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Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第16816号 / 工博第3537号 / 新制||工||1535(附属図書館) / 29491 / 京都大学大学院工学研究科社会基盤工学専攻 / (主査)教授 松岡 俊文, 教授 垣内 隆, 准教授 西山 哲 / 学位規則第4条第1項該当

The diploma thesis deals with post-polymerization hydroxylation of polypropylene in solid state. Regarding the literature review, polypropylene was hydroxylated by radical grafting in aqueous solution of potassium persulfate at 100 °C, under nitrogen atmosphere for 60 minutes. Hydroxylation of polypropylene was performed at different concentrations of potassium persulfate (1; 5; 10 mol. %) and two different water/potassium persulfate molar ratios. The effects of reaction system composition and reaction conditions on reaction efficiency, extent of side reactions, thermal and rheological properties of hydroxylated polypropylene were evaluated. The presence and concentration of hydroxyl groups on polypropylene surface was determined by structural analysis (FTIR, XPS), while the highest efficiency was achieved in the presence of nonionic wetting agents, using 10 mol. % potassium persulfate and at lower water/potassium persulfate molar ratio. Based on changes in polypropylene structure, the modification took place mainly in the amorphous phase of the polymer. In addition to hydroxylation, concurrent side reactions have been reported, in particular the oxidation of wetting agents and polypropylene, which has resulted in chain cleavage, reducing the average molecular weight of the polypropylene.

SidA from Aspergillus fumigatus is an N-hydroxylating monooxygenase that catalyzes the committed step in siderophore biosynthesis. This gene is essential for virulence making it an excellent drug target. In order to design an inhibitor against SidA a greater understanding of the mechanism and structure is needed. We have determined the crystal structure of SidA in complex with NADP+, Ornithine, and FAD at 1.9 ? resolution. The crystal structure has provided insight into substrate and coenzyme selectivity as well as residues essential for catalysis. In particular, we have chosen to study the interactions of Arg 279, shown to interact with the 2'phosphate of the adenine moiety of NADP+ as well as the adenine ring itself. The mutation of this residue to alanine makes the enzyme have little to no selectivity between coenzymes NADPH and NADH which supports the importance of the ionic interaction between Arg279 and the 2'phosphate. Additionally, the mutant enzyme is significantly more uncoupled than WT enzyme with NADPH. We see that the interactions of the guanadinyl group of Arg279 and the adenine ring are also important because KM and Kd values for the mutant enzyme are shifted well above those of wild type with coenzyme NADH. The data is further supported by studies on the reductive and oxidative half reactions. We have also explored the allosteric effect of L-arginine. We provide evidence that an enzyme/coenzyme/L-arginine complex is formed which improves coupling, oxygen reactivity, and reduction in SidA; however more work is needed to fully understand the role of L-arginine as an allosteric effector. / Master of Science in Life Sciences

Metal and oxide interactions are of broad scientific and technological interest in areas such as heterogeneous catalysis, microelectronics, composite materials, and corrosion. In the real world, such interactions are often complicated by the presence of interfacial impurities and/or high electric fields that may change the thermodynamic and kinetic behaviors of the metal/oxide interfaces. This research includes: (1) the surface hydroxylation effects on the aluminum oxide interactions with copper adlayers, and (2) effects of high electric fields on the interface of thin aluminum oxide films and Ni3Al substrate. X-ray photoelectron spectroscopy (XPS) studies and first principles calculations have been carried out to compare copper adsorption on heavily hydroxylated a- Al2O3(0001) with dehydroxylated surfaces produced by Argon ion sputtering followed by annealing in oxygen. For a heavily hydroxylated surface with OH coverage of 0.47 monolayer (ML), sputter deposition of copper at 300 K results in a maximum Cu(I) coverage of ~0.35 ML, in agreement with theoretical predictions. Maximum Cu(I) coverage at 300 K decreases with decreasing surface hydroxylation. Exposure of a partially dehydroxylated a-Al2O3(0001) surface to either air or 2 Torr water vapor results in recovery of surface hydroxylation, which in turn increases the maximum Cu(I) coverage. The ability of surface hydroxyl groups to enhance copper binding suggests a reason for contradictory experimental results reported in the literature for copper wetting of aluminum oxide. Scanning tunneling microscopy (STM) was used to study the high electric field effects on thermally grown ultrathin Al2O3 and the interface of Al2O3 and Ni3Al substrate. Under STM induced high electric fields, dielectric breakdown of thin Al2O3 occurs at 12.3 } 1.0 MV/cm. At lower electric fields, small voids that are 2-8 A deep are initiated at the oxide/metal interface and grow wider and deeper into the metal substrate, which eventually leads to either physical collapse or dielectric breakdown of the oxide film on top.

