Chemical composition measurements of cloud condensation nuclei and ice nuclei by aerosol mass spectrometry

In this study the Aerodyne Aerosol Mass Spectrometer (AMS) was used during three laboratory measurement campaigns, FROST1, FROST2 and ACI-03. The FROST campaigns took place at the Leipzig Aerosol Cloud Interaction Simulator (LACIS) at the IfT in Leipzig and the ACI-03 campaign was conducted at the AIDA facility at the Karlsruhe Institute of Technology (KIT). In all three campaigns, the effect of coatings on mineral dust ice nuclei (IN) was investigated. During the FROST campaigns, Arizona Test Dust (ATD) particles of 200, 300 and 400 nm diameter were coated with thin coatings (< 7 nm) of sulphuric acid. At these very thin coatings, the AMS was operated close to its detection limits. Up to now it was not possible to accurately determine AMS detection limits during regular measurements. Therefore, the mathematical tools to analyse the detection limits of the AMS have been improved in this work. It is now possible to calculate detection limits of the AMS under operating conditions, without losing precious time by sampling through a particle filter. The instrument was characterised in more detail to enable correct quantification of the sulphate loadings on the ATD particle surfaces. Correction factors for the instrument inlet transmission, the collection efficiency, and the relative ionisation efficiency have been determined. With these corrections it was possible to quantify the sulphate mass per particle on the ATD after the condensation of sulphuric acid on its surface. The AMS results have been combined with the ice nucleus counter results. This revealed that the IN-efficiency of ATD is reduced when it is coated with sulphuric acid. The reason for this reduction is a chemical reaction of sulphuric acid with the particle's surface. These reactions are increasingly taking place when the aerosol is humidified or heated after the coating with sulphuric acid. A detailed analysis of the solubility and the evaporation temperature of the surface reaction products revealed that most likely aluminium sulphate is produced in these reactions.

Technology Development and Consumer Acceptance of Innovation in Fruit Production

Precision Agriculture (PA) and the more specific branch of Precision Horticulture are two very promising sectors. They focus on the use of technologies in agriculture to optimize the use of inputs, so to reach a better efficiency, and minimize waste of resources. This important objective motivated many researchers and companies to search new technology solutions. Sometimes the effort proved to be a good seed, but sometimes an unfeasible idea. So that PA, from its birth more or less 25 years ago, is still a “new” management, interesting for the future, but an actual low adoption rate is still reported by experts and researchers. This work aims to give a contribution in finding the causes of this low adoption rate and proposing a methodological solution to this problem. The first step was to examine prior research about Precision Agriculture adoption, by ex ante and ex post approach. It was supposed as important to find connections between these two phases of a purchase experience. In fact, the ex ante studies dealt with potential consumer’s perceptions before a usage experience occurred, therefore before purchasing a technology, while the ex post studies described the drivers which made a farmer become an end-user of PA technology. Then, an example of consumer research is presented. This was an ex ante research focused on pre-prototype technology for fruit production. This kind of research could give precious information about consumer acceptance before reaching an advanced development phase of the technology, and so to have the possibility to change something with the least financial impact. The final step was to develop the pre-prototype technology that was the subject of the consumer acceptance research and test its technical characteristics.

