The characteristics of cement kiln dusts (CKDs) and their effects as partial replacement of Portland Cement (PC) were studied in this research program. The materials used in this study were two different types of PC (normal and moderate sulfate resistant) and seven CKDs. The CKDs used in this study were selected to provide a representation of those available in North America from the three major types of cement manufacturing processes: wet, long-dry, and preheater/precalciner. Two fillers (limestone powder and quartz powder) were also used to compare their effects to that of CKDs at an equivalent replacement of PC. It was found that CKDs can contain significant amounts of amorphous material (>30%) and clinker compounds (>20%) and small amounts of slag and/or flyash (<5%) and calcium langbeinite (<5%). The study found that CKDs from preheater/precalciner kilns have different effects on workability and heat evolution than CKDs from wet and long-dry kilns due to the presence of very reactive and high free lime contents (>20%). The blends with the two CKDs from preheater/precalciner plants had higher paste water demand, lower mortar flows, and higher heat generation during initial hydrolysis in comparison to all other CKD-PC blends and control cements. The hardened properties of CKD as a partial substitute of PC appear to be governed by the sulfate content of the CKD-PC blend (the form of the CKD sulfate is not significant). According to analysis of the ASTM expansion in limewater test results, the CKD-PC blend sulfate content should be less than ~0.40% above the optimum sulfate content of the PC. It was also found that the sulfate contribution of CKD behaves similar to gypsum. Therefore, CKD-PC blends could be optimized for sulfate content by using CKD as a partial substitute of gypsum during the grinding process to control the early hydration of C3A. The wet and long-dry kiln CKDs contain significant amounts of calcium carbonate (>20%) which could also be used as partial replacement of limestone filler in PC.

Entomopathogenic fungi (EPF) are the one of the potential cause of the morbidity and mortality of insects. In agro-forestry uses, they are applied mainly in the form of conidial preparations in dry, aqueous or oil formulations. This approach, while practical, works in a hit and miss fashion leading to a frustrating dilemma of why successes and failure perpetuate. The fundamental solution is to bridge gaps in our knowledge about conidia of EPF in varied environments where they confront a diversity of insect hosts to start their pathogenesis.<p>This thesis was undertaken to examine the effects of hydration and the regulatory role of ambient pH on proteases which are the primary pathogenicity determinants in Beauveria bassiana and Metarhizium anisopliae. The approaches used were those of biochemical, proteomics and functional proteomics. <p>Novel aspects of pH regulation/homeostasis during the soaking of conidia in water, (type II water, which had a maximum electrical conductivity of 1ìS/ cm at 298K/ 25° C) were identified. Hydrated conidia showed swelling in type II water as assessed by (Multisizer IIITM (Coulter CounterTM). Release of proteases, metabolic activity through liberation of ammonia and citrate and synthesis of protein, RNA and DNA was established. It was deduced that conidial enzymes are either attached by loose hydrogen bonding or were associated to the spore membranes. Water soaked or hydrated conidia can secrete citrate and ammonia to modify the ambient pH and maximize the activity of secreted proteases. <p>Pr1- and- Pr2-like proteases were liberated by washing conidia in tween (Tw), water (Ww) and buffer. The washing of conidia in buffers (pH 4-10) affected the release/activity of Pr1 and Pr2. The thesis shows a newly designed native IPG strip zymography to identify the release of 4 and 8 isoforms of proteases, respectively from conidia. The 2-DE zymography (copolymerized gelatin) of protease from Tw of <i>B. bassiana</i> and <i>M. anisopliae </i> indicated one band (Mr 70 kDa; pI 6.3) and six isozymes (Mr 115-129 kDa; pI 3.7-9.0), respectively, which were identified using mass