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To improve the properties of thermochemical heat storage materials, salt mixtures were evaluated for their heat storage capacity and cycle stability as part of the innovation incubator project “Thermochemical battery” of the Leuphana university Lüneburg. Based on naturally occurring compound minerals, 16 sulfates, 18 chlorides and 5 chloride multi-mixtures, 18 bromides and 5 intermixtures between sulfates, chlorides and bromides were synthesized either from liquid solution or by dry mixing for TGA/DSC screening before continuing the heat storage evaluation with five different measurement setups at a laboratory scale. The TGA/DSC analysis served as a screening process to reduce the number of testing materials for the upscaled experiments. The evaluation process consisted of a three-cycle dehydration/hydration measurement at Tmax = 100°C and Tmax = 200°C. In case of the bromide samples a measurement of hydration conditions with Tmax = 110°C and a water flow at e = 18.68mbar, were added to the procedure to detect the maximum water uptake temperature. Also, a single dehydration to a temperature of Tmax = 500°C was implemented to observe melting behavior and to easier calculate the samples’ stages of hydration from the remaining anhydrous mass. Materials which showed high energy storage density and improved cycle stability during this first evaluation were cleared for multi-cycle measurements of 10 to 25 dehydration and hydration cycles at Tmax = 100 to 120°C and the evaluations at m = 20 to 100g scale. An estimate for the specific heat capacities at different temperatures of the materials which passed the initial stage was calculated from the TGA/DSC results as well. The laboratory scale measurement setup went through five stages of refining, which led to reducing the intended maximum sample mass from m = 100g to m = 20g. A switch from supplied liquid water to water vapor as the used reactant was also implemented in exchange for improved dehydration conditions. Introducing a vacuum pump for evaporating the water limited the influence of outside heat sources during hydration and in-situ dehydration was enabled as to not disturb the state the samples were settling in between measurements. Baseline calculation from blanc measurements with glass powder and attempts to calculate the specific heat capacity cp of the tested materials by 6 applying the Joule-Lenz-law to the measurement apparatus was another step of method development. The evaluation process of the laboratory scale tests at the final setting consisted of 1 to 5 cycle measurements of in-situ dehydration and hydrations with applied vacuum for t = 30 minutes at p ~ 30mbar. Upscaling the sample mass to m = 20g allowed for a close observation of different material behaviors. Agglomeration, melting and dissolving of the m = 10mg samples during the TGA/DSC analysis can be deducted from the recorded measurement curves and the state of the sample after measurement. However, at laboratory scale the visible volume changes, observed sample consistency after agglomeration and an automatic removal of molten and dissolved sample mass during the measurement allowed for a better characterization and understanding of the magnitude of the actual changes. This was done for the first time, particularly for mixed salts. Of the original number of 62 samples, 4 mixtures which passed the initial TGA/DSC screening namely {2MgCl2+ KCl}, {2MgCl2+CaCl2}, {5SrBr2+8CaCl2} and {2ZnCl2 + CaCl2} were chosen for further evaluation. The multi-cycle TGA/DSC measurements of {2MgCl2+ KCl}, {2MgCl2+CaCl2} and {5SrBr2+8CaCl2} showed an improved cycle stability for all three materials over the untreated educts. Of the four materials {2ZnCl2 + CaCl2} displayed the strongest deliquescence during hydration in the upscaled experimental setup. {2MgCl2+CaCl2} proved to be the most stable material regarding the heat storage density. The {MgCl2} content of the mixture is likely to partially or completely react to {Mg(OH)Cl} at temperatures of T > 110°C, which however does not impede the heat storage density. {5SrBr2+8CaCl2} displayed a low melting point in hydrated state, causing a fast material loss. This makes it an undesirable storage material. A lower heating rate may still help to avoid an early melting. The {2MgCl2+KCl} mixture was the most temperature stable of the mixtures showing no melting or dissolving behavior. A reaction of the {MgCl2} component of the mixture to {Mg(OH)Cl} was not observed within the applied temperature range of T = 25 to 200°C.
