Dipodal Ferrocene Derivatives for Nanostructured Redox-Functionalised Surfaces

Self-assembled monolayers (SAMs) on solid surfaces are of great current interest in science and nanotechnology. This thesis describes the preparation of several symmetrically 1,1’-substituted ferrocene derivatives that contain anchoring groups suitable for chemisorption on gold and may give rise to SAMs with electrochemically switchable properties. The binding groups are isocyano (-NC), isothiocyanato (-NCS), phosphanyl (-PPh2), thioether (-SR) and thienyl. In the context of SAM fabrication, isothiocyanates and phosphanes are adsorbate systems which, surprisingly, have remained essentially unexplored. SAMs on gold have been fabricated with the adsorbates from solution and investigated primarily by X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy. The results of these analytical investigations are presented and discussed in matters of the film quality and possible binding modes. The quality of self-assembled monolayers fabricated from 1,1’-diisocyanoferrocene and 1,1’-diisothiocyanatoferrocene turned out to be superior to that of films based on the other adsorbate species investigated. Films of those absorbates as well as of dppf afforded well-defined SAMs of good quality. All other films of this study based on sulfur containing anchoring groups exhibit chemical inhomogeneity and low orientational order of the film constituents and therefore failed to give rise to well-defined SAMs. Surface coordination chemistry is naturally related to molecular coordination chemistry. Since all SAMs described in this thesis were prepared on gold (111) surfaces, the ferrocene-based ligands of this study have been investigated in their ability for complexation towards gold(I). The sulfur-based ferrocene ligands [fc(SR)2] failed to give stable gold(I) complexes. In contrast, 1,1’-diisocyanoferrocene (1) proved to be an excellent ligand for the complexation of gold(I). Several complexes were prepared and characterised utilising a series of gold(I) acetylides. These complexes show interesting structural motifs in the solid state, since intramolecular aurophilic interactions lead to a parallel orientation of the isocyano moieties, combined with an antiparallel alignment of neighbouring units. The reaction of 1 with the gold(I) acetylide [Au(C≡C–Fc)]n turned out to be very unusual, since the two chemically equivalent isocyano groups undergo a different reaction. One group shows an ordinary coordination and the other one undergoes an extraordinary 1,1-insertion into the Au-C bond. As a sideline of the research of this thesis several ferrocene derivatives have been tested for their suitability for potential surface reactions. Copper(I) mediated 1,3-dipolar cycloadditions of azidoferrocene derivatives with terminal alkynes appeared very promising in this context, but failed to a certain extent in terms of ‘click’ chemistry, since the formation of the triazoles depended on the strict exclusion of oxygen and moisture and yields were only moderate. Staudinger reactions between dppf and azidoferrocene derivatives were also tested. The nucleophilic additions of secondary amines to 1,1’-diisothiocyanatoferrocene led to the respective thiourea derivatives in quantitative yields.