L'activation de molécules inertes telles que les alcanes constitue l'un des défis les plus difficiles en catalyse, du fait de la grande stabilité de la liaison C-H. Pour répondre aux principes de la chimie verte, les méthodes de fonctionnalisation doivent respecter un certain nombre d'exigences, telles que l'utilisation de solvants et de réactifs non toxiques, la réduction des apports énergétiques, en association avec une activité élevée. Afin de satisfaire ces conditions, nous nous sommes dirigés vers l'utilisation d'un système enzymatique. En effet, les liaisons C-H non activées peuvent être fonctionnalisées en conditions douces par des monooxygénases, telles que les cytochromes P450, mais leur activité est relativement faible. Dans le but de disposer de cytochromes P450 plus actifs sur les alcanes, nous décrivons la fusion entre un membre de la famille des CYP153 et un partenaire donneur d'électrons. Cette protéine de fusion a été caractérisée, et ses propriétés catalytiques étudiées. Nous avons montré que la fusion augmente de manière considérable l'activité alcane hydroxylase. Nous avons, dans un second temps, continué d'exploiter le fort potentiel de ce biocatalyseur en tentant de réduire le volume de son site actif par mutagénèse dirigée, en vue de l'hydroxylation des alcanes gazeux, notamment le méthane. Enfin, différentes modifications des conditions réactionnelles nous ont permis d'atteindre une activité non égalée pour l'hydroxylation terminale de l'octane. / Activation of inert molecules such as alkanes is considered as one of the most difficult challenges in catalysis, due to the high stability of the C-H bond. To comply with the principles of green chemistry, functionalization methods must respect multiple requirements, such as the use of non-toxic solvents and reagents, in addition to reducing energy usage whilst maintaining maximal activity. To satisfy these conditions, we decided to focus on the use of an enzymatic system. Indeed, unactivated C-H bonds can be functionalized under mild conditions by monooxygenases, such as cytochrome P450s, but their activity is relatively limited. In order to have cytochrome P450s more active on alkanes, we describe the fusion between a member of the CYP153 family and an electron donor partner. This fusion protein has been characterized and its catalytic properties studied. We have shown that the fusion increases significantly the alkane hydroxylase activity. Our second step was to continue to exploit the potential of this biocatalyst by attempting to reduce the volume of its active site using site-directed mutagenesis for the hydroxylation of gaseous alkanes, including methane. Finally, various modifications of the reaction conditions allowed us to achieve the terminal hydroxylation of octane with a previously unequalled activity.