spectrometry (MALDI-TOF) as a serine-like protease. <p>Six metalloprotease isozymes from <i>M. anisopliae</i> but only one from <i>B. bassiana</i> was documented by 1-DE native zymography combined with 2-D spot densitometry scans. Cationic PAGE native zymography separated two basic protease isozymes from Tw extract of M. anisopliae depending upon the pH of the incubation buffer. However, one activity band was identified from <i>B. bassiana</i>. Furthermore, only one activity band was apparent during 1st and 2nd Ww up to day 2 for both EPF. SDS PAGE (non-dissociating) zymogram of secreted protease isozymes from Tw of <i>B. bassiana</i> revealed three bands of Mr100, 60, and 36.3 kDa. The isozymes observed at day 2 and 3 had a Mrs of 35.4 and 25 kDa, and 24.7 and 20.3 kDa at day 4. The SDS PAGE zymograms for <i>M. anisopliae</i> indicated two isozymes of Mr 103 and 12 kDa, respectively. During the 1st Ww and incubation of spores at day 2 and 3, a 12 kDa band was observed. These results confirm the presence of diversity of proteases and their isozymes with unique molecular sizes.<p>This thesis research discovered and characterized a diversity of proteins/enzymes not previously reported from any other fungi. A newly designed enzyme overlay membrane (EOM) technique revealed three isoforms of Pr1-like subtilisin from Tw of <i>M. anisopliae </i>(pI 8.1-9.7) and <i>B. bassiana</i> (pI 8.4-9.7). Conversely, only one isoform of Pr2-like trypsin was identified from <i>M. anisopliae</i> and no Pr2-like activity was observed from <i>B. bassiana</i>. Use of metalloprotease (MEP) inhibitors in conjunction with EOM analysis revealed their release during treatment in Tw. In <i>M. anisopliae</i> four activities (pI 4.4-7.5) of thermolysin-like MEP were observed. However, Tw of <i>B. bassiana</i> showed one activity band (pI 5.5). In addition, an isozyme of neutral MEP containing Zinc from <i>M. anisopliae </i>(pI 6.1) and one from <i>B. bassiana</i> (pI 6.5-7.6), respectively, was identified. MALDI-TOF and Q-TOF analysis revealed the presence of proteins similar to ROD 1, Ü- and â-glucanases, elastase, lipase 5 and galectin 7, which are important during the initial phase of germination and pathogenesis. <p>In addition subtilisin (Pr1-like), trypsin (Pr2-like) and NAGase synthesis from the germinating conidia and mycelia under the supply of different carbon and nitrogen (C/ N) sources was studied. The regulation of the synthesis of cuticle-degrading enzymes (CDE) from germinating conidia and mycelia was hypothesized to be controlled through regulatory derepression and nutritional starvation. Pr1 and Pr2 are regulated in a different manner in conidia and mycelia. Both enzymes are regulated through a multiple control mode. It was concluded that C/ N repression occurs only when it is necessary for infective structures to establish a nutritional relationship with the host cuticular structures. In addition, C/ N sources have a significant effect upon pH modulation, ammonia production and protease secretion. Furthermore, the synthesis of Pr1 and Pr2 from germinating conidia was affected by the (inducer pH) pHi of the growth media. Growing mycelia of <i>B. bassiana</i> under acidic (4.0), neutral (7.0) and basic (11.0) pH conditions produce ammonia which modifies the pH thereby creating environments suitable for protease. Growth, morphology, radial extension rate and conidiation at different pHi revealed that both EPF modify the pH of growth medium effectively as opposed to the saprophytic fungus, <i>Aspergillus nidulans</i>. <p>The presence of MEPs and Pr2-like trypsin suggests that these enzymes can act as a back up system for Pr1 to breach the cuticle and facilitate penetration before appressoria formation. The diversity of isozymes released from conidia suggests that the EPF are pre-adapted to pathogenic mode of life style, further contributing complexity to their interaction with host insects. Such isozymes can circumvent protease inhibitors present in the insect cuticle and the hemolymph. In addition, these isozymes may offer selective advantages in exploring new habitats (substrates) either as pathogen or saprophyte.

