Dosisexposition der Lymphabflussgebiete bei Bestrahlung des Mammakarzinoms unter brusterhaltender Therapie

Die vorliegende Dissertation untersucht die Dosisexposition der axillären und parasternalen Lymphabflussgebiete der Brustdrüse bei Bestrahlung mit Tangentenfeldern nach brusterhaltender Therapie des Mammakarzinoms. 144 Patientinnen, die im Jahre 2012 an der Uniklinik Rostock bestrahlt wurden, wurden in diese Arbeit eingeschlossen. Nach ausführlicher Fehlerbetrachtung, ergibt sich eine relevante Exposition des Axilla-Level I bei 43% und des Axilla-Level II bei 19% der Patientinnen. Eine individuelle Prognose aus Dosiskennwerten der Standardstrukturen erwies sich nicht als möglich

Atomically resolved TEM imaging of covalently functionalised graphene

Covalent functionalisation can be a powerful lever to tune the properties and processability of graphene. After overcoming the low chemical reactivity of graphene, covalent functionalisation led to the generation of new hybrid materials, applicable in a broad variation of fields. Although the process of functionalising graphene is nowadays firmly established, fundamental aspects of the produced hybrid materials remain to be clarified. Especially the atomically resolved imaging is only scarcely explored. Here we show aberration corrected in situ high resolution TEM imaging of dodecyl functionalised monolayer graphene at atomic resolution after an effective mechanical filtering approach. The mechanical filtering allows to separate adsorbed contamination from the covalently bound functional molecules and thus opens the possibility for the observation of this hybrid material. The obtained data is validated by DFT calculations and by a novel image simulation approach based on molecular dynamics (MD) simulations at room temperature

Highly strained, radially π-conjugated porphyrinylene nanohoops

Small π-conjugated nanohoops are difficult to prepare, but offer an excellent platform for studying the interplay between strain and optoelectronic properties, and, increasingly, these shape-persistent macrocycles find uses in host-guest chemistry and self-assembly. We report the synthesis of a new family of radially π-conjugated porphyrinylene/phenylene nanohoops. The strain energy in the smallest nanohoop [2]CPT is approximately 54 kcal mol⁻¹, which results in a narrowed HOMO-LUMO gap and a red shift in the visible part of the absorption spectrum. Because of its high degree of preorganization and a diameter of ca. 13 Å, [2]CPT was found to accommodate C₆₀ with a binding affinity exceeding 10⁸ M⁻¹ despite the fullerene not fully entering the cavity of the host (X-ray crystallography). Moreover, the ?-extended nanohoops [2]CPTN, [3]CPTN, and [3]CPTA (N for 1,4-naphthyl; A for 9,10-anthracenyl) have been prepared using the same strategy, and [2]CPTN has been shown to bind C₇₀ 5 times more strongly than [2]CPT. Our failed synthesis of [2]CPTA highlights a limitation of the experimental approach most commonly used to prepare strained nanohoops, because in this particular case the sum of aromatization energies no longer outweighs the buildup of ring strain in the final reaction step (DFT calculations). These results indicate that forcing ring strain onto organic semiconductors is a viable strategy to fundamentally influence both optoelectronic and supramolecular properties

Lamellar Liquid Crystals of In-Plane Lying Rod-Like Mesogens with Designer Side-Chains: the Case of Sliding vs Locked Layers

The dimensionality of self-assembled nano-structures plays an essential role for their properties and applications. Here we provide an understanding of the transition from weakly to strongly coupled lamellea in soft matter systems involving in-plane organized π-conjugated rods. For this purpose bolaamphiphilic triblock molecules consisting of a rigid biphenyl core, polar glycerol groups at the ends, and a branched (swallow-tail) or linear alkyl or semiperfluoroalkyl chain in lateral position have been synthesized and investigated. Besides weakly coupled lamellar isotropic (LamIso), lamellar nematic (LamN) and sliding lamellar smectic phases (LamSm) a sequence of three distinct types of strongly coupled (correlated) lamellar smectic phases with either centered (c2mm) or non-centered rectangular (p2mm) lattice and an intermediate oblique lattices (p2) were observed depending on chain length, chain branching and degree of chain fluorination. This new sequence is explained by the strengthening of the layer coupling and the competition between energetic packing constraints and the entropic contribution of either longitudinal or tangential fluctuations. This example of directed side chain engineering of small generic model compounds provides general clues for morphological design of two-dimensional and three-dimensionally coupled lamellar systems involving larger π-conjugated molecular rods and molecular or supramolecular polymers, being of contemporary interest

A twisted bay-substituted quaterrylene phosphorescing in the NIR spectral region

The preparation of the first soluble quaterrylene derivative featuring peripheral tert-butyl substituents and sterically hindering, core-anchored triflate groups has been achieved. This involves a facile synthetic route based on an oxidative coupling of perylene precursors in the presence of H2O2 as oxidant. The steric hindrance between the TfO substituents at the central bay position of the quaterrylene board triggers a strong deformation of the central perylene planarity, which forces the quaterrylene platform to adopt a twisted geometry as shown by X-ray analysis. Exceptionally, photophysical investigations show that the core-twisted quaterrylene phosphoresces in the NIR spectral region at 1716 nm. Moreover, third-order nonlinear optical measurements on solutions and thin film containing the relevant molecule showed very large second hyperpolarizability values, as predicted by theoretical calculations at the CAM-B3LYP/6-31G** level of theory, making this material very appealing for photonic applications