the mesogenic behavior of hydrogen-bonded bent core liquid crystal, a series of hydrogen-bonded bent core liquid crystal containing a bent-core pyridyl acceptor and four siloxane acid donors liquid crystal compounds were synthesized. The chemical structures of these compounds were characterized by 1H-NMR, IR spectra, MS as well as elemental analyses, and the liquid crystalline phases and mesomorphic behavior of all the compounds were identified from the results of DSC, POM, electro-optical measurement and GISAXS. Only the compound of POSS8-NBF14 can’t exhibit any mesophases, the other all exhibit, S1-NBF14 is a hydrogen-bonded complex with a linear siloxane units exhibited a series of general tilt smectic (SmCG) phases with highly ordered layer structures. POSS1-NBF14 is a hydrogen-bonded complex with a huge siloxane units exhibited a general tilt smectic (SmCG) phases with highly ordered layer structures. C4-NBF14 is a hydrogen-bonded complex with a cyclic siloxane units exhibited a highly ordered layer structures.

The thesis explores the mechanistic aspects of transfer hydrogenation of ketones and hydrosilylation of imines; two commonly used organic transformations catalyzed by ruthenium half-sandwich complexes of 2-oxazolidinethiones, 2-thiozolidinethiones, and orthometallated ligands. Hydrosilylation of imines catalyzed by group 6-NHC complexes is also presented. A series of NHC complexes of chromium, molybdenum, and tungsten are synthesized by the carbene transfer reaction from the corresponding Ag-NHC complexes and the metal hexacarbonyl complexes. These NHC complexes are examined for their catalytic activity in the hydrosilylation of N-benzylideneaniline. The reactions carried out in refluxing ethanol under nitrogen for 24 h give the products in reasonable yields. The effect of additives like peroxides and Me3NO, and U.V irradiation to promote the reaction is also studied. Four of the representative complexes are examined for hydrosilylation of various aldimines with different electronic and steric properties. These studies show that the homoleptic carbonyls of Cr, Mo, and W which show very low catalytic activity in the hydrosilylation reactions can be made to catalyze the hydrosilylation by substitution of a CO with an NHC ligand. The catalytic activity improves when two carbonyls are substituted with a biscarbene ligand as compared with monocarbene complexes. This trend points to the importance of the increased electron density on the metal center for catalytic activity. In summary, the thesis presents mechanistic aspects of transfer hydrogenation and hydrosilylation using a variety of metal complexes and hydrogen donors

Refcoal is a carbon precursor obtained by alkali-mediated extraction of coal with aprotic solvents such as DMF. Refcoal can be converted into a graphitic material through appropriate heat treatment. Graphitisable materials require the development of an intermediate liquid crystalline mesophase. Thus formation of a mesophase during the carbonisation of Refcoal is essential for obtaining highly graphitisable anisotropic cokes suitable for nuclear graphite applications. Anisotropic carbons are even more important in other commercial and industrial application because of their distinctive properties. The formation of anisotropic carbon depends on the nature of the parent precursor, temperature and carbonisation conditions, especially the molecular mobility during the mesophase stage. High-temperature extraction of coal produces Refcoal that yield cokes with a low level of anisotropy. Good control of the mesophase stage during carbonisation may lead to the development of anisotropic cokes. Hydrogen donor additives increase the molecular mobility in the liquid phase by stabilising the free radicals formed by thermal decomposition of coal. Hydrogen donor additives also increase the temperature range over which fluidity occurs, thereby allowing the formation of large sized mosaic structures. Mittal pitches (CTP) and tetralin were examined for their effectiveness as hydrogen donor additives. Refcoal blends containing 10 to 50% by mass additive were prepared by mixing and carbonisation conducted at temperatures ranging form 400 to 1000 °C. Samples were analysed using thermogravimetric analysis (TGA), diffuse reflectance infrared Fourier transform (DRIFT), optical microscope techniques, scanning electron microscopy (SEM), Raman spectroscopy and X-ray diffraction (XRD). It was found that addition of at least 10% tetralin improves the optical texture of Refcoal cokes and also increases the carbon yield. In both tetralin and pitch addition, 20% additive gave coarse circular anisotropic cokes after carbonisation at 650°C. However the carbon yield was reduced for the Refcoal coke treated with Mittal pitch. In fact the yield roughly decreases with an increase in pitch content. Although the cokes from pitch treated Refcoals showed a low ratio of d/g (where d indicates the degree of disordering and g the degree of ordering), Raman and XRD results indicate little further improvement in crystallinity but SEM showed development of a smooth morphology with increasing pitch content. Previous literature results suggest that this indicates that the material must have passed through a mesophase stage. Surprisingly, the addition of tetralin yielded cokes with high ratio of d/g, but improved the carbon yield and optical anisotropy. Increasing tetralin content in the carbonising system increased the size of anisotropic textures but the SEM micrographs show rough morphology with compounds that appear to inhibit mesophase spheres coalescence.
Dissertation (MSc)--University of Pretoria, 2009.
Chemistry
unrestricted