Gender and Space in Tehran

Abstract: This dissertation generally concentrates on the relationships between “gender” and “space” in the present time of urban life in capital city of Tehran. “Gender” as a changing social construct, differentiated within societies and through time, studied this time by investigation on “gender attitude” or “gender identity” means attitudes towards “gender” issues regarding Tehran residences. “Space” as a concept integrated from physical and social constituents investigated through focus on “spatial attitude” means attitudes towards using “living spaces” including private space of “house”, semi private semi public space of neighborhood and finally public spaces of the city. “Activities and practices” in space concentrated instead of “physical” space; this perspective to “space” discussed as the most justified implication of “space” in this debate regarding current situations in city of Tehran. Under a systematic approach, the interactions and interconnections between “gender” and “space” as two constituent variables of social organization investigated by focus on the different associations presented between different “gender identities” and their different “spatial identities”; in fact, “spatial identity” manifests “gender identity” and in opposite direction, “spatial identity” influences to construction of “gender identity”. The hypotheses of case study in Tehran defined as followed: • “Gender identity” is reflected on “spatial identity”. Various “gender identities” in Tehran present different perspectives of “space” or they identify “space” by different values. • As “gender identity” internalizes patriarchal oppression, it internalizes associated “spatial” oppression too. • Within the same social class, different “gender identities” related to men and women, present interconnected qualities, compared with “gender identities” related to men or women of different social classes. This situation could be found in the “spatial” perspectives of different groups of men and women too. • Following the upper hypotheses, “spatial” oppression differs among social classes of Tehran living in different parts of this city. This research undertook a qualitative study in Tehran by interviewing with different parents of both young daughter and son regarding their attitudes towards gender issues from one side and activities and behaviors of their children in different spaces from the other side. Results of case study indicated the parallel changes of parents’ attitudes towards “gender” and “spatial” issues; it means strong connection between “gender” and “space”. It revealed association of “equal” spatial attitudes with “open, neutral” gender attitudes, and also the association of “biased, unequal” spatial identities with “conservative patriarchal” gender identities. It was cleared too that this variable concept – gender space - changes by “sex”; mothers comparing fathers presented more equitable notions towards “gender spatial” issues. It changes too by “social class” and “educational level”, that means “gender spatial” identity getting more open equitable among more educated people of middle and upper classes. “Breadwinning status in the family” also presents its effect on the changes of “gender spatial” identity so participant breadwinners in the family expressed relatively more equitable notions comparing householders and housekeepers. And finally, “gender spatial” identity changes through “place” in the city and regarding South – North line of the city. The illustration of changes of “gender spatial” identity from “open” to “conservative” among society indicated not only vertical variation across social classes, furthermore the horizontal changing among each social class. These results also confirmed hypotheses while made precision on the third one regarding variable of sex. More investigations pointed to some inclusive spatial attitudes throughout society penetrated to different groups of “gender identities”, to “opens” as to “conservatives”, also to groups between them, by two opposite features; first kind, conservative biased spatial practices in favor of patriarchal gender relations and the second, progressive neutral actions in favor of equal gender relations. While the major reason for the inclusive conservative practices was referred to the social insecurity for women, the second neutral ones associated to more formal & safer spaces of the city. In conclusion, while both trends are associated deeply with the important issues of “sex” & “body” in patriarchal thoughts, still strong, they are the consequences of the transitional period of social change in macro level, and the challenges involved regarding interactions between social orders, between old system of patriarchy, the traditional biased “gender spatial” relations and the new one of equal relations. The case study drew an inhomogeneous illustration regarding gender spatial aspects of life in Tehran, the opposite groups of “open” and “conservative”, and the large group of “semi open semi conservative” between them. In macro perspective it presents contradicted social groups according their general life styles; they are the manifestations of challenging trends towards tradition and modernity in Iranian society. This illustration while presents unstable social situations, necessitates probing solutions for social integration; exploring the directions could make heterogeneous social groups close in the way they think and the form they live in spaces. Democratic approaches like participatory development planning might be helpful for the city in its way to more solidarity and sustainability regarding its social spatial – gender as well – development, in macro levels of social spatial planning and in micro levels of physical planning, in private space of house and in public spaces of the city.

Effects of plant diversity on bioenergy parameters in grassland biomass

Extensive grassland biomass for bioenergy production has long been subject of scientific research. The possibility of combining nature conservation goals with a profitable management while reducing competition with food production has created a strong interest in this topic. However, the botanical composition will play a key role for solid fuel quality of grassland biomass and will have effects on the combustion process by potentially causing corrosion, emission and slagging. On the other hand, botanical composition will affect anaerobic digestibility and thereby the biogas potential. In this thesis aboveground biomass from the Jena-Experiment plots was harvested in 2008 and 2009 and analysed for the most relevant chemical constituents effecting fuel quality and anaerobic digestibility. Regarding combustion, the following parameters were of main focus: higher heating value (HHV), gross energy yield (GE), ash content, ash softening temperature (AST), K, Ca, Mg, N, Cl and S content. For biogas production the following parameters were investigated: substrate specific methane yield (CH4 sub), area specific methane yield (CH4 area), crude fibre (CF), crude protein (CP), crude lipid (CL) and nitrogen-free extract (NfE). Furthermore, an improvement of the fuel quality was investigated through applying the Integrated generation of solid Fuel and Biogas from Biomass (IFBB) procedure. Through the specific setup of the Jena-Experiment it was possible to outline the changes of these parameters along two diversity gradients: (i) species richness (SR; 1 to 60 species) and (ii) functional group (grasses, legumes, small herbs and tall herbs) presence. This was a novel approach on investigating the bioenergy characteristic of extensive grassland biomass and gave detailed insight in the sward-composition¬ - bioenergy relations such as: (i) the most relevant SR effect was the increase of energy yield for both combustion (annual GE increased by 26% from SR8→16 and by 65% from SR8→60) and anaerobic digestion (annual CH4 area increased by 22% from SR8→16 and by 49% from SR8→60) through a strong interaction of SR with biomass yield; (ii) legumes play a key role for the utilization of grassland biomass for energy production as they increase the energy content of the substrate (HHV and CH4 sub) and the energy yield (GE and CH4 area); (iii) combustion is the conversion technique that will yield the highest energy output but requires an improvement of the solid fuel quality in order to reduce the risk of corrosion, emission and slagging related problems. This was achieved through applying the IFBB-procedure, with reductions in ash (by 23%), N (28%), K (85%), Cl (56%) and S (59%) and equal levels of concentrations along the SR gradient.

