Alpha, Omega end group functionalization of RAFT polymers based on pentafluorophenyl esters and methane thiosulfonates

While polymers with different functional groups along the backbone have intensively been investigated, there is still a challenge in orthogonal functionalization of the end groups. Such well-defined systems are interesting for the preparation of multiblock (co) polymers or polymer networks, for bio-conjugation or as model systems for examining the end group separation of isolated polymer chains. rnHere, Reversible Addition Fragmentation Chain Transfer (RAFT) polymerization was employed as method to investigate improved techniques for an a, w end group functionalization. RAFT produces polymers terminated in an R group and a dithioester-Z group, where R and Z stem from a suitable chain transfer agent (CTA). rnFor alpha end group functionalization, a CTA with an activated pentafluorophenyl (PFP) ester R group was designed and used for the polymerization of various methacrylate monomers, N-isopropylacrylamide and styrene yielding polymers with a PFP ester as a end group. This allowed the introduction of inert propyl amides, of light responsive diazo compounds, of the dyes NBD, Texas Red, or Oregon Green, of the hormone thyroxin and allowed the formation of multiblocks or peptide conjugates. rnFor w end group functionalization, problems of other techniques were overcome through an aminolysis of the dithioester in the presence of a functional methane thiosulfonate (MTS), yielding functional disulfides. These disulfides were stable under ambient conditions and could be cleaved on demand. Using MTS chemistry, terminal methyl disulfides (enabling self-assembly on planar gold surfaces and ligand substitution on gold and semiconductor nanoparticles), butynyl disulfide end groups (allowing the “clicking” of the polymers onto azide functionalized surfaces and the selective removal through reduction), the bio-target biotin, and the fluorescent dye Texas Red were introduced into polymers. rnThe alpha PFP amidation could be performed under mild conditions, without substantial loss of DTE. This way, a step-wise synthesis produced polymers with two functional end groups in very high yields. rnAs examples, polymers with an anchor group for both gold nanoparticles (AuNP) and CdSe / ZnS semi-conductor nanoparticles (QD) and with a fluorescent dye end group were synthesized. They allowed a NP decoration and enabled an energy transfer from QD to dye or from dye to AuNP. Water-soluble polymers were prepared with two different bio-target end groups, each capable of selectively recognizing and binding a certain protein. The immobilization of protein-polymer-protein layers on planar gold surfaces was monitored by surface plasmon resonance.Introducing two different fluorescent dye end groups enabled an energy transfer between the end groups of isolated polymer chains and created the possibility to monitor the behavior of single polymer chains during a chain collapse. rnThe versatility of the synthetic technique is very promising for applications beyond this work.

Interactions of gold nanoparticles with polymeric membranes

This thesis focuses on the interactions of nanoparticles with artificial membranes. The synthesis of the block copolymer poly(dimethylsiloxane)-block-poly(2-methyloxazoline) (PDMS-b-PMOXA) is described, as well as the formation of polymersomes in water. These polymersomes act as minimal cell models, consisting of an artificial bilayer membrane only, allowing the study of the interactions between nanoparticles and polymeric membranes. Both spherical and rod-shaped gold nanoparticles (AuNPs) were used in this study and they were characterized using light scattering (PCS), transmission electron microscopy (TEM), UV/Vis spectroscopy, and polarization anisotropy measurements. The polymer grafting on the spherical cores is asymmetric (shell asphericity) but is parallel to the inherent, due to polycrystallinity, core anisotropy, resulting in a characteristic scattering of the AuNPs in PCS.rnInteractions of polymersomes and AuNPs were investigated by PCS, cryo-TEM and UV/Vis. Three possible scenarios upon mixing of polymersomes and AuNPs can be distinguished by using only PCS: (i) no interactions between particles and vesicles, (ii) attachment of the particles to the outer side of the vesicles (decoration), and (iii) uptake of particles into the vesicles. It is shown that all three scenarios are possible, solely depending on the particle’s surface functionalization. In addition, it was revealed that the AuNPs need to be attached to the inner side of the membrane instead of diffusing freely within the vesicle. The present experimental findings essentially help with the understanding of the interactions of nanoparticles with membranes and show that the process of endocytosis can be attributed to physical processes only. rn