碩士
國立臺灣大學
化學研究所
93
Remote control of hydrogen bond strengths can be modulated in a three-component system consisting of a hydrogen bonding site (pyrrole), a conjugated bridge and a reaction center (imine). Protonation of the reaction center can trigger intramolecular charge transfer thus altering the binding ability of the remote hydrogen-bonding site. The signaltransduction from the reaction center to the hydrogen-bonding site can be easily observed. In the first part of the study, we investigated the effect of non-planarity in the π-conjugated system has on the binding strength in the three-component system. Computational study showed that the torsion angle between the binding site and the bridging unit could greatly influence the remote signal communication in our three-component system. Dihedral angle drive calculations on the hydrogen-bonding site were performed to show how the binding energies behaved as the torsion angle is varied. The results showed decay in the binding strength and transduction sensitivity as the torsion angle is increased. Small decrease in the binding energies is observed when the torsion angle is within 45°, so that intramolecular charge transfer is not seriously affected by small distortion in the torsion angle. When we compare the CH=CH bridge and N=N bridge, the N=N bridge, which displays more efficient charge-transfer ability than the CH=CH bridge in planar configuration, is less affected by the variation of the torsion angle, as long as the torsion angle is within 30°. In general, the decrease of binding energy in the α-systems is slightly more than the β-systems as the three-component systems become nonplanar. In the second part of the study, we observed the extent of charge transfer that was induced by metalation and compared it with protonation-induced charge transfer. We studied four three-component systems: system A (pure CH=CH-CH=CH bridge), system B (with two substituted CN groups in the CH=CH-CH=CH bridge), system C (with two substituted CN groups in the reaction center), and system D (with four substituted CN groups in the reaction center). The results showed that the abilities of charge transfer and sensitivity for metalation with M2+ ions are similar to protonation in all four systems. However, the abilities of charge transfer and sensitivity for metalation with M+ ions are very weak and are similar to the neutral state. The binding energies of different metals with the same oxidation state are similar (Ru2+ > Zn2+ = Mg2+ ; Li+ > Na+). The strengths of binding energies ordered from high to low observed in the four systems are system B > system D > system C > system A and sensitivities ordered from high to low in four systems are system D > system C > system B > system A. When we observed the bridge length effect on the four systems, the charge-transfer ability of system B is the least affected as the length of the bridge increase. Our studies have provided great insights in the understanding of remote hydrogen bond communication in our three-component systems and they could provide guidelines for the synthetic design of these materials.

A systematic study of propylene polymerization using a 4th generation Ziegler-Natta catalyst is presented in this thesis. The apparent kinetic rate constants for propylene polymerization were estimated in the presence and absence of hydrogen and/or donor. The estimated activation energies for activation, propagation, and deactivation were found to be close to values previously reported in the literature for similar catalysts. The polypropylene samples were characterized using high-temperature gel permeation chromatography (GPC), carbon-13 nuclear magnetic resonance (13C NMR), and crystallization elution fractionation (CEF). The effect of hydrogen and external electron donor on polypropylene microstructure was investigated at two polymerization temperatures. In addition to the expected electron donor positive effect on tacticity, hydrogen was also found to increase polypropylene tacticity. The effect of changing these polymerization conditions on molecular weight and polydispersity was also investigated. Finally, CEF profiles show how the distribution of polypropylene crystallizability changes by adding hydrogen and electron donor to the reactor. The concentrations of hydrogen and external donor were also varied to study their effect of polymerization kinetics and polymer microstructure. The estimated activation energies were close to those found in the first part of this investigation in the presence and/or absence of donor and hydrogen. A polypropylene microstructural study showed a positive effect of hydrogen concentration on mmmm pentad at low donor concentration, likely due to an increase in stereoselectivity of the aspecific sites by hydrogen. However, increasing donor concentration over a given threshold seems to transform the aspecific sitess into stereospecific sites that are no longer significantly affected by hydrogen. These experimental results were compared to a previously developed Monte Carlo model and found to agree with the trends predicted by simulation. Finally, the effect of diisopropyldimethoxysilane (P), n-propyltrimethoxysilane (N), paraethoxyethylbenzoate (PEEB), and dicyclopentyldimethoxysilane (D) external donors on catalyst activity and stereoselectivity was investigated. P and D donors were more stereoselective than N and PEEB donors; however, D donor had the best activity among all donors investigated. Therefore, D donor was mixed with PEEB to combine its high activity with the self-extinguishing properties of PEEB. The D/PEEB 90/10 (mol/mol) mixture generated a catalyst with good stereoselectivity but poor activity. When the ratio was increased to 95/5 and 98/2, the resulting catalyst had high activity and good stereoselectivity. Interestingly, the D/PEEB combination with just a small fraction of PEEB has a positive effect on the catalysts activation term which may decrease polymerization costs with this system.

