Scherhaftuntersuchung zu selbstkonditionierenden Adhäsiven an Schmelz und Dentin im Vergleich zu klassischen Adhäsivsystemen der vierten und fünften Generation

Mit einem Abscherverfahren wurde in vitro die Scherhaftung (SBS) von 4 kommerziell erhältlichen Adhäsiven der 4., 5. und 6. Generation (Optibond FL, Excite, Gluma Comfort Bond, Prompt L-Pop) und 7 experimentellen Einflaschen- (Capo E1, Capo E2, Capo Water, ENA) oder selbstkonditionierenden Adhäsiven (AC, AC+Desensitizer, Resulcin Aqua Prime N) an Schmelz/Dentin untersucht.Alle Adhäsive wurden entsprechend Herstellerangaben auf flache Schmelz-/Dentinflächen appliziert. Auf alle Adhäsivflächen wurden 3,5x2mm große Tetric Ceram Prüfkörper aufgebracht. Die Proben wurden vor Thermocycling 24h in Kochsalzlösung gelagert. Anschließend wurden die SBS-Werte gemessen.Das Mehrflaschensystem Optibond (33.2/34.4) zeigte signifikant (p<0.05) höhere Werte an Schmelz und Dentin als alle experimentellen Einflaschen- und alle selbstkonditionierenden Adhäsive. Die kommerziell erhältlichen 5. Generation Bondings tendieren zu höheren Werten als die selbstkonditionierenden Adhäsive, liegen aber unter denen der 4. Generation. AC (28.1/27.0)

Generation of a NG2-EYFP mouse for studying the properties of NG2-expressing cells

A range of vectors were made in which the EYFP gene or the Cre gene were inserted in the start codon of the NG2 gene. The NG2-EYFP vectors were used to generate NG2-EYFP “knockin” mice by homologous recombination. The F1 generation showed lack of EYFP expression, due to NeoR cassette interference. Excision of the NeoR, by breeding the F1 generation to ELLA-Cre mice allowed proper expression of EYFP. NG2-EYFP heterozygous mice were characterized in detail for astrocytic, neurogenic and oligodendrocytic properties through antibody labeling. NG2-EYFP+ cells did not label for the astrocyte marker GFAP, but some cells did express S100 Beta. The cells did not label with any neuronal markers like Beta III tubulin, Neun, and double cortin, but many of the NG2-EYFP+ cells made intimate contacts to the neurons. These contacts are widespread throughout the grey and white matter of the brain. The NG2-EYFP+ cells did label for oligodendrocyte markers like PDGFα-R, NG2, Olig2, O4, and Sox 10. There were a few cells termed phantom cells that did label for NG2, but had no EYFP expression. This could have been caused by improper excision of the NeoR cassette in the F2 generation. The heterozygous mouse is a tool to allow the characterization of the in vivo properties of the NG2+ cells. Breeding of these mice to homozygosity yielded an NG2-knockout mouse, which was also subjected to initial characterization. The NG2-EYFP homozygous showed equivalent cell labeling results to the NG2-EYFP heterozygous mouse, but the phantom cells disappeared in the knockout. The results show that the NG2 cells are a heterogenous population that does not express astrocytic or neuronal markers. The homozygous mouse is an ideal tool to further dissect the properties of the cells, lacking NG2 in vivo.

In vitro generation and characterization of acute myeloid leukemia-reactive CD8 + cytotoxic T-lymphocyte clones from healthy donors