From carbazole-containing and pi-expanded triangular trinuclear porphyrinoids

Zusammenfassung:rnDie vorliegende Arbeit beschreibt das Design und die Synthese neuartiger Porphyrinoide anhand der Modifikation und der π-Systemausdehnung an der Peripherie des Porphyrin-Gerüsts. Die Darstellung künstlicher Porphyrine ist von Interesse, da neue physiko-chemischen Eigenschaften erhalten und untersucht werden können. Die in dieser Arbeit vorgestellten Porphyrinoide wurden mit Hilfe von modernen Synthesemethoden wie den metallkatalysierten Kreuzkupplungen und somit durch Aryl-Aryl Verknüpfungen aufgebaut.rnDer erste Teil dieser Arbeit befasst sich mit der Modifikation des Porphyrin-Gerüsts. Porphyrine bestehen aus jeweils zwei Pyrrol- und Pyrrolenin-Einheiten, welche systematisch ausgetauscht wurden. Die Pyrrol-Einheiten wurden durch Carbazol ersetzt, das sich formal vom Pyrrol durch Anfügen von zwei Benzogruppen ableitet und deshalb besonders gut geeignet ist. Die Pyrrolenin-Einheiten wurden aus folgenden Gründen durch andere Heterozyklen wie Pyridin, Pyrrol oder Triazol ersetzt: rn* Nachbildung des stabilen Porphyrin trans-NH-Tautomers (Carbazol und Pyridin)rn* Nachbildung von (NH)4-Liganden wie Calix[4]pyrrol (Carbazol und Pyrrol)rn* Vereinigung von N-H und C-H Wasserstoffbrücken-Donor-Einheiten in einem Makrozyklus (Carbazol und Triazol)rnDie Synthese eines drei-Zentren Porphyrinoids mit ausgedehntem π-System wird im zweiten Teil der vorliegenden Arbeit beschrieben. Dieses Thema basiert auf der aktuellen Entwicklung von nicht-Edelmetall basierten Katalysatoren für die Reduktion von Sauerstoff. Hier werden derzeit N4 makrozyklische Metallkomplexe, die mehrere katalytisch aktive Stellen aufweisen, untersucht. In diesem Zusammenhang, hat die Gruppe von Prof. Müllen einen neuartigen drei-Zentren-Komplex entwickelt. Ausgehend von diesen Erkenntnissen, dient diese Arbeit zur Verbesserung der katalytischen Aktivität des drei-Zentren-Komplex durch die Variation von verschieden Substituenten. Hierbei wurden zwei wesentliche Konzepte verfolgt:rn* Vernetzung durch die Bildung von Netzwerken oder durch Pyrolyse in der Mesophasern* Verbesserung des Katalysator-Trägermaterial-KontaktsrnNeben den Synthesen wurden die Eigenschaften und möglichen Anwendungen dieser neuartigen Materialen untersucht, wie z.B. als Liganden für Übergangsmetalle, als Anionenrezeptoren oder als Elektrokatalysatoren für die Reduktion von Sauerstoff. rn

Regenwald in Guyana und Suriname : Institutionen und Akteure der Inwertsetzung des Regenwaldes durch Goldbergbau, Forstwirtschaft und Tourismus

Die südamerikanischen Staaten Guyana und Suriname sind ehemalige Kolonien, die über gigantische Rohstoffressourcen verfügen. In den Regenwäldern, die die Länder zu 80 - 90% bedecken, lagern Gold und Bauxit und es wachsen wertvolle Hölzer. Außerdem haben beide Länder das Potential für eine touristische Inwertsetzung ihres Landesinneren. rnEbenso vielfältig wie die Ressourcen der Guayanas sind die Interessen daran. International agierende Unternehmen, einheimische Goldsucher sowie Indigene, Naturschützer und Dienstleister aus der Tourismusbranche stellen sich widersprechende Ansprüche an Rohstofflagerstätten sowie an touristisch vermarktbare Landschaft und Natur. Die Regierungen stehen vor der Herausforderung, die politischen Rahmenbedingungen für die Nutzung der Ressourcen des Regenwaldes festzulegen. rnDie vorliegende empirische Studie analysiert vergleichend die Motivationen der Akteure und den Einfluss von Institutionen auf die Akteure in den unterschiedlichen politischen Systemen der Staaten Guyana und Suriname. Um die Strategien der Akteure zu verstehen, wird geklärt, welche institutionelle und länderspezifische Regelungssysteme – formeller und informeller Art – die Akteure beeinflussen und inwiefern sich dabei der Einfluss der kolonialen Vergangenheit beider Staaten bemerkbar macht. rnIm Fokus der Untersuchung stehen Akteure, die an der Inwertsetzung des Regenwaldes durch Bergbau, Forstwirtschaft und (Natur-)Tourismus auf lokaler Ebene beteiligt sind sowie länderspezifischen Institutionen, die den Handlungsrahmen für diese Akteure definieren. rn