La fonctionnalisation tardive de molécules (Late stage functionalization – LSF) offre l’opportunité d’explorer l’espace chimique plus efficacement, en particulier en considérant les liaisons C-H aromatiques comme des points potentiels de diversification pour générer de nouveaux analogues directement en une seule étape au lieu de faire une synthèse totale dite de novo. La fonctionnalisation directe de composés élaborés peut en particulier se faire en utilisant la technologie superacide comme démontré par les nombreux travaux du professeur Jacquesy. L’un des meilleurs exemples de cette stratégie est certainement la transformation directe de la vinorelbine (Navelbine®) par fluoration en conditions superacides pour conduire à son analogue difluoré (Vinflunine), commercialisé par les laboratoires Pierre Fabre comme agent anticancéreux Javlor®. C’est dans ce contexte que ce travail de thèse a porté sur le développement de nouvelles méthodes de fonctionnalisation directe de composés aromatiques azotés.Il s’agissait effectivement de développer de nouveaux outils de synthèse en conditions superacides afin :1. d’hydroxyler directement des composés aromatiques par voie électrophile;2. d’halogéner des composés aromatiques azotés allant d’anilines simples à des composés élaborés naturels ou de synthèse;3. d’appliquer ces méthodes à la synthèse de molécules marquées par des isotopes stables. / Late-stage functionalization can now be considered as a synthetic tool of choice to create molecular diversity, especially in a medicinal chemistry context. For example, aromatic C-H bonds can be regarded as functional groups and points of potential diversification to generate new analogs of a lead structure without resorting to de novo synthesis.The direct functionalization of elaborated compounds can also be done using superacid chemistry as demonstrated by the previous work of professor Jacquesy. One of the best examples of this strategy is certainly the direct transformation of vinorelbine (Navelbine®) by fluorination in superacid conditions to lead to its difluorinated analogue (Vinflunine), marketed by Pierre Fabre laboratories as an anticancer agent Javlor®.In this context, these studies focused on the development of new methods for the direct functionalization of aromatic nitrogen containing compounds.In particular, this work aimed at developing new synthetic tools in superacid for:1. the direct hydroxylation of aromatic compounds;2. the halogenation of aromatic nitrogen compounds from simple anilines to naturally occurring or synthetic compounds;3. the synthesis of labelled compounds with stable isotopes.

Master of Science / Department of Grain Science and Industry / Xiuzhi Susan Sun / Plant oil-based raw materials have become more attractive alternatives in polymer industry as fossil resources depletion and environmental concerns continue to arise. Camelina (camelina sativa L.) seed contains about 45% of oil and about 90% of the oil is unsaturated fatty acids such as linoleic acid, α-linolenic acid, and erucic acids. It also provides the advantages of low cost and low fertilizer demand. Functionalized oils such as epoxidized camelina oil (ECO) and di-hydroxyl camelina oil (DCO) can be used for resins, adhesives, coatings, etc. The objectives of this work were to synthesize and characterize ECO and DCO from camelina oil. The epoxidation reaction of camelina oil was completed with formic acid and hydrogen peroxide. Catalyst ratio, reaction time, and temperature effects on the epoxidation reaction were studied. The optimum epoxy content of 7.52 wt% with a conversion rate of 76.34% was obtained from camelina oil using excess hydrogen peroxide and a molar ratio of formic acid of less than 1 for 5 hours in 50 °C. Camelina oil yields higher epoxy content (7.52 wt%) than soybean oil (6.53 wt%); however, soybean oil had a higher conversion rate of 80.16% compared to camelina oil because of uniform fatty acids distribution. In this study, we found that epoxidation efficiency is significantly affected by fatty acids composition, structure, and distribution. DCO was synthesized from ECO with different reaction parameters. The ring opening of ECO was performed with water, perchloric acid, and THF as proton donor, catalyst, and solvent respectively. Hydroxyl value of DCO was measured, and the maximal hydroxyl value was 369.24 mg KOH/g. physical properties of DCO were characterized by acid value and moisture content; thermal properties of DCO were obtained using different scanning calorimeter (DSC), thermalgravimetric analysis (TGA). Amount of solvent and acid catalyst addition affected the hydroxyl value and residual acid in DCO. Heat capacity, phase transition temperatures, and thermal stability of DCO were obtained and showed higher values than ECO’s. The DCO showed higher peel adhesion when it was formulated with epoxidized soybean oils through UV curing because camelina oil allows higher epoxy content, which results in higher hydroxyl values.