Donor-derived CD8+ cytotoxic T lymphocytes (CTLs) eliminating host leukemic cells mediate curative graft-versus-leukemia (GVL) reactions after allogeneic hematopoietic stem cell transplantation (HSCT). The leukemia-reactive CTLs recognize hematopoiesis-restricted or broadly expressed minor histocompatibility and leukemia-associated peptide antigens that are presented by human leukocyte antigen (HLA) class I molecules on recipient cells. The development of allogeneic CTL therapy in acute myeloid leukemia (AML) is hampered by the poor efficiency of current techniques for generating leukemia-reactive CTLs from unprimed healthy donors in vitro. In this work, a novel allogeneic mini-mixed lymphocyte/leukemia culture (mini-MLLC) approach was established by stimulating CD8+ T cells isolated from peripheral blood of healthy donors at comparably low numbers (i.e. 10e4/well) with HLA class I-matched primary AML blasts in 96-well microtiter plates. Before culture, CD8+ T cells were immunomagnetically separated into CD62L(high)+ and CD62L(low)+/neg subsets enriched for naive/central memory and effector memory cells, respectively. The application of 96-well microtiter plates aimed at creating multiple different responder-stimulator cell compositions in order to provide for the growth of leukemia-reactive CTLs optimized culture conditions by chance. The culture medium was supplemented with interleukin (IL)-7, IL-12, and IL-15. On day 14, IL-12 was replaced by IL-2. In eight different related and unrelated donor/AML pairs with complete HLA class I match, numerous CTL populations were isolated that specifically lysed myeloid leukemias in association with various HLA-A, -B, or -C alleles. These CTLs recognized neither lymphoblastoid B cell lines of donor and patient origin nor primary B cell leukemias expressing the corresponding HLA restriction element. CTLs expressed T cell receptors of single V-beta chain families, indicating their clonality. The vast majority of CTL clones were obtained from mini-MLLCs initiated with CD8+ CD62L(high)+ cells. Using antigen-specific stimulation, multiple CTL populations were amplified to 10e8-10e10 cells within six to eight weeks. The capability of mini-MLLC derived AML-reactive CTL clones to inhibit the engraftment of human primary AML blasts was investigated in the immunodeficient nonobese diabetic/severe combined immune deficient IL-2 receptor common γ-chain deficient (NOD/SCID IL2Rγnull) mouse model. The leukemic engraftment in NOD/SCID IL2Rγnull was specifically prevented if inoculated AML blasts had been pre-incubated in vitro with AML-reactive CTLs, but not with anti-melanoma control CTLs. These results demonstrate that myeloid leukemia-specific CTL clones capable of preventing AML engraftment in mice can be rapidly isolated from CD8+ CD62L(high)+ T cells of healthy donors in vitro. The efficient generation and expansion of these CTLs by the newly established mini-MLLC approach opens the door for several potential applications. First, CTLs can be used within T cell-driven antigen identification strategies to extend the panel of molecularly defined AML antigens that are recognizable by T cells of healthy donors. Second, because these CTLs can be isolated from the stem cell donor by mini-MLLC prior to transplantation, they could be infused into AML patients as a part of the stem cell allograft, or early after transplantation when the leukemia burden is low. The capability of these T cells to expand and function in vivo might require the simultaneous administration of AML-reactive CD4+ T cells generated by a similar in vitro strategy or, less complex, the co-transfer of CD8-depleted donor lymphocytes. To prepare clinical testing, the mini-MLLC approach should now be translated into a protocol that is compatible with good manufacturing practice guidelines.

LRP1 modulates APP trafficking and APP metabolism within compartments of the secretory pathway. Increased AICD generation is ineffective in nuclear translocation and transcriptional activation