Innovative asymmetric organocatalytic processess: en route to the synthesis of biologically relevant compounds

This doctoral thesis deals with the development of novel organocatalytic strategies for asymmetric transformation. The intrinsic versatility of organocatalysis and the use of different activation modes have been exploited to achieve new catalytic enantioselective processes, towards the synthesis of biologically relevant scaffolds. The most investigated organocatalytic system have been those based on H-bond interaction (such as chiral thioureas or phosphoric acids) as well as the ones based on aminocatalysis. Despite conceptually distinct, the transformations detailed in this Thesis are linked together by simple and recurring modes of activation, induction and reactivity, promoted by the catalysts employed. The chemical diversity of the challenges encountered allows to get a precious overall view on organocatalysis, highlighting that enormous chemical diversity can be created by judicious choice of select catalyst.

Synthesis of novel cobalt and iron complexes for sustainable catalytic hydrogenations

Aim of the present work of thesis is to synthesize new non-noble metal based complexes to be employ in redox reactions by a metal-ligand cooperative mechanism. The need of replacing toxic and expensive precious metal complexes with more available and benign metals, has led to the development of new compounds based on cobalt and iron, which are the metals investigated in this study. A carbonyl-tetrahydroborato-bis[(2-diisopropylphosphino)ethyl]amine-cobalt complex bearing a PNP-type ligand is synthesized by a three-step route. Optimization attempt of reaction route were assessed in order to lowering reaction times and solvent waste. New cobalt complex has been tested in esters hydrogenation as well as in acceptorless dehydrogenative coupling of ethanol. Other varieties of substrates were also tested in order to evaluate any possible applications. Concerning iron complex, dicarbonyl-(η4-3,4-bis(4-methoxyphenyl)-2,5-diphenylcyclopenta-2,4-dienone)(1,3-dimethyl-ilidene)iron is synthesized by a three steps route, involving transmetallation of a silver complex, derived from an imidazolium salt, to iron complex. In order to avoid solvent waste, optimization is assessed. Studies were performed to assess activity of triscarbonyl iron precursor toward imidazolium salt and silver complexes.

From polyarylated cycloparaphenylenes to carbon nanotube segments and metallo N 4-macrocycles as fuel cell catalysts

In this work the synthesis of polyarylated cycloparaphenylenes (CPPs) is described in order to form structurally defined carbon nanotube (CNT) segments by the Scholl reaction. Therefore, polyphenylene macrocycles in different sizes and substitution patterns were synthesized. The influence of the ring-strain on the oxidative cyclodehydrogenation of these macrocycles towards CNT segments was investigated. It was demonstrated that a selective solution based bottom-up synthesis of CNT segments could be accomplished, having polyarylated CPPs, sufficient in size and with the right substituents at the critical positions. These findings mark an important step towards the bottom-up synthesis of length- and diameter defined ultrashort CNTsrnIn the second part of this work, novel non-precious metal catalysts (NPMCs) based on phenanthroline-indole macrocycles were synthesized and their electrocatalytic performance in the cathodic oxygen reduction was investigated. It could be demonstrated that all catalysts contributed to the direct 4-electron reduction of oxygen to water in alkaline media and a superior long-term stability was observed. Since these NPMCs are not heat pre-treated, the catalytically active site was structurally well-defined, allowing the investigation of the structure-property relationship. Moreover, it could be shown that these novel NPMCs act as efficient ORR catalysts and could replace the expensive and scarce platinum in fuel cell applications.rn