Despite the great progress that has been made in the prophylaxis of oral diseases over the past decades, dental caries and periodontal diseases remain major challenges in the field of dentistry. Biofilm formation on dental hard tissues is strongly associated with the etiology of these oral diseases. Therefore, the process of bioadhesion and biofilm formation on tooth surfaces is of particular interest for dental research. The first stage of bioadhesion on dental surfaces is the formation of the pellicle layer. This mainly acellular film, composed largely of adsorbed proteins, glycoproteins, and lipids, is distinguished from the microbial biofilm (plaque). As the interface between teeth and the oral environment, the pellicle plays a key role in the maintenance of oral health and is of great physiological and pathophysiological importance. On the one hand, the pellicle shows protective properties for the underlying dental hard tissues. On the other hand, it also serves as the basis for dental plaque and therefore, for the development of oral diseases such as caries and periodontitis. Hydrophobic interactions, which are governed by lipophilic substances, are of high relevance for bacterial adherence. Therefore, pellicle lipids, which are a significant constituent of this biological structure, are an interesting target for dental research, as they could modulate oral surfaces, influence microbial interactions, and potentially impede bacterial adherence. Compared to the extensive work on the pellicle´s ultrastructure and protein/amino acid composition, little attention has been given to its lipid profile. Knowledge of the lipid composition of the pellicle may provide insight into several oral pathological states, including caries, dental erosion, and periodontal disease processes and could contribute to novel approaches in preventive dentistry. The principle aim of this thesis was the comprehensive characterization of the fatty acid (FA) profile of the in situ formed pellicle layer. This includes the influence of pellicle maturation on the FA profile as well as intra- and interindividual differences. Furthermore, investigations on the effect of rinses with edible oils on the pellicle´s FA composition were a focus of this work. For these purposes, an analytical method based on a combination of innovative specimen generation and convenient sample preparation with sensitive mass spectrometric analysis was successfully developed and comprehensively validated within this thesis. Pellicle samples were formed in situ on bovine enamel slabs mounted on individual upper jaw splints. After a comprehensive sample preparation, gas chromatography coupled with electron impact ionization mass spectrometry (GC-EI/MS) was used in order to characterize qualitatively and quantitatively a wide range of FA (C12-C24). The individual FA profiles of pellicle and saliva samples collected from ten research participants were investigated. The relative FA profiles of the pellicle samples gained from the different subjects were very similar, whereas the amount of FAs showed significant interindividual variability. Compared to the pellicle´s characteristic FA profile, higher proportions of unsaturated FAs were detected in the saliva samples, highlighting that FAs available in saliva are not adsorbed equivalently to the pellicle layer. This, in turn, shows that pellicle formation is a highly selective process that does not correlate directly with salivary composition. Additionally, pellicle samples collected after 3, 30, 60, 120, and 240 min of intraoral exposure were analyzed. It could be shown that pellicle maturation has only a minor impact on the FA composition. However, the FA content increased substantially with increasing oral exposure time. Modifying the pellicle´s lipid composition by using edible oils as a mouthwash could alter the physicochemical characteristics of the pellicle and strengthen its protective properties by delaying bacterial adhesion. Therefore, the impact of rinses with safflower oil on the pellicle´s FA composition was determined. The application of rinses with safflower oil resulted in an accumulation of its specific FAs in the pellicle, thus representing a possibility for modifying the pellicle´s lipid profile. The present work is the first to apply a validated method that combines in situ pellicle formation, sample preparation, and the comprehensive determination of FAs via a sensitive analytical method. The results provide valuable information regarding the pellicle´s FA composition which closes an existing knowledge gap in pellicle research. A broader knowledge of the lipid composition of the pellicle contributes to the understanding of oral bioadhesion processes and may help facilitate novel approaches in preventive dentistry.