LRP1 modulates APP trafficking and metabolism within compartments of the secretory pathway The amyloid precursor protein (APP) is the parent protein to the amyloid beta peptide (Abeta) and is a central player in Alzheimer’s disease (AD) pathology. Abeta liberation depends on APP cleavage by beta- and gamma-secretases. To date, only a unilateral view of APP processing exists, excluding other proteins, which might be transported together and/or processed dependent on each other by the secretases described above. The low density lipoprotein receptor related protein 1 (LRP1) was shown to function as such a mediator of APP processing at multiple steps. Newly synthesized LRP1 can interact with APP, implying an interaction between these two proteins early in the secretory pathway. Therefore, we wanted to investigate whether LRP1 can mediate APP trafficking along the secretory pathway, and, if so, whether it affects APP processing. Indeed, we demonstrate that APP trafficking is strongly influenced by LRP1 transport through the endoplasmic reticulum (ER) and Golgi compartments. LRP1-constructs with ER- and Golgi-retention motifs (LRP-CT KKAA, LRP-CT KKFF) had the capacity to retard APP trafficking at the respective steps in the secretory pathway. Here, we provide evidence that APP metabolism occurs in close conjunction with LRP1 trafficking, highlighting a new role of lipoprotein receptors in neurodegenerative diseases. Increased AICD generation is ineffective in nuclear translocation and transcriptional activity A sequence of amyloid precursor protein (APP) cleavages gives rise to the APP intracellular domain (AICD) together with amyloid beta peptide (Abeta) and/or p3 fragment. One of the environmental factors identified favouring the accumulation of AICD appears to be a rise in intracellular pH. This accumulation is a result of an abrogated cleavage event and does not extend to other secretase substrates. AICD can activate the transcription of artificially expressed constructs and many downstream gene targets have been discussed. Here we further identified the metabolism and subcellular localization of the constructs used in this well documented gene reporter assay. We also co-examined the mechanistic lead up to the AICD accumulation and explored possible significances for its increased expression. We found that most of the AICD generated under pH neutralized conditions is likely that cleaved from C83. Furthermore, the AICD surplus is not transcriptionally active but rather remains membrane tethered and free in the cytosol where it interacts with Fe65. However, Fe65 is still essential in AICD mediated transcriptional transactivation although its exact role in this set of events is unclear.

Charge generation, transport and recombination in organic solar cells

This thesis presents a study of the charge generation, transport, and recombination processes in organic solar cells performed with time-resolved experimental techniques. Organic solar cells based on polymers can be solution-processed on large areas and thus promise to become an inexpensive source of renewable energy. Despite significant improvements of the power conversion efficiency over the last decade, the fundamental working principles of organic solar cells are still not fully understood. It is the aim of this thesis to clarify the role of different performance limiting processes in organic solar cells and to correlate them with the molecular structure of the studied materials, i.e. poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM). By combining time-of-flight charge transport measurements, transient absorption spectroscopy, a newly developed experimental technique called time delayed double pulse experiment and drift-diffusion simulations a comprehensive analysis of the working principles of P3HT:PCBM solar cells could be performed. It was found that the molecular structure of P3HT (i.e. the regioregularity) has a pronounced influence on the morphology of thin films of pristine P3HT and of blends of P3HT with PCBM. This morphology in turn affected the charge transport properties as well as the charge generation and recombination kinetics. Well-ordered regioregular P3HT was found to be characterized by a high charge carrier mobility, efficient charge generation and low but field-dependent (non-geminate) recombination. Importantly, the charge generation yield was found to be independent of temperature and applied electric field as opposed to the expectations of the Onsager-Braun model that is commonly applied to describe the temperature and field dependence of charge generation in organic solar cells. These properties resulted in a reasonably good power conversion efficiency. In contrast to this, amorphous regiorandom P3HT was found to show poor charge generation, transport and recombination properties that combine to a much lower power conversion efficiency.

Proton magnetic resonance with parahydrogen induced polarization : Imaging strategies and continuous generation

A major challenge in imaging is the detection of small amounts of molecules of interest. In the case of magnetic resonance imaging (MRI) their signals are typically concealed by the large background signal of e.g. the tissue of the body. This problem can be tackled by hyperpolarization which increases the NMR signals up to several orders of magnitude. However, this strategy is limited for 1H, the most widely used nucleus in NMR andrnMRI, because the enormous number of protons in the body screen the small amount of hyperpolarized ones.Here, I describe a method giving rise to high 1H MRI contrast for hyperpolarized molecules against a large background signal. The contrast is based on the J-coupling induced rephasing of the NMR signal of molecules hyperpolarized via parahydrogen induce polarization (PHIP) and it can easily be implemented in common pulse sequences.rnrnHyperpolarization methods typically require expensive technical equipment (e.g. lasers or microwaves) and most techniques work only in batch mode, thus the limited lifetime of the hyperpolarization is limiting its applications. Therefore, the second part of my thesis deals with the simple and efficient generation of an hyperpolarization.These two achievements open up alternative opportunities to use the standard MRI nucleus 1H for e.g. metabolic imaging in the future.