Ancient Greek harbours used as geo-archives for palaeotsunami research : case studies from Krane (Cefalonia), Lechaion (Gulf of Corinth) and Kyllini (Peloponnese)

Since historical times, coastal areas throughout the eastern Mediterranean are exposed to tsunami hazard. For many decades the knowledge about palaeotsunamis was solely based on historical accounts. However, results from timeline analyses reveal different characteristics affecting the quality of the dataset (i.e. distribution of data, temporal thinning backward of events, local periodization phenomena) that emphasize the fragmentary character of the historical data. As an increasing number of geo-scientific studies give convincing examples of well dated tsunami signatures not reported in catalogues, the non-existing record is a major problem to palaeotsunami research. While the compilation of historical data allows a first approach in the identification of areas vulnerable to tsunamis, it must not be regarded as reliable for hazard assessment. Considering the increasing economic significance of coastal regions (e.g. for mass tourism) and the constantly growing coastal population, our knowledge on the local, regional and supraregional tsunami hazard along Mediterranean coasts has to be improved. For setting up a reliable tsunami risk assessment and developing risk mitigation strategies, it is of major importance (i) to identify areas under risk and (ii) to estimate the intensity and frequency of potential events. This approach is most promising when based on the analysis of palaeotsunami research seeking to detect areas of high palaeotsunami hazard, to calculate recurrence intervals and to document palaeotsunami destructiveness in terms of wave run-up, inundation and long-term coastal change. Within the past few years, geo-scientific studies on palaeotsunami events provided convincing evidence that throughout the Mediterranean ancient harbours were subject to strong tsunami-related disturbance or destruction. Constructed to protect ships from storm and wave activity, harbours provide especially sheltered and quiescent environments and thus turned out to be valuable geo-archives for tsunamigenic high-energy impacts on coastal areas. Directly exposed to the Hellenic Trench and extensive local fault systems, coastal areas in the Ionian Sea and the Gulf of Corinth hold a considerably high risk for tsunami events, respectively.Geo-scientific and geoarcheaological studies carried out in the environs of the ancient harbours of Krane (Cefalonia Island), Lechaion (Corinth, Gulf of Corinth) and Kyllini (western Peloponnese) comprised on-shore and near-shore vibracoring and subsequent sedimentological, geochemical and microfossil analyses of the recovered sediments. Geophysical methods like electrical resistivity tomography and ground penetrating radar were applied in order to detect subsurface structures and to verify stratigraphical patterns derived from vibracores over long distances. The overall geochronological framework of each study area is based on radiocarbon dating of biogenic material and age determination of diagnostic ceramic fragments. Results presented within this study provide distinct evidence of multiple palaeotsunami landfalls for the investigated areas. Tsunami signatures encountered in the environs of Krane, Lechaion and Kyllini include (i) coarse-grained allochthonous marine sediments intersecting silt-dominated quiescent harbour deposits and/or shallow marine environments, (ii) disturbed microfaunal assemblages and/or (iii) distinct geochemical fingerprints as well as (iv) geo-archaeological destruction layers and (v) extensive units of beachrock-type calcarenitic tsunamites. For Krane, geochronological data yielded termini ad or post quem (maximum ages) for tsunami event generations dated to 4150 ± 60 cal BC, ~ 3200 ± 110 cal BC, ~ 650 ± 110 cal BC, and ~ 930 ± 40 cal AD, respectively. Results for Lechaion suggest that the harbour was hit by strong tsunami impacts in the 8th-6th century BC, the 1st-2nd century AD and in the 6th century AD. At Kyllini, the harbour site was affected by tsunami impact in between the late 7th and early 4th cent. BC and between the 4th and 6th cent. AD. In case of Lechaion and Kyllini, the final destruction of the harbour facilities also seems to be related to the tsunami impact. Comparing the tsunami signals obtained for each study areas with geo-scientific data from palaeotsunami events from other sites indicates that the investigated harbour sites represent excellent geo-archives for supra-regional mega-tsunamis.