The influence of supplementary materials such as slag, metakaolin and limestone in steam-cured ternary and quaternary cement blends on physical and chemical hydration mechanisms was studied by analyzing the evolution of non-evaporable water content, hydration products and compressive strength. The role of limestone in hydration reactions of cement was also investigated. These properties were studied through the use of differential thermal and thermogravimetric analyses, as well as the loss-on-ignition, X-ray diffraction and compressive strength tests at 1, 3, 7, and 28 days. Research findings revealed that it is possible to replace up to 40% cement with other materials and still achieve compressive strengths similar to mixtures with a 25% cement replacement at 0.34 w/b ratio. Additionally, ternary limestone mixtures exhibited superior mechanical properties to ternary metakaolin mixtures. Lastly, limestone powder was determined to behave as inert filler, accelerating hydration at early ages through heterogeneous nucleation.

The influence of supplementary materials such as slag, metakaolin and limestone in steam-cured ternary and quaternary cement blends on physical and chemical hydration mechanisms was studied by analyzing the evolution of non-evaporable water content, hydration products and compressive strength. The role of limestone in hydration reactions of cement was also investigated. These properties were studied through the use of differential thermal and thermogravimetric analyses, as well as the loss-on-ignition, X-ray diffraction and compressive strength tests at 1, 3, 7, and 28 days. Research findings revealed that it is possible to replace up to 40% cement with other materials and still achieve compressive strengths similar to mixtures with a 25% cement replacement at 0.34 w/b ratio. Additionally, ternary limestone mixtures exhibited superior mechanical properties to ternary metakaolin mixtures. Lastly, limestone powder was determined to behave as inert filler, accelerating hydration at early ages through heterogeneous nucleation.

The characteristics of cement kiln dusts (CKDs) and their effects as partial replacement of Portland Cement (PC) were studied in this research program. The materials used in this study were two different types of PC (normal and moderate sulfate resistant) and seven CKDs. The CKDs used in this study were selected to provide a representation of those available in North America from the three major types of cement manufacturing processes: wet, long-dry, and preheater/precalciner. Two fillers (limestone powder and quartz powder) were also used to compare their effects to that of CKDs at an equivalent replacement of PC. It was found that CKDs can contain significant amounts of amorphous material (>30%) and clinker compounds (>20%) and small amounts of slag and/or flyash (<5%) and calcium langbeinite (<5%). The study found that CKDs from preheater/precalciner kilns have different effects on workability and heat evolution than CKDs from wet and long-dry kilns due to the presence of very reactive and high free lime contents (>20%). The blends with the two CKDs from preheater/precalciner plants had higher paste water demand, lower mortar flows, and higher heat generation during initial hydrolysis in comparison to all other CKD-PC blends and control cements. The hardened properties of CKD as a partial substitute of PC appear to be governed by the sulfate content of the CKD-PC blend (the form of the CKD sulfate is not significant). According to analysis of the ASTM expansion in limewater test results, the CKD-PC blend sulfate content should be less than ~0.40% above the optimum sulfate content of the PC. It was also found that the sulfate contribution of CKD behaves similar to gypsum. Therefore, CKD-PC blends could be optimized for sulfate content by using CKD as a partial substitute of gypsum during the grinding process to control the early hydration of C3A. The wet and long-dry kiln CKDs contain significant amounts of calcium carbonate (>20%) which could also be used as partial replacement of limestone filler in PC.