Generation of FLT3-ITD-reactive T-cell populations from different sources

Approximately 25% of acute myeloid leukemias (AMLs) carry internal tandem duplications (ITD) of various lengths within the gene encoding the FMS-like tyrosine kinase receptor 3 (FLT3). Although varying duplication sites exist, most of these length mutations affect the protein´s juxtamembrane domain. FLT3-ITDs support leukemic transformation by constitutive phosphorylation resulting in uncontrolled activation, and their presence is associated with worse prognosis. As known form previous work, they represent leukemia- and patient-specific neoantigens that can be recognized by autologous AML-reactive CD8+ T cells (Graf et al., 2007; Graf et al., unpublished). Herein, in patient FL, diagnosed with FLT3-ITD+ AML and in first complete remission after induction chemotherapy, T cells against her leukemia´s individual FLT3-ITD were detected at a frequency up to 1.7x10-3 among peripheral blood CD8+ T lymphocytes. This rather high frequency suggested, that FLT3-ITD-reactive T cells had been expanded in vivo due to the induction of an anti-leukemia response.rnrnCell material from AML patients is limited, and the patients´ anti-leukemia T-cell repertoire might be skewed, e.g. due to complex previous leukemia-host interactions and chemotherapy. Therefore, allogeneic sources, i.e. buffy coats (BCs) from health donors and umbilical cord blood (UCB) donations, were exploited for the presence and the expansion of FLT3-ITD-reactive T-cell populations. BC- and UCB-derived CD8+ T cells, were distributed at 105 cells per well on microtiter plates and, were stimulated with antigen-presenting cells (APCs) transfected with in vitro-transcribed mRNA (IVT-mRNA) encoding selected FTL3-ITDs. APCs were autologous CD8- blood mononuclear cells, monocytes or FastDCs.rnrnBuffy coat lymphocytes from 19 healthy individuals were analyzed for CD8+ T-cell reactivity against three immunogenic FLT3-ITDs previously identified in patients VE, IN and QQ and designated as VE_, IN_ and QQ_FLT3-ITD, respectively. These healthy donors carried at least one of the HLA I alleles known to present an ITD-derived peptide from one of these FLT3-ITDs. Reactivities against single ITDs were observed in 8/19 donors. In 4 donors the frequencies of ITD-reactive T cells were determined and were estimated to be in the range of 1.25x10-6 to 2.83x10-7 CD8+ T cells. These frequencies were 1,000- to 10,000-fold lower than the frequency of autologous FLT3-ITD-reactive T cells observed in patient FL. Restricting HLA I molecules were identified in two donors. In one of them, the recognition of VE_FLT3-ITD was found to be restricted by HLA-C*07:02, which is different from the HLA allele restricting the anti-ITD T cells of patient VE. In another donor, the recognition of IN_FLT3-ITD was restricted by HLA-B*35:01, which also had been observed in patient IN (Graf et al., unpublished). By gradual 3´-fragmentation of the IN_FLT3-ITD cDNA, the 10-mer peptide CPSDNEYFYV was identified as the target of allogeneic T cells against IN_FLT3-ITD. rnLymphocytes in umbilical cord blood predominantly exhibit a naïve phenotype. Seven UCB donations were analyzed for T-cell responses against the FLT3-ITDs of patients VE, IN, QQ, JC and FL irrespective of their HLA phenotype. ITD-reactive responses against all stimulatory FLT3-ITDs were observed in 5/7 UCB donations. The frequencies of T cells against single FLT3-ITDs in CD8+ lymphocytes were estimated to be in the range of 1.8x10-5 to 3.6x10-6, which is nearly 15-fold higher than the frequencies observed in BCs. Restricting HLA I molecules were identified in 4 of these 5 positive UCB donations. They were mostly different from those observed in the respective patients. But in one UCB donation T cells against the JC_FLT3-ITD had exactly the same peptide specificity and HLA restriction as seen before in patient JC (Graf et al., 2007). Analyses of UCB responder lymphocytes led to the identification of the 10-mer peptide YESDNEYFYV, encoded by FL_FLT3-ITD, that was recognized in association with the frequent allele HLA-A*02:01. This peptide was able to stimulate and enrich ITD-reactive T cells from UCB lymphocytes in vitro. Peptide responders not only recognized the peptide, but also COS-7 cells co-transfected with FL_FLT3-ITD and HLA-A*02:01.rnrnIn conclusion, T cells against AML- and individual-specific FLT3-ITDs were successfully generated not only from patient-derived blood, but also from allogeneic sources. Thereby, ITD-reactive T cells were detected more readily and at higher frequencies in umbilical cord blood than in buffy coat lymphocytes. It occurred that peptide specificity and HLA restriction of allogeneic, ITD-reactive T cells were identical to autologous patient-derived T cells. As shown herein, allogeneic, FLT3-ITD-reactive T cells can be used for the identification of FLT3-ITD-encoded peptides, e.g. for future therapeutic vaccination studies. In addition, these T cells or their receptors can be applied to adoptive transfer.