Recent studies have confirmed that the aquatic ecosystem is being polluted with an unknown cocktail of pharmaceuticals, their metabolites and/or their transformation products (TPs). Although individual pharmaceuticals are typically present at low concentrations, their continuous input into the aquatic ecosystem and their toxic and persistent presence are the major environmental concerns. Therefore, it is necessary to assess the environmental risk caused by these aquatic pollutants. Data on exposure are required for quantitative risk assessment of parent compounds and their transformation products (TPs) and/or metabolites. Such data are mostly missing, especially for TPs, because of the non-availability of TPs and very often metabolites for experimental testing. Therefore, the application of different in silico tools for qualitative risk assessment can be used. Also, the presence of these micro-pollutants (active pharmaceutical ingredients, APIs) in the aquatic cycle are increasingly seen as a challenge to the sustainable management of water resources worldwide due to ineffective effluent treatment and other measures for their input prevention. Given the poor prognosis for effluent treatment (‘end of the pipe’ approach) for input prevention of APIs in the environment, it is necessary to focus on the ‘beginning of the pipe’ strategy. The very beginning of the pipe is the molecules themselves. Therefore, novel approaches are needed like designing greener pharmaceuticals, i.e. better biodegradable ones in the aquatic environment after their release. Therefore, the present research work focused on two important topics a) assessment of the environmental risk associated with the presence of highly prescribed drugs and their TPs; b) demonstrating the feasibility of the ‘benign by design’ concept for designing biodegradable drug derivatives, which will have the better biodegradability in the environment after their release. The present thesis includes four research articles (1-4) which address these approaches. The first article is about the qualitative environmental risk assessment using the example of transformation products formed during photolysis (photo-TPs) of Diatrizoic acid (DIAT). Photolysis is the chemical reaction in which the compound is broken down by photons and often in combination with hydroxyl radicals. Photolysis is the most common abatement process of micro-pollutants in the environment. The qualitative risk assessment of DIAT and selected photo-TPs was performed by the PBT approach (i.e. Persistence, Bioaccumulation and Toxicity), using chemical analysis, experimental biodegradation test assays, QSAR models with several different toxicological endpoints and in silico read-across approaches. The second article addresses a tiered approach of implementing green and sustainable chemistry principles for theoretically designing better biodegradable and pharmacologically potent pharmaceuticals derivatives. Photodegradation process coupled with LC-MSn analysis, biodegradability testing and in silico tools such as quantitative structure-activity relationships (QSAR) analysis and molecular docking proved to be a very significant approach for the preliminary stages of designing chemical structures that would fit into the ´benign by design´ concept in the direction of green and sustainable pharmacy. Metoprolol (MTL) was used as an example. The third article was also the conceptual framework to get new drug derivatives that are biodegradable in order to tackle the global challenge of micro-pollutants in the aquatic cycle. This study increased the knowledge about the role of the attachment of certain functionalities to the parent drug molecule for its biodegradability whilst conserving drug-likeness. This approach was in the past a totally neglected issue within drug development. Atenolol (ATL), a selective β1 blocker, was selected as an example to incorporate the additional attribute such as biodegradability into its molecular structure while conserving its substructures responsible for β adrenergic receptor blocker activity. In fourth article, the concept of designing green biodegradable pharmaceuticals has been proven through expanded experimental analysis setting out from the experiences collected as described in article two and three. This study could be considered as a more extensive feasibility study of rational design of green drug derivatives. The non-selective β-blocker Propranolol (PPL) was used as an example. The risk assessment study (Article #1) contributes in enhancing the existing knowledge about the life cycle and behavior (fate) of pharmaceuticals with a special focus on photo-TPs which are generally formed during advanced effluent treatment and enter as such into the environment. Based on the obtained results, the application of the in silico tools for qualitative risk assessment analysis increased knowledge space about the environmental fate of TPs in case of their non-availability for experimental testing. The benign by design studies (Article #2-4) were based on the knowledge and experience collected during the work on DIAT. It demonstrated the feasibility of a novel approach of designing comparatively better degradable and pharmacological potent derivatives through the implementation of ´green chemistry´ principles. However, the present approach is in the juvenile stage and further knowledge has to be collected beforehand for the full implementation of this approach into drug development.