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2009. / Aromatic precursor compounds are derivatives that play an important role in biosystems and are useful in the production of fine chemicals. This work focuses on the catalytic synthesis of 2-methyl-1, 4-naphthoquinone and cresols (para- and ortho) using aqueous hydrogen peroxide as an oxidant in liquidphase oxidation of 2-methylnaphthalene and toluene over titanium-substituted zeolite TS-1 or Ti-MCM-41. Catalysts synthesised in this work were calcined at 550°C, extensively characterised using techniques such as X-ray Fluorescence for determining the catalyst chemical composition; BET for surface area, pore size and micropore volume; Powder X-ray diffraction for determining their crystallinity and phase purity and SEM was used to investigate the catalyst morphologies. The BET surface areas for Ti-MCM-41 showed a surface area of 1025 m2/g, and a 0.575 cm3/g micropore volume. However, zeolite TS-1 showed a BET surface area of 439 m2/g and a 0.174 cm3/g micropore volume. The initial experiments on 2-methylnaphthalene hydroxylation were performed using the normal batch method. After a series of batch runs, without any success as no products were generated as confirmed by GC, a second experimental tool was proposed. This technique made use of the reflux system at reaction conditions similar to that of the batch system. After performing several experimental runs and optimising the system to various reactor operating conditions and without any products formed, the thought of continuing using the reflux was put on hold. Due to this, a third procedure was brought into perspective. This process made use of PTFE lined Parr autoclave. The reactor operating conditions were changed in order to suit the specifications and requirements of the autoclave. This process yielded promising results and the formation of 2-MNQ was realised. There was a drawback when using an autoclave as only one data point was obtained, at the end of each run. Therefore, it was not possible to investigate reaction kinetics in terms of time. Addition of aqueous hydrogen peroxide (30 wt-%) solution in the feed was done in one lot at the beginning of each reaction in all oxidation reactions, to a reactor containing 2-methylnaphthalene and the catalyst in an appropriate solvent of choice (methanol, acetonitrile, 2-propanol, 1-propanol, 1-pentanol, and butanol), with sample withdrawal done over a period of 6 hours (excluding catalytic experiments done with a Parr autoclave as sampling was impossible). As expected, 2-methylnaphthalene oxidation reactions with medium pore zeolite TS-1 yielded no formation of 2-methyl-1, 4-naphthoquinone using various types of solvents, with a batch reactor, reflux system, or a Parr PTFE autoclave. This was attributed to the fact that 2-methylnaphthalene is a large compound and hinders diffusion into zeolite channels. With the use of an autoclave, Ti-MCM-41 catalysed reactions showed that the choice of a solvent and reaction temperature strongly affect 2- methylnaphthalene conversion and product selectivity. This was proven after comparing a series of different solvents (such as methanol, isopropanol, npropanol, isobutanol, n-pentanol and acetonitrile) at different temperatures. Only reactions using acetonitrile as a solvent showed 2-MNQ. Formation of 2- MNQ, indicating that acetonitrile is an appropriate choice of solvent for this system. The highest 2-methylnaphthalene conversion (92%) was achieved at 120 ˚C, with a relative product selectivity of 51.4 %. Temperature showed a major effect on 2-MN conversion as at lower reaction temperature 100˚C, the relative product selectivity (72%) seems to enhance; however, the drawback is the fact that lower 2-methylnaphthalene conversions (18%) are attained. Another important point to note is the fact that using an autoclave (with acetonitrile as a solvent), 2-methyl-1-naphthol was generated as a co-product. In conclusion, it has been shown that the hydroxylation of different aromatic compounds over zeolites conducted in this study generated interesting findings. In 2-MN hydroxylation over Ti-MCM-41 as a catalyst, only acetonitrile is an appropriate choice of solvent using an autoclave. In addition, zeolite TS-1 is not a suitable catalyst for 2-MN hydroxylation reactions. It is ideal to optimise an autoclave in order to investigate reaction kinetics and optimum selectivity. Toluene hydroxylation reactions yielded para and ortho-cresol as expected with either water or acetonitrile as a solvent. No meta-cresol was formed. The kinetic model fitted generated a good fit with water as a solvent or excess toluene, with acetonitrile as a solvent generating a reasonable fit.