Entomopathogenic fungi (EPF) are the one of the potential cause of the morbidity and mortality of insects. In agro-forestry uses, they are applied mainly in the form of conidial preparations in dry, aqueous or oil formulations. This approach, while practical, works in a hit and miss fashion leading to a frustrating dilemma of why successes and failure perpetuate. The fundamental solution is to bridge gaps in our knowledge about conidia of EPF in varied environments where they confront a diversity of insect hosts to start their pathogenesis.<p>This thesis was undertaken to examine the effects of hydration and the regulatory role of ambient pH on proteases which are the primary pathogenicity determinants in Beauveria bassiana and Metarhizium anisopliae. The approaches used were those of biochemical, proteomics and functional proteomics. <p>Novel aspects of pH regulation/homeostasis during the soaking of conidia in water, (type II water, which had a maximum electrical conductivity of 1ìS/ cm at 298K/ 25° C) were identified. Hydrated conidia showed swelling in type II water as assessed by (Multisizer IIITM (Coulter CounterTM). Release of proteases, metabolic activity through liberation of ammonia and citrate and synthesis of protein, RNA and DNA was established. It was deduced that conidial enzymes are either attached by loose hydrogen bonding or were associated to the spore membranes. Water soaked or hydrated conidia can secrete citrate and ammonia to modify the ambient pH and maximize the activity of secreted proteases. <p>Pr1- and- Pr2-like proteases were liberated by washing conidia in tween (Tw), water (Ww) and buffer. The washing of conidia in buffers (pH 4-10) affected the release/activity of Pr1 and Pr2. The thesis shows a newly designed native IPG strip zymography to identify the release of 4 and 8 isoforms of proteases, respectively from conidia. The 2-DE zymography (copolymerized gelatin) of protease from Tw of <i>B. bassiana</i> and <i>M. anisopliae </i> indicated one band (Mr 70 kDa; pI 6.3) and six isozymes (Mr 115-129 kDa; pI 3.7-9.0), respectively, which were identified using mass spectrometry (MALDI-TOF) as a serine-like protease. <p>Six metalloprotease isozymes from <i>M. anisopliae</i> but only one from <i>B. bassiana</i> was documented by 1-DE native zymography combined with 2-D spot densitometry scans. Cationic PAGE native zymography separated two basic protease isozymes from Tw extract of M. anisopliae depending upon the pH of the incubation buffer. However, one activity band was identified from <i>B. bassiana</i>. Furthermore, only one activity band was apparent during 1st and 2nd Ww up to day 2 for both EPF. SDS PAGE (non-dissociating) zymogram of secreted protease isozymes from Tw of <i>B. bassiana</i> revealed three bands of Mr100, 60, and 36.3 kDa. The isozymes observed at day 2 and 3 had a Mrs of 35.4 and 25 kDa, and 24.7 and 20.3 kDa at day 4. The SDS PAGE zymograms for <i>M. anisopliae</i> indicated two isozymes of Mr 103 and 12 kDa, respectively. During the 1st Ww and incubation of spores at day 2 and 3, a 12 kDa band was observed. These results confirm the presence of diversity of proteases and their isozymes with unique molecular sizes.<p>This thesis research discovered and characterized a diversity of proteins/enzymes not previously reported from any other fungi. A newly designed enzyme overlay membrane (EOM) technique revealed three isoforms of Pr1-like subtilisin from Tw of <i>M. anisopliae </i>(pI 8.1-9.7) and <i>B. bassiana</i> (pI 8.4-9.7). Conversely, only one isoform of Pr2-like trypsin was identified from <i>M. anisopliae</i> and no Pr2-like activity was observed from <i>B. bassiana</i>. Use of metalloprotease (MEP) inhibitors in conjunction with EOM analysis revealed their release during treatment in Tw. In <i>M. anisopliae</i> four activities (pI 4.4-7.5) of thermolysin-like MEP were observed. However, Tw of <i>B. bassiana</i> showed one activity band (pI 5.5). In addition, an isozyme of neutral MEP containing Zinc from <i>M. anisopliae </i>(pI 6.1) and one from <i>B. bassiana</i> (pI 6.5-7.6), respectively, was identified. MALDI-TOF and Q-TOF analysis revealed the presence of proteins similar to ROD 1, Ü- and â-glucanases, elastase, lipase 5 and galectin 7, which are important during the initial phase of germination and pathogenesis. <p>In addition subtilisin (Pr1-like), trypsin (Pr2-like) and NAGase synthesis from the germinating conidia and mycelia under the supply of different carbon and nitrogen (C/ N) sources was studied. The regulation of the synthesis of cuticle-degrading enzymes (CDE) from germinating conidia and mycelia was hypothesized to be controlled through regulatory derepression and nutritional starvation. Pr1 and Pr2 are regulated in a different manner in conidia and mycelia. Both enzymes are regulated through a multiple control mode. It was concluded that C/ N repression occurs only when it is necessary for infective structures to establish a nutritional relationship with the host cuticular structures. In addition, C/ N sources have a