Perfluoroalkyl and polyfluoroalkyl substances (PFASs) have been widely used since 1950 in various consumer products as well as in industrial applications owing to their unique properties, e.g. being hydrophobic and lipophobic at the same time. Nowadays, some of these persistent and man-made PFASs can ubiquitously be found in humans, wildlife and various environmental media. One prominent representative of concern, belonging to the subgroup of perfluorocarboxylates (PFCs) and their conjugate acids (PFCAs), is perfluorooctanoat (PFO) and its conjugate acid (PFOA). Because of its adverse effects on human health and its persistency in the environment industry has started to replace PFO(A) and related long chain chemicals (with seven and more fully fluorinated carbon atoms) with so-called short chain PFASs (less than seven fully fluorinated carbon atoms), including precursors of PFC(A)s. Also these short chain PFC(A)s are persistent and can already be found in humans, ground- and drinking water and in remote regions. However, knowledge gaps exist in understanding the partitioning and the resulting mobility of short chain PFC(A)s in the environment. This is due to the fact that partitioning data of PFC(A)s from standardised experiments can easily be biased by various artefacts, e.g. self-aggregation of the molecules. Therefore, the objectives of this thesis are (i) to quantify the partitioning of PFC(A)s into mobile environmental media, (ii) to show how results from non-standard tests can be used to assess substance properties of concern and (iii) to conclude on whether the environmental exposure to short chain PFC(A)s is of concern from a regulatory point of view. In the first part of this thesis, the environmental mobility of short chain C4-7-PFC(A)s was investigated by quantifying their partitioning under non-standardised semi-environmental conditions into mobile environmental media, focusing on water and air, and comparing it to long chain PFC(A)s. Results are: Partitioning between water and particles in the aeration tank, primary and secondary clarifier of a wastewater treatment plant (WWTP) showed no distinct differences for short chain PFC(A)s compared to their long chain homologues (Paper 1). In a water-saturated sandy sediment column short chain PFC(A)s were not retarded, whereas long chain homologues were retarded by sorption to the sediment (Paper 2). Atmospheric particle-gas partitioning showed a lower fraction sorbed to particles for short chain PFC(A)s compared to long chain ones in samples from a WWTP (Paper 3). Air-water concentration ratios based on samples from the tanks of a WWTP were found to be higher for short chain PFC(A)s compared to long chain PFC(A)s (Paper 1). Additionally, in a newly developed experimental set-up the water to air transfer was used to derive that the pKa of C4-11-PFCAs must be <1.6 instead of up to 3.8 as reported in the literature (Paper 4). Overall, in the investigated systems short chain PFC(A)s showed a higher mobility due to a more pronounced partitioning into mobile environmental media compared to long chain PFC(A)s. In the second part of the thesis it was shown how PFO(A) - owing to its persistent, bioaccumulative and toxic (PBT-)properties – was in the context of this thesis successfully assessed as a substance of very high concern according to the criteria of the European REACH Regulation (EC No 1907/2006) by using data from non-standard tests (Paper 5). In conclusion, based on the knowledge of the high environmental mobility of short chain PFC(A)s and taking into account the argumentation of the PBT-concern of PFO(A), environmental exposure to short chain PFC(A)s is of concern and existing knowledge is already sufficient to initiate measures to prevent emissions of short chain PFC(A)s and their precursors into the environment.