Charge generation and recombination in hybrid organic,inorganic solar cells

This thesis deals with the investigation of exciton and charge dynamics in hybrid solar cells by time-resolved optical spectroscopy. Quasi-steady-state and transient absorption spectroscopy, as well as time-resolved photoluminescence spectroscopy, were employed to study charge generation and recombination in solid-state organic dye-sensitized solar cells, where the commonly used liquid electrolyte is replaced by an organic solid hole transporter, namely 2,2′7,7′-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9′-spirobifluorene (spiro-MeOTAD), and polymer-metal oxide bulk heterojunction solar cells, where the commonly used fullerene acceptor [6,6]-phenyl C61 butyric acid methyl ester (PCBM) is replaced by zinc oxide (ZnO) nanoparticles. By correlating the spectroscopic results with the photovoltaic performance, efficiency-limiting processes and processes leading to photocurrent generation in the investigated systems are revealed. rnIt is shown that the charge generation from several all-organic donor-π-bridge-acceptor dyes, specifically perylene monoimide derivatives, employed in solid-state dye-sensitized solar cells, is strongly dependent on the presence of a commonly used additive lithium bis(trifluoromethanesulphonyl)imide salt (Li-TFSI) at the interface. rnMoreover, it is shown that charges can not only be generated by electron injection from the excited dye into the TiO2 acceptor and subsequent regeneration of the dye cation by the hole transporter, but also by an alternative mechanism, called preceding hole transfer (or reductive quenching). Here, the excited dye is first reduced by the hole transporter and the thereby formed anion subsequently injects an electron into the titania. This additional charge generation process, which is only possible for solid hole transporters, helps to overcome injection problems. rnHowever, a severe disadvantage of solid-state dye-sensitized solar cells is re-vealed by monitoring the transient Stark effect on dye molecules at the inter-face induced by the electric field between electrons and holes. The attraction between the negative image charge present in TiO2, which is induced by the positive charge carrier in the hole transporter due to the dielectric contrast between the organic spiro-MeOTAD and inorganic titania, is sufficient to at-tract the hole back to the interface, thereby increasing recombination and suppressing the extraction of free charges.rnBy investigating the effect of different dye structures and physical properties on charge generation and recombination, design rules and guidelines for the further advancement of solid-state dye-sensitized solar cells are proposed.rnFinally, a spectroscopic study on polymer:ZnO bulk heterojunction hybrid solar cells, employing different surfactants attached to the metal oxide nanoparticles, was performed to understand the effect of surfactants upon photovoltaic behavior. By applying a parallel pool analysis on the transient absorption data, it is shown that suppressing fast recombination while simultaneously maintaining the exciton splitting efficiency by the right choice of surfactants leads to better photovoltaic performances. Suppressing the fast recombination completely, whilst maintaining the exciton splitting, could lead to a doubling of the power conversion efficiency of this type of solar cell.