significant effect upon pH modulation, ammonia production and protease secretion. Furthermore, the synthesis of Pr1 and Pr2 from germinating conidia was affected by the (inducer pH) pHi of the growth media. Growing mycelia of <i>B. bassiana</i> under acidic (4.0), neutral (7.0) and basic (11.0) pH conditions produce ammonia which modifies the pH thereby creating environments suitable for protease. Growth, morphology, radial extension rate and conidiation at different pHi revealed that both EPF modify the pH of growth medium effectively as opposed to the saprophytic fungus, <i>Aspergillus nidulans</i>. <p>The presence of MEPs and Pr2-like trypsin suggests that these enzymes can act as a back up system for Pr1 to breach the cuticle and facilitate penetration before appressoria formation. The diversity of isozymes released from conidia suggests that the EPF are pre-adapted to pathogenic mode of life style, further contributing complexity to their interaction with host insects. Such isozymes can circumvent protease inhibitors present in the insect cuticle and the hemolymph. In addition, these isozymes may offer selective advantages in exploring new habitats (substrates) either as pathogen or saprophyte.

Portland cement hydration is an exothermic process. The heat evolved during the hydration process is especially important in mass concrete, and hot and cold weather concreting. Heat of hydration is affected by several factors like chemical composition of cement, fineness of cement and ambient temperature. The major aim of this thesis is to investigate the effect of cement composition and fineness, amount and composition of the fine portion (&lt / 45 &micro / m) of natural pozzolan-incorporated cement on hydration heat. For this purpose, a portland cement and pozzolan-incorporated blended cements containing different amounts of natural pozzolan (trass) were used. The heat of hydration was measured using isothermal calorimetry. The values of heat of hydration for mixtures with different finenesses containing different amounts of added pozzolan were determined. The results obtained were used to find a correlation between the fineness, composition of cement and heat of hydration. According to this study, pozzolan incorporation in small amounts accelerates hydration. A similar effect was obtained for higher pozzolan amounts. Finer cements react faster and result in higher amounts of early heat evolved compared to coarser cements. In addition, it was found that the sum of the heat of hydration values of fine and coarse portion of cements was less than the total heat of hydration of blended cements. Moreover, a satisfactory correlation could not be established between results of isothermal calorimetry, and adiabatic calorimetry, setting time, and strength.

Dual phase magnesia-zirconia ceramics were developed, characterized, and evaluated as a potential matrix material for use in light water reactor inert matrix fuel intended for the disposition of plutonium and minor actinides. Ceramics were fabricated from the oxide mixture using conventional pressing and sintering techniques. Characterization of the final product was performed using optical microscopy, scanning electron microscopy, x-ray diffraction analysis, and energy-dispersive x-ray analysis. The final product was found to consist of two phases: cubic zirconia-based solid solution and cubic magnesia. Evaluation of key feasibility issues was limited to investigation of long-term stability in hydrothermal conditions and assessment of the thermal conductivity. With respect to hydrothermal stability, it was determined that limited degradation of these ceramics at 300^oC occurred due to the hydration of the magnesia phase. Normalized mass loss rate, used as a quantitative indicator of degradation, was found to decrease exponentially with the zirconia content in the ceramics. The normalized mass loss rates measured in static 300^oC de-ionized water for the magnesia-zirconia ceramics containing 40, 50, 60, and 70 weight percent of zirconia are 0.00688, 0.00256, 0.000595, 0.000131 g/cm2/hr respectively. Presence of boron in the water had a dramatic positive effect on the hydration resistance. At 300^oC the normalized mass loss rates for the composition containing 50 weight percent of zirconia was 0.00005667 g/cm2/hr in the 13000 ppm aqueous solution of the boric acid. With respect to thermal conductivity, the final product exhibits values of 5.5-9.5 W/(m deg) at 500^oC, and 4-6 W/(m deg) at 1200^oC depending on the composition. This claim is based on the assessment of thermal conductivity derived from thermal diffusivity measured by laser flash method in the temperature range from 200 to 1200^oC, measured density, and heat capacity calculated using rule of mixtures. Analytical estimates of the anticipated maximum temperature during normal reactor operation in a hypothetical inert matrix fuel rod based on the magnesia-zirconia ceramics yielded the values well below the melting temperature and well below current maximum temperatures authorized in light water reactors.