Herbizide, die durch Spray-Drift, Volatilisation oder Winderosion aus landwirtschaftlichen Flächen ausgetragen werden können wiederum auf Nichtzielpflanzen gelangen. Es wird angenommen, dass Wälder eine Senke für luftgetragene Pestizide darstellen. Wirkungen von luftgetragenen Herbiziden auf Nichtzielpflanzen können nicht ausgeschlossen werden. An Blättern von Nichtzielpflanzen haftende Herbizide können wiederum durch Regenereignisse aus der Laubschicht ausgewaschen werden und in den Boden gelangen. Welche Stoffe nach deren Deposition ausgewaschen werden oder aber in der Laubschicht verbleiben hängt vom Verteilungsverhalten an der Blattoberfläche ab. In der vorliegenden Dissertation wurde das Verteilungsverhalten von current-use Herbiziden und einiger ihrer Abbauprodukte an der Oberfläche von Nichtzielpflanzen bestimmt. Als Modellorganismus diente die Waldkiefer Pinus Sylvestris L. mit deren Nadeln Versuche zur Charakterisierung des Adsorptions- und Desorptionsverhaltens von 55 Herbiziden aus wässrigen Lösungen durchgeführt wurden. Es wurden Verteilungsversuche sowohl mit rekonstituiertem epikutikulärem Wachs als auch mit intakten Kiefernnadeln durchgeführt. Für den Stoff Terbuthylazin konnte bei Versuchen mit rekonstituierten epikutikulären Wachsen eine Aufnahme aus der wässrigen Lösung in das Wachs festgestellt werden. Der Verteilungskoeffizient zwischen Wachs und Wasser betrug für die Adsorption log KWachsW = 3, 0. Für die Desorption wurde ein höherer Verteilungskoeffizient von log KWachsW = 3, 3 ermittelt und auf Grund der Differenz eine teilweise irreversible Bindung des Terbuthylazins an das epikutikuläre Wachs angenommen. Sorptionsversuche mit wässrigen Lösungen und intakten Kiefernnadeln zeigten für 19 weitere Herbizide mit einem log KOW > 3,8 eine schnelle Adsorption aus der wässrigen Phase an die Nadeloberfläche mit einer mittleren Lebensdauer für die Adsorption von 12 Minuten (Aclonifen, Bifenox, Bromoxynil-octanoat, Diflufenican, Fenoxaprop-p-ethyl, Fluazifop-p-butyl, Fluroxypyrmeptyl, Haloxyfop-ethoxyethyl, Haloxyfop-methyl, Mefenpyr-diethyl, PCP, Pendimethalin, Picolinafen, Propaquizafop, Prosulfocarb, Pyridate, Quizalofop-ethyl, Triallate und Trifluralin). Die für diese Stoffe ermittelten Kutikula/Wasser-Verteilungskoeffizienten liegen im Bereich log KCW = 3,3 bis 4,8. Für 7 Stoffe war nach einer schnellen Verringerung der Konzentration in der wässrigen Phase eine weitere stetige Abnahme der Herbizidkonzentration mit einer Lebensdauer unter 2000 Minuten zu beobachten (Fluroxypyr-meptyl, Fenoxaprop-p-ethyl, Propaquizafop, Quizalofop-ethyl, Trifluralin, Fluazifop-p-butyl und Haloxyfop-methyl), was durch eine Aufnahme der Stoffe über die epikutikuläre Wachsschicht in das innere Gewebe der Kiefernnadeln erklärt werden kann. Die Stoffe Bromoxynil-octanoat, Fluroxypyr-meptyl, Propaquizafop, Quizalofop-ethyl und Trifluralin zeigten eine irreversible Aufnahme aus wässrigen Lösungen in Kiefernnadeln. In einem Laborversuch wurde die Deposition von Herbiziden auf intakten Kiefernnadeln simuliert. Die Verteilung zwischen der epikutikulären Wachsschicht, Niederschlagswasser und den nach Extraktion mit Dichlormethan verbleibenden Nadeln wurde für das Herbizid Isoproturon und seine Abbauprodukte ermittelt. Das hierfür entwickelte Versuchsdesign erlaubte die Messung der Verteilungsvorgänge an intakten, noch am Zweig befindlichen Kiefernnadeln. Die Translokation, Volatilisation und die Bildung von Abbauprodukten konnten quantifiziert werden. Die Laborversuche ergaben, dass Isoproturon bei Kontakt mit wässrigen Lösungen sofort (Lebensdauer unter 1 Minute) von der Oberfläche der Kiefernnadeln desorbiert und nicht in das innere Gewebe der Kiefernnadel aufgenommen wird. Darüber hinaus treten bei Driftrückständen kleiner Stoffmenge und Schichtdicke (1 ng/mm²) für Isoproturon hohe Verluste (zwischen 47 und 88 % der ursprünglich applizierten Menge) durch Volatilisation und abiotischen Abbau auf. Aus den Ergebnissen der Laborversuche können Rückschlüsse zum Verbleib des Herbizids Isoproturon im Waldökosystem getroffen werden. Sie zeigen, dass Driftrückstände von polaren Herbiziden durch Regenereignisse aus der Vegetationsoberfläche von Nichtzielpflanzen ausgetragen werden und in andere Umweltkompartimente gelangen können.