Heat stress response for physiological traits in dairy and dual purpose cattle populations on phenotypic and genetic scales

The main objective of this thesis was to determine the potential impact of heat stress (HS) on physiological traits of lactating cows and semen quality of bulls kept in a temperate climate. The thesis is comprised of three studies. An innovative statistical modeling aspect common to all three studies was the application of random regression methodology (RRM) to study the phenotypic and genetic trajectory of traits in dependency of a continuous temperature humidity index (THI). In the first study, semen quality and quantity traits of 562 Holstein sires kept on an AI station in northwestern Germany were analyzed in the course of THI calculated from data obtained from the nearest weather station. Heat stress was identified based on a decline in semen quality and quantity parameters. The identified general HS threshold (THI = 60) and the thermoneutal zone (THI in the range from 50 to 60) for semen production were lower than detected in studies conducted in tropical and subtropical climates. Even though adult bulls were characterized by higher semen productivity compared to younger bulls, they responded with a stronger semen production loss during harsh environments. Heritabilities (low to moderate range) and additive genetic variances of semen characteristics varied with different levels of THI. Also, based on genetic correlations genotype, by environment interactions were detected. Taken together, these findings suggest the application of specific selection strategies for specific climate conditions. In the second study, the effect of the continuous environmental descriptor THI as measured inside the barns on rectal temperatures (RT), skin temperatures (ST), vaginal temperatures (VT), respiration rates (RR), and pulse rate (PR) of lactating Holstein Friesian (HF) and dual-purpose German black pied cattle (DSN) was analyzed. Increasing HS from THI 65 (threshold) to THI 86 (maximal THI) resulted in an increase of RT by 0.6 °C (DSN) and 1 °C (HF), ST by 3.5 °C (HF) and 8 °C (DSN), VT by 0.3 °C (DSN), and RR by 47 breaths / minute (DSN), and decreased PR by 7 beats / minute (DSN). The undesired effects of rising THI on physiological traits were most pronounced for cows with high levels of milk yield and milk constituents, cows in early days in milk and later parities, and during summer seasons in the year 2014. In the third study of this dissertation, the genetic components of the cow’s physiological responses to HS were investigated. Heat stress was deduced from indoor THI measurements, and physiological traits were recorded on native DSN cows and their genetically upgraded crosses with Holstein Friesian sires in two experimental herds from pasture-based production systems reflecting a harsh environment of the northern part of Germany. Although heritabilities were in a low range (from 0.018 to 0.072), alterations of heritabilities, repeatabilities, and genetic components in the course of THI justify the implementation of genetic evaluations including heat stress components. However, low repeatabilities indicate the necessity of using repeated records for measuring physiological traits in German cattle. Moderate EBV correlations between different trait combinations indicate the potential of selection for one trait to simultaneously improve the other physiological attributes. In conclusion, bulls of AI centers and lactating cows suffer from HS during more extreme weather conditions also in the temperate climate of Northern Germany. Monitoring physiological traits during warm and humid conditions could provide precious information for detection of appropriate times for implementation of cooling systems and changes in feeding and management strategies. Subsequently, the inclusion of these physiological traits with THI specific breeding values into overall breeding goals could contribute to improving cattle adaptability by selecting the optimal animal for extreme hot and humid conditions. Furthermore, the recording of meteorological data in close distance to the cow and visualizing the surface body temperature by infrared thermography techniques might be helpful for recognizing heat tolerance and adaptability in cattle.