碩士
國立臺灣師範大學
化學研究所
92
The importance of hydrogen bonding has prompted us to investigate systems in which the strengths of hydrogen bonds can be modulated at will by external stimuli. Three-component systems consisting of a hydrogen-bonding site (electron donor), a bridge, and a reaction center (electron acceptor) have been designed to achieve this goal of hydrogen-bonding modulation. When the reaction center was protonated, a signal was sent out to the other end of the three-component molecule via intramolecular charge transfer (ICT) and thus affected the binding ability of the binding site. It has been found that the constituents of the bridge greatly influence the efficiency of remote signal communication between the reaction and binding centers. In the current theoretical study, we focused on the carbon-based conjugated bridges and studied the effects of bridge structure and substituents on signal transduction. It was found that the quinoidal bridges or bridges with cyano substitutions near the reaction center were more effective than the parent unsubstituted transoid (CH=CH)3 bridge. For bridges such as (CR1=CR2)n or (CR1=CR1-CR2=CR2)n, signal reduction due to longer bridge lengths could be minimized if R2 are substituted with electron-withdrawing substituents such as F and CN. Finally, the (C(CN)=C(CN))n bridges are signal amplifying, i.e., longer bridge lengths cause stronger binding change at the binding site.

碩士
國立中央大學
化學研究所
97
Remote control of hydrogen bond strengths can be modulated in a three-component system containing a hydrogen bonding site(pyrrole),a conjugated bridge and a reaction center (porphyrin). Metalation of the reaction center can trigger intramolecular charge transfer(ICT), thus altering the binding ability of the remote hydrogen-bonding site. In our computational study, we have investigated two topics. The first one is to study the effect of metalation in the porphyrin three-component systems with different bridge positions. In this case, we have found that the porphyrin ring does not induce ICT in the metalated states, so we changed the reaction center to heteroporphyrins. Remote control of hydrogen bond strengths was successfully achieved with heteroporphyrins. The second topic is to construct two different types of multiple-way control systems which have multiple binding sites controlled by one metalation center. One has the similar binding strengths at all binding sites and the other has different binding strengths. We also compare the effectiveness of metalation in terms of remote control in single-way and multiple-way systems.

Using a hydrogen donor and a catalyst for upgrading and increasing oil recovery during in situ combustion is a known and proven technique. Based on research conducted on this process, it is clear that widespread practice in industry is the usage of tetralin as a hydrogen donor. The objective of the study is to find a cheaper hydrogen donor with better or the same upgrading performance. Decalin (C10H18) is used in this research as a hydrogen donor. The experiments have been carried out using field oil and water saturations, field porosity and crushed core for porous medium. Four in situ combustion runs were performed with Gulf of Mexico heavy oil, and three of them were successful. The first run was a control run without any additives to create a base for comparison. The next two runs were made with premixed decalin (5 percent by oil weight) and organometallic catalyst (750 ppm). The following conditions were kept constant during all experimental runs: air injection rate at 3.1 L/min and combustion tube outlet pressure at 300 psig. Analysis of the performance of decalin as a hydrogen donor in in-situ combustion included comparison of results with an experiment where tetralin was used. Data from experiments of Palmer (Palmer-Ikuku, 2009) was used for this purpose, where the same oil, catalyst and conditions were used. Results of experiments using decalin showed better quality of produced oil, higher recovery factor, faster combustion front movement and higher temperatures of oxidation. API gravity of oil in a run with decalin is higher by 4 points compared to a base run and increased 5 points compared to original oil. Oil production increased by 7 percent of OOIP in comparison with base run and was 2 percent higher than the experiment with tetralin. The time required for the combustion front to reach bottom flange decreased 1.6 times compared to the base run. The experiments showed that decalin and organometallic catalysts perform successfully in in situ combustion, and decalin is a worthy replacement for tetralin.