Today, with increasing global awareness and regulation of air pollution, interest in the smog-abating property of photocatalytic materials is increasing. Titanium dioxide (TiO2) is the most well known photocatalytic semiconductor and is often considered as one way of solving pollution by a passive but an effective way, particularly to reduce atmospheric nitrogen oxides (NOx=NO+NO2). This relatively new technology is already being used in some of the countries as a construction material, commercially sold as photocatalytic cement, photocatalytic pavement, self-cleaning tiles, and self-cleaning glass. Prior research has examined the photocatalytic properties of TiO2 itself, as well as TiO2-containing cement-based materials. The majority of this effort has been on characterizing and enhancing the photocatalytic efficiency. However, relatively little research was performed to assess the potential impact of the photocatalytic reaction on the "parent" or "host" material. In this research, the focus is on the effect of photocatalysis on the composition, structure, and properties of cementitious materials, which contain titania nanoparticles at early and late ages. Fundamental examinations on the addition of these chemically non-reactive nanoparticles to cement-based materials are performed. The high surface area of nanoparticles could alter early age properties of cementitious materials, such as setting time, dimensional stability, and hydration rate. Various experimental techniques as well as mathematical modeling were used to examine and explain the early age hydration of cementitious materials when TiO2 nanoparticles are present. Further, the effects of the TiO2 on the long term durability of cement-based materials are investigated to demonstrate their suitability for long-term use in the field. The photocatalytic NOx oxidation efficiency and NOx binding capability of TiO2 containing cementitious materials are experimentally investigated. The durability of TiO2-cement is examined by various techniques on samples that went through extensive photocatalysis and environmental exposures. These investigations have led to tentative conclusions on the use of TiO2 nanoparticles in cementitious materials, and suggest avenues for future study.

Ziel dieser Arbeit war die Untersuchung des Hydratationsverhaltens von alkylsubstituierten Aminen und deren korrespondierenden Ammoniumionen mit Hilfe von Car-Parrinello-Moleküldynamik Simulationen (CPMD). Dabei konnten Fragestellungen hinsichtlich der Koordinationszahlen, des Lösungsmittelaustausches und der molekülspezifischen pKB-Werte beantwortet werden. Des Weiteren lässt die Arbeit Aussagen über einen Zusammenhang von Hydratation und anormaler Basiszitätsreihenfolge der Amine zu und ermöglicht zusätzlich die Beschreibung von Systemen mit mehreren Aminfunktionen durch die Anwendung der gewählten Bedingungen. Zur Simulation des Hydratationsverhaltens wurden Wasser enthaltende Lösungsmittelboxen erstellt, bei denen das zu untersuchende Molekül zentral angeordnet war. Nach dem Ausschluss dimensionsabhängiger Effekte durch die Equilibrierung auf Grundlage einer kraftfeldbasierten Moleküldynamik, konnte eine geeignete Boxgröße bestimmt werden, die neben der Berechnung der ersten Hydratationssphäre auch die Beschreibung einer möglichen zweiten Hydratationssphäre erlaubt. Anhand der erhaltenen CPMD-Trajektorien aus den erfolgreichen Simulation