B3a km 19 - ein linienbandkeramischer Fundplatz bei Friedberg, Wetteraukreis

Durch den Straßenbau an der Bundesstraße B3a veranlasst, wurden im Zeitraum vom 13.08.2007 bis zum 07.12.2007 archäologische Untersuchungen im Bereich der Streckenkilometer 19 bis 22 durch die Firma Archbau Essen, unter Kontrolle des Landesamtes für Denkmalpflege Hessen und der Kreisarchäologie Wetteraukreis durchgeführt. Bei km 19 wurde dabei eine Siedlung mit angrenzendem Gräberfeld aus der Linienbandkeramik (im Folgenden als LBK bezeichnet) festgestellt. Daneben ergaben sich eine Bestattung und ein Erdwerk der Michelsberger Kultur, Grubenkomplexe und ein Bronzehort aus der Urnenfelderkultur sowie eine mittelalterliche Straße.Heute liegt die Fundstelle Friedberg B3a km 19 in der südlichen Wetterau 30 km nördlich von Frankfurt am Main in Hessen an der Wetter 140 m über NN und gehört zum Wetteraukreis. rnDie 21 ha messende Ausgrabungsfläche umfasste insgesamt 344 Befunde. Die Identifikation der bandkeramischen Strukturen erfolgte hierbei vorwiegend durch die vergesellschaftete Keramik. Von zentraler Bedeutung sind die fünf Hausgrundrisse A bis E im nördlichen Sektor der Fundstelle, wobei die Präsenz zahlreicher „Dreipfostenriegel“ sowie die Nordost-Südwest Ausrichtung der Strukturen als Belege für eine Zeitstellung innerhalb der LBK angesehen werden. Über die Korrespondenzanalyse der bei den Siedlungsstrukturen angetroffenen Keramik konnte darüber hinaus eine Abfolge von Hausgenerationen erstellt werden. Daneben existierten eine Reihe weiterer Befunde von LBK-zeitlichen Pfostenstellungen, bei denen es sich um Zäune oder Palisaden gehandelt haben könnte. Südwestlich dieser Hausgrundrisse wurde bei den Ausgrabungen eine Grabenstruktur geschnitten, für die eine Funktion als Einfassung der bandkeramischen Siedlungsstrukturen möglich ist. Südlich dieser Grabenstruktur konnten sechs Hockerbestattungen der LBK festgestellt werden. Die räumliche Anordnung im Bereich der westlichen Grabungsgrenze lässt den Schluss zu, dass es sich hierbei um ein Gräberfeld handelt, welches bisher nur zu einem geringen Teil ergraben wurde. Ein Zusammenhang zu den Hausgrundrissen A bis E kann erwogen werden. Der nördliche Sektor der Fundstelle umfasste außerdem zahlreiche Grubenbefunde der LBK sowie einige Grubenkomplexe, wobei letztere als Lehmentnahmegruben anzusprechen sind. Abschließend soll hier noch auf die Existenz zweier bandkeramischer Öfen, darunter ein Grubenofen, im Südosten von Friedberg B3a km 19 hingewiesen werden. rnDen mit Abstand größten Anteil am bandkeramischen Fundmaterial aus Friedberg B3 km 19 hatte die Keramik mit 3428 Elementen. An Steingeräten konnten nur 12 Silices sowie 4 Beile und 14 Mahlsteine über die Typologie und die vergesellschaftete Keramik in die LBK eingeordnet werden. Bei den Knochengeräten zeigte sich ein einzelner beschädigter Kamm. Der Fokus der Analysen des bandkeramischen Fundmaterials aus Friedberg B3a km 19 lag auf der Keramik und deren Auswertung innerhalb von Seriation und Korrespondenzanalyse. Um den Untersuchungen mehr Validität zu verleihen und eine optimale Einordnung zu erreichen, wurden die Keramik-Daten aus Friedberg B3a km 19 mit anderen Datensätzen aus Südhessen kombiniert. Dabei war nicht nur die räumliche Nähe der Fundstellen entscheidend, sondern auch die stilistisch-typologische Nähe der Inventare. In Friedberg B3a km 19 waren die Phasen nach Meier-Arendt von einem frühen III bis zum Ende der Phase V anwesend. Phase II kann nur als marginal angesprochen werden. Es ließ sich kein Übergang zum Mittelneolithikum fassen. Nach der Interpretation aller relativchronologischer Daten könnte es sich in Friedberg B3a km 19 um eine Hausentwicklung mit sieben Phasen à 25 Jahren über 175 bis zu 200 Jahren handeln, die eine kontinuierliche Belegung des Platzes von der mittleren bis zum Ende der jüngsten LBK beschreibt. Insgesamt pflegt sich die Fundstelle Friedberg B3a km 19 so in die bandkeramische Siedlungslandschaft der südlichen Wetterau ein.