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 2010. / ENGLISH ABSTRACT: Partially oxygenated aromatic compounds, e.g. quinones, hydroquinones and cresols, play a vital role in the fine chemical industry and were initially prepared by stoichiometric oxidation processes that produce toxic products that are hazardous towards the environment. As a result, it was important to investigate environmentally friendly processes for the hydroxylation of aromatic compounds. This resulted in newer methods using Ti-substituted microporous zeolites as catalysts with hydrogen peroxide as oxidant in the presence of a solvent. However, the methods were found to be ineffective for large, bulky substrates due to the small pore structure. This led to using Ti-mesoporous materials as catalysts but suffered from two drawbacks; the hydrophilic nature and low hydrothermal stability of the catalyst structure. Ti-microporous and Ti-mesoporous materials acting as catalysts for the oxidation of bulky substrates achieved environmentally friendly processes but obtained low conversions and quinone yields. Therefore, the challenge has been to develop a process that is environmentally friendly, achieves high conversions, where the catalyst acts truly heterogeneous and obtains high quinone yields for the hydroxylation of bulky substrates. Recently, micropores/mesopores catalysts incorporating advantages of both micropores and mesopores materials were synthesised and seemed promising for the hydroxylation of bulky substrates. This study focuses on synthesising and evaluating the feasibility of various Ti-substituted catalysts for improving the hydroxylation of the bulky substrate, 2-methylnaphthalene (2MN) with hydrogen peroxide as oxidant in the presence of a solvent, acetonitrile. The oxidation of 2MN produces 2-methyl-1,4-naphthoquinone (2MNQ). 2MNQ is also known as menadione or Vitamin K3 and acts as a blood coagulating agent. The catalysts synthesised for this study were mesoporous catalysts, Ti- MCM-41 and Ti-MMM-2 and microporous/mesoporous catalysts, Ti-MMM-2(P123) and a highly ordered mesoporous material. The main objective of this study was to design an efficient process that is environmentally friendly and achieves high 2MN conversions and 2MNQ yields. This was achieved by evaluating the various catalysts synthesised, reaction conditions, testing if the catalyst was truly heterogeneous and identifying the products formed from the process. The designed process was proved to be environmentally friendly because the system did not produce products that were harmful towards the environment. The products identified in this study were 2MNQ, 2-methyl-1-naphthol, 2-naphthaldehyde, 3-ethoxy-4-methoxybenzaldehyde and menadione epoxide. An investigation was conducted to determine which catalyst synthesised favoured this process by quantifying the effect reaction conditions have on the various catalysts. The reaction conditions were defined in terms of the hydrogen peroxide volume, catalyst amount, solvent volume, substrate amount, reaction time and reaction temperature. The desired catalyst for this study obtained the highest 2MN conversions in comparison with the other catalysts and favoured the formation of 2MNQ. The catalyst achieving the highest conversions and favouring 2MNQ in most cases for this investigation was the highly ordered mesoporous material. Improving operating conditions to obtain high 2MNQ yields for the oxidation of 2MN to 2MNQ over the highly ordered mesoporous material was determined by varying the reaction conditions with the one factor at a time approach and a factorial design. The one factor at a time approach showed that best 2MNQ yields were obtained at 1 g substrate when investigating a change in substrate amount between 0.5 g and 2 g. Best 2MNQ yields were obtained at 10 ml solvent when investigating a change of solvent volume between 5 ml and 20 ml. The 2MNQ yield increased with increasing the catalyst amount (50 mg to 200 mg), hydrogen peroxide volume (1 ml to 6 ml) and increasing the reaction times (2 hour to 6 hours) at reaction temperatures, 120°C and 150°C. The yield decreased with increasing the reaction time (2 hours to 6 hours) at reaction temperature, 180°C. A preliminary 2 level factorial design was prepared to observe if there were any important interactions affecting the 2MNQ yield. The results from the factorial design indicated that the hydrogen peroxide volume had the most influence on the 2MNQ yield followed by the reaction time-reaction temperature interaction and reaction temperature. From the factorial design, the yield increased by increasing the hydrogen peroxide volume and reaction temperature whilst decreasing the reaction temperature-reaction time interaction. The highest 2MNQ yields and 2MN conversions obtained for the hydroxylation of 2MN to 2MNQ over the highly ordered mesoporous material in this study were in the ranges 48-50 % and 97-99 %, respectively. This study indicates that the process system, reaction conditions and catalyst type have an impact on the products formed, 2MN conversion, 2MNQ selectivity and 2MNQ yield. The highly ordered mesoporous material was found to be truly heterogeneous because no leaching occurred and the catalyst could be recycled without losing its catalytic activity and selectivity for at least two catalyst cycles. It can be concluded that the highly ordered mesoporous material is therefore a promising catalyst for the selective oxidation of bulky substrates with aqueous H2O2 because it produces an environmentally friendly process, achieves high conversions, obtains high quinone yields and the catalyst truly acts heterogeneous. / AFRIKAANSE OPSOMMING: Gedeeltelik geoksideerde aromatiese verbindings (bv. kinone, hidrokinone en kresole) speel ‘n belangrike rol in die fynchemiebedryf. Hierdie verbindings is aanvanklik voorberei deur stoïchiometriese oksidasie prosesse wat gifstowwe nadelig vir die omgewing veroorsaak. Daarom is dit belangrik om omgewingsvriendelike prosesse vir die hidroksilering van aromatiese verbindings te ondersoek. Hierdie ondersoeke het gelei tot nuwe metodes wat Ti-vervangde mikroporeuse seoliete as katalisator met waterstofperoksied as oksideermiddel in die teenwoordigheid van ʼn oplosmiddel benut. Dit is egter gevind dat hierdie metodes oneffektief is vir groot, lywige substrate weens die fyn poriestruktuur van die katalisator. Dit lei tot die gebruik van Ti-mesoporeuse materiale as katalisators, maar toon twee tekortkominge, naamlik die hidrofiliese aard en lae hidrotermiese stabiliteit van die katalisatorstruktuur. Ti-mikroporeuse en Ti-mesoporeuse materiale benut as katalisators vir die oksidasie van lywige substrate lewer omgewingsvriendelike prosesse, maar vermag lae omsetting en kinoonopbrengs. ʼn Uitdaging is dus om ʼn omgewingsvriendelike proses te ontwikkel met hoë omsetting, waar die katalisator werklik heterogeen optree en hoë kinoonopbrengs lewer vir die hidroksilering van lywige substrate. Katalisators vir die hidroksilering van lywige substrate wat die voordele van beide mikroporieë/mesoporieë ten toon stel is onlangs gesintetiseer, met belowende resultate. Hierdie studie is ingestel op die sintetisering en evaluering van uitvoerbaarheid van verskeie Tivervangde katalisators vir die optimering van die hidroksilering van die lywige substraat, 2- metielnaftaleen (2MN), met waterstofperoksied as oksideermiddel met asetonitriel as oplosmiddel. Die oksidering van 2MN produseer 2-metiel-1,4-naftokinoon (2MNK), ook bekend as vitamien K3, ʼn bloedstollingsmiddel. Die katalisators vervaardig vir hierdie studie was die mesoporeuse katalisators, Ti-MCM-41 en Ti-MMM-2, en die mikroporeuse/mesoporeuse katalisor Ti-MMM-2(P123), sowel as ʼn hoogs geordende mesoporeuse materiaal. Die hoofdoel van hierdie studie was om ʼn doeltreffende, omgewingsvriendelike proses met hoë 2MN omsetting en 2MNK opbrengs te ontwerp. Voorgenoemde is