wurden Verteilungsfunktionen berechnet. Der Vergleich dieser Ergebnisse mit experimentell bekannten Werten und Berechnungen an reinem Wasser zeigte, dass das System real vorliegende Bedingungen wiedergibt. Die ermittelten gNO(r) -Verteilungsfunktionen der Amine bzw. deren korrespondierender Ammoniumionen weisen signifikante Unterschiede auf und spiegeln einen grundsätzlich verschiedenen Aufbau der Hydratationssphären wieder. Dabei besitzen alle freien Amine eine starke Wasserstoffbrückenbindung unter Einbeziehung des freien Elektronenpaares am Stickstoffatom, während sich an den Aminwasserstoffatomen nur sehr schwache Wechselwirkungen beobachten ließen. Abgesehen vom Trimethylamin sind die Hydratationssphären der Amine wenig strukturiert und der Wasseraustausch zwischen erster und zweiter Hydratationssphäre verläuft sehr schnell. Im Gegensatz dazu ist die Umgebung der Ammoniumionen stark strukturiert. Alle Ammoniumwasserstoffatome sind in Wasserstoffbrückenbindungen einbezogen und es existiert ein vergleichsweise langlebiger Käfig aus Wassermolekülen um das Ammoniumion. Zusätzlich befindet sich zeitweise ein weiteres, wesentlich mobileres Wassermolekül in der ersten Hydratationssphäre, das in der Lage ist einen Wasseraustausch einzuleiten. Dabei konnten für das Ammoniumion und das Methylammoniumion konkrete Mechanismen des Wasseraustausches bestimmt werden. Die Berechnung der pKB- bzw. pKA -Werte für die untersuchten Systeme war ein weiterer Bestandteil der Arbeit. Dazu wurde ein statistischer Ansatz zur Ermittlung der freien Energie herangezogen, bei dem die Mittelwerte der Verteilungsfunktionen verwendet werden, so dass die zu erwartende Genauigkeit eng mit der Simulationszeit verknüpft ist. Auf Grundlage von Strukturoptimierungen an Ammoniumionen, die mit wenigen Wassermolekülen umgeben waren, konnten unter Variation der NH-Bindungslängen Energiegradienten ermittelt werden, die eine Aussage über die möglichen Übergangszustände bei der Deprotonierung lieferten. Als gute Näherung des Übergangszustandes kann demnach für alle Methylammoniumionen eine NH-Bindungslänge von 1,22 Ǻ in Betracht gezogen werden. Mit Hilfe dieser Bindungslänge wurde die Wahrscheinlichkeit der Deprotonierung für alle Ammoniumionen berechnet, wobei Simulationen bei denen ein spontaner Protonenübergang auftrat keine Berücksichtigung fanden. Die Ergebnisse der methylsubstituierten Amine zeigen eine gute Übereinstimmung mit den experimentellen Werten mit einer Abweichung von maximal +0,3 pK-Einheiten. Diese Abweichung entspricht in etwa 1,5 kJ/mol, was für theoretische Arbeiten einen sehr kleinen Fehler darstellt. Auf Grund der gewählten Bedingungen ist beim Ammoniumion die Wahrscheinlichkeit für die Deprotonierung unterschätzt wurden. Dadurch ist der entsprechende pKB -Wert kleiner als der experimentell ermittelte Wert. Im Verlauf der Arbeit konnte weiterhin gezeigt werden, dass das Verfahren und die gewählten Bedingungen auch für ethylsubstituierte Alkylamine und deren korrespondierende Ammoniumionen angewendet werden können. Die Genauigkeit der Ergebnisse hängt dabei hauptsächlich von der Simulationszeit ab. Ein entscheidender Punkt der Arbeit ist der Nachweis, das mit Hilfe dieser Moleküldynamik-Simulationen auch Moleküle mit mehreren Aminfunktionen berechnet werden können. Es ist somit möglich Differenzierungen in der Protonierung und Hydratation der einzelnen Aminfunktionen vorherzusagen.