Computer Aided Surgery for Percutaneous Nephrolithotomy: Clinical Requirement Analysis and System Design

Percutaneous nephrolithotomy (PCNL) for the treatment of renal stones and other related renal diseases has proved its efficacy and has stood the test of time compared with open surgical methods and extracorporal shock wave lithotripsy. However, access to the collecting system of the kidney is not easy because the available intra-operative image modalities only provide a two dimensional view of the surgical scenario. With this lack of visual information, several punctures are often necessary which, increases the risk of renal bleeding, splanchnic, vascular or pulmonary injury, or damage to the collecting system which sometimes makes the continuation of the procedure impossible. In order to address this problem, this paper proposes a workflow for introduction of a stereotactic needle guidance system for PCNL procedures. An analysis of the imposed clinical requirements, and a instrument guidance approach to provide the physician with a more intuitive planning and visual guidance to access the collecting system of the kidney are presented.

Nephrolithiasis-associated bone disease: pathogenesis and treatment options

Nephrolithiasis remains a formidable health problem in the United States and worldwide. A very important but underaddressed area in nephrolithiasis is the accompanying bone disease. Epidemiologic studies have shown that osteoporotic fractures occur more frequently in patients with nephrolithiasis than in the general population. Decreased bone mineral density and defects in bone remodeling are commonly encountered in patients with calcium nephrolithiasis. The pathophysiologic connection of bone defects to kidney stones is unknown. Hypercalciuria and hypocitraturia are two important risk factors for stone disease, and treatments with thiazide diuretics and alkali, respectively, have been shown to be useful in preventing stone recurrence in small prospective trials. However, no studies have examined the efficacy of these agents or other therapies in preventing continued bone loss in calcium stone formers. This manuscript reviews the epidemiology, pathophysiology, and potential treatments of bone disease in patients with nephrolithiasis.

Transport of Functionally Appropriate Tools by Capuchin Monkeys (Cebus apella)

Capuchin monkeys are notable among New World monkeys for their widespread use of tools. They use both hammer tools and insertion tools in the wild to acquire food that would be unobtainable otherwise. Evidence indicates that capuchins transport stones to anvil sites and use the most functionally efficient stones to crack nuts. We investigated capuchins’ assessment of functionality by testing their ability to select a tool that was appropriate for two different tool-use tasks: A stone for a hammer task and a stick for an insertion task. To select the appropriate tools, the monkeys investigated a baited tool-use apparatus (insertion or hammer), traveled to a location in their enclosure where they could no longer see the apparatus, made a selection between two tools (stick or stone), and then could transport the tool back to the apparatus to obtain a walnut. Four capuchins were first trained to select and use the appropriate tool for each apparatus. After training, they were then tested by allowing them to view a baited apparatus and then travel to a location 8 m distant where they could select a tool while out of view of the apparatus. All four monkeys chose the correct tool significantly more than expected and transported the tools back to the apparatus. Results confirm capuchins’ propensity for transporting tools, demonstrate their capacity to select the functionally appropriate tool for two different tool-use tasks, and indicate that they can retain the memory of the correct choice during a travel time of several seconds.