vermag deur verskeie gesintetiseerde katalisators en reaksiekondisies te evalueer, om te toets of katalisators werklik heterogeen is, en om die prosesprodukte te identifiseer. Die ontwerpte proses kan beskou word as omgewingsvriendelik, aangesien die stelsel geen produkte lewer wat skade aan die natuur kan veroorsaak nie. 2MNK, 2-metiel-1-naftol, 2-naftaldehied, 3- etoksi-4-metoksibensaldehied en menadioonepoksied is in hierdie studie geïdentifiseer as prosesprodukte. Om te bepaal watter gesintetiseerde katalisators hierdie proses begunstig, is ʼn ondersoek geloods om die effek van reaksiekondisies op die verskeie katalisators te kwantifiseer. Die reaksiekondisies is omskryf in terme van waterstofperoksiedkonsentrasie, katalisatorhoeveelheid, oplosmiddelvolume, substraathoeveelheid, reaksietyd en reaksietemperatuur. Die gewenste katalistor vir hierdie proses was die katalisator wat die hoogste 2MN omsetting lewer en die vorming van 2MNK bevorder. Die hoogs geordende mesoporeuse materiaal was in hierdie ondersoek die katalisator met die hoogste omsetting wat ook 2MNK-vorming bevorder het in die meeste gevalle. Om die beste bedryfstoestande vir hoë 2MNK opbrengs vanaf die oksidering van 2MN oor hoogs geordende mesoporeuse materiaal te bepaal, is die reaksiekondisies verander deur met een faktor op ʼn slag te verander, sowel as faktorverandering volgens ʼn faktoriaalontwerp. Die een-faktor-op-‘nslag benadering het getoon dat die 2MNK opbrengs ʼn maksimum bereik waar die substraathoeveelheid tussen 0.5 g en 2 g wissel, met die oplosmiddelvolume tussen 5 ml en 20 ml. Die opbrengs het ietwat verbeter met ʼn groter hoeveelheid katalisatorhoeveelheid (van 50 mg na 200 mg), terwyl die opbrengs drasties verbeter het waar die waterstofperoksiedvolume van 3 ml tot 6 ml verhoog is. Die opbrengs het ook verbeter met ʼn styging in reaksietemperatuur (van 120°C tot 180°C) met reaksietydintervalle van 1 tot 6 ure. Die opbrengs het egter gedaal by 180°C waar reaksietye langer as 2 ure. Volgens die resultate van die een-faktor-op-‘n-slag benadering blyk dit dat reaksietemperatuur, waterstofperoksiedvolume, katalisatorhoeveelheid en reaksietyd faktore is wat verhoogde 2MNK opbrengs bevorder. Hierdie reaksiekondisies is geselekteer vir die faktoriaalontwerp. ʼn Voorlopige 2- vlak faktoriaalontwerp is voorberei om te bepaal of daar enige belangrike interaksies is wat die 2MNK opbrengs beïnvloed. Die resultate van die faktoriaalontwerp het aangetoon dat waterstofperoksiedvolume die grootste invloed op 2MNK opbrengs het, gevolg deur die interaksie van reaksietyd en reaksietemperatuur, en dan reaksietemperatuur. Die faktoriaalontwerp resultate toon verder dat opbrengs verhoog met toenemende waterstofperoksiedvolume en reaksietemperatuur, terwyl die opbrengs verlaag soos wat die reaksietyd-reaksietemperatuur interaksie toeneem. Hierdie studie het hoogste 2MNK opbrengs van 48-50% en 2MN omsetting van 97-99% vir die hidroksilering van 2MN na 2MNK oor hoogs geordende mesoporeuse materiale behaal. Hierdie studie bevestig bevindinge van die literatuur dat die prosesstelsel, reaksiekondisies en katalisatortipe ʼn groot impak het op prosesprodukte, 2MN omsetting, 2MNK selektiwiteit en 2MNK opbrengs. In hierdie navorsingstudie is bevind dat hoë 2MN omsetting en 2MNK opbrengs behaal word by hoë reaksietemperature met kort reaksietye en hoë waterstofperoksiedvolumes. Dit is gevind dat die hoogs geordende mesoporeuse materiaal werklik heterogeen is, aangesien geen loging plaasgevind het nie, en aangesien die katalisator hergebruik kon word sonder verlies aan katalisatoraktiwiteit en –selektiwiteit, vir ten minste twee katalisatorsiklusse. ʼn Gevolgtrekking kan gemaak word dat die hoogs geordende mesoporeuse materiaal ʼn belowende katalisator vir die selektiewe oksidering van lywige substrate met waterige H2O2 is, aangesien dit ʼn omgewingsvriendelike proses lewer met hoë omsetting, hoë kinoonopbrengs en katalisatorgedrag wat waarlik heterogeen is.