On Ribosome Load, Codon Bias and Protein Abundance

Different codons encoding the same amino acid are not used equally in protein-coding sequences. In bacteria, there is a bias towards codons with high translation rates. This bias is most pronounced in highly expressed proteins, but a recent study of synthetic GFP-coding sequences did not find a correlation between codon usage and GFP expression, suggesting that such correlation in natural sequences is not a simple property of translational mechanisms. Here, we investigate the effect of evolutionary forces on codon usage. The relation between codon bias and protein abundance is quantitatively analyzed based on the hypothesis that codon bias evolved to ensure the efficient usage of ribosomes, a precious commodity for fast growing cells. An explicit fitness landscape is formulated based on bacterial growth laws to relate protein abundance and ribosomal load. The model leads to a quantitative relation between codon bias and protein abundance, which accounts for a substantial part of the observed bias for E. coli. Moreover, by providing an evolutionary link, the ribosome load model resolves the apparent conflict between the observed relation of protein abundance and codon bias in natural sequences and the lack of such dependence in a synthetic gfp library. Finally, we show that the relation between codon usage and protein abundance can be used to predict protein abundance from genomic sequence data alone without adjustable parameters.

On Ribosome Load, Codon Bias and Protein Abundance

Different codons encoding the same amino acid are not used equally in protein-coding sequences. In bacteria, there is a bias towards codons with high translation rates. This bias is most pronounced in highly expressed proteins, but a recent study of synthetic GFP-coding sequences did not find a correlation between codon usage and GFP expression, suggesting that such correlation in natural sequences is not a simple property of translational mechanisms. Here, we investigate the effect of evolutionary forces on codon usage. The relation between codon bias and protein abundance is quantitatively analyzed based on the hypothesis that codon bias evolved to ensure the efficient usage of ribosomes, a precious commodity for fast growing cells. An explicit fitness landscape is formulated based on bacterial growth laws to relate protein abundance and ribosomal load. The model leads to a quantitative relation between codon bias and protein abundance, which accounts for a substantial part of the observed bias for E. coli. Moreover, by providing an evolutionary link, the ribosome load model resolves the apparent conflict between the observed relation of protein abundance and codon bias in natural sequences and the lack of such dependence in a synthetic gfp library. Finally, we show that the relation between codon usage and protein abundance can be used to predict protein abundance from genomic sequence data alone without adjustable parameters.

A VEGETATION RECONSTRUCTION OF UNION COUNTY, PENNSYLVANIA DURING THE EARLY HISTORICAL PERIOD (1755-1855)

This thesis assesses relationships between vegetation and topography and the impact of human tree-cutting on the vegetation of Union County during the early historical era (1755-1855). I use early warrant maps and forestry maps from the Pennsylvania historical archives and a warrantee map from the Union County courthouse depicting the distribution of witness trees and non-tree surveyed markers (posts and stones) in early European settlement land surveys to reconstruct the vegetation and compare vegetation by broad scale (mountains and valleys) and local scale (topographic classes with mountains and valleys) topography. I calculated marker density based on 2 km x 2 km grid cells to assess tree-cutting impacts. Valleys were mostly forests dominated by white oak (Quercus alba) with abundant hickory (Carya spp.), pine (Pinus spp.), and black oak (Quercus velutina), while pine dominated what were mostly pine-oak forests in the mountains. Within the valleys, pine was strongly associated with hilltops, eastern hemlock (Tsuga canadensis) was abundant on north slopes, hickory was associated with south slopes, and riparian zones had high frequencies of ash (Fraxinus spp.) and hickory. In the mountains, white oak was infrequent on south slopes, chestnut (Castanea dentata) was more abundant on south slopes and ridgetops than north slopes and mountain coves, and white oak and maple (Acer spp.) were common in riparian zones. Marker density analysis suggests that trees were still common over most of the landscape by 1855. The findings suggest there were large differences in vegetation between valleys and mountains due in part to differences in elevation, and vegetation differed more by topographic classes in the valleys than in the mountains. Possible areas of tree-cutting were evenly distributed by topographic classes, suggesting Europeans settlers were clearing land and harvesting timber in most areas of Union County.