Generation and characterisation of acute myeloid leukaemia-reactive CD4 + T cells and their potential to eliminate human leukaemia blasts in NSG mice

Acute myeloid leukaemia (AML) is a cancer of the haematopoietic system, which can in many cases only be cured by haematopoietic stem cell transplantation (HSCT) and donor lymphocyte infusion (DLI) (Burnett et al., 2011). This therapy is associated with the beneficial graft-versus-leukaemia (GvL) effect mediated by transplanted donor T and NK cells that either recognise mismatch HLA molecules or polymorphic peptides, so-called minor histocompatibility antigens, leukaemia-associated or leukaemia-specific antigens in the patient and thus eliminate remaining leukaemic blasts. Nevertheless, the mature donor-derived cells often trigger graft-versus-host disease (GvHD), leading to severe damages in patients’ epithelial tissue, mainly skin, liver and intestine (Bleakley & Riddell, 2004). Therefore, approaches for the selective mediation of strong GvL effects are needed, also in order to prevent relapse after transplantation. One promising opportunity is the in vitro generation of AML-reactive CD4+ T cells for adoptive transfer. CD4+ T cells are advantageous compared to CD8+ T cells, as HLA class II molecules are under non-inflammatory conditions only expressed on haematopoietic cells; a fact that would minimise GvHD (Klein & Sato, 2000). In this study, naive CD4+ T cells were isolated from healthy donors and were successfully stimulated against primary AML blasts in mini-mixed lymphocyte/leukaemia cell cultures (mini-MLLC) in eight patient/donor pairs. After three to seven weekly restimulations, T cells were shown to produce TH1 type cytokines and to be partially of monoclonal origin according to their TCR Vβ chain usage. Furthermore, they exhibited lytic activity towards AML blasts, which was mediated by the release of granzymes A and B and perforin. The patient/donor pairs used in this study were fully HLA-class I matched, except for one pair, and also matched for HLA-DR and -DQ, whereas -DP was mismatched in one or both alleles, reflecting the actual donor selection procedure in the clinic (Begovich et al., 1992). Antibody blocking experiments suggested that the generated CD4+ T cells were directed against the HLA-DP mismatches, which could be confirmed by the recognition of donor-derived lymphoblastoid cell lines (LCLs) electroporated with the mismatched DP alleles. Under non-inflammatory conditions primary fibroblasts did not express HLA-DP and were thus not recognised, supporting the idea of a safer application of CD4+ T cells regarding induction of GvHD. For the assessment of the biological significance of these T cells, they were adoptively transferred into NSG mice engrafted with human AML blasts, where they migrated to the bone marrow and lymphoid tissue and succeeded in eliminating the leukaemic burden after only one week. Therefore, AML-reactive CD4+ T cells expanded from the naive compartment by in vitro stimulation with primary leukaemia blasts appear to be a potent tool for DLI in HSCT patients and promise to mediate specific GvL effects without causing GvHD.

Optimized scheduling in real-time environments with column generation

Im Bereich sicherheitsrelevanter eingebetteter Systeme stellt sich der Designprozess von Anwendungen als sehr komplex dar. Entsprechend einer gegebenen Hardwarearchitektur lassen sich Steuergeräte aufrüsten, um alle bestehenden Prozesse und Signale pünktlich auszuführen. Die zeitlichen Anforderungen sind strikt und müssen in jeder periodischen Wiederkehr der Prozesse erfüllt sein, da die Sicherstellung der parallelen Ausführung von größter Bedeutung ist. Existierende Ansätze können schnell Designalternativen berechnen, aber sie gewährleisten nicht, dass die Kosten für die nötigen Hardwareänderungen minimal sind. Wir stellen einen Ansatz vor, der kostenminimale Lösungen für das Problem berechnet, die alle zeitlichen Bedingungen erfüllen. Unser Algorithmus verwendet Lineare Programmierung mit Spaltengenerierung, eingebettet in eine Baumstruktur, um untere und obere Schranken während des Optimierungsprozesses bereitzustellen. Die komplexen Randbedingungen zur Gewährleistung der periodischen Ausführung verlagern sich durch eine Zerlegung des Hauptproblems in unabhängige Unterprobleme, die als ganzzahlige lineare Programme formuliert sind. Sowohl die Analysen zur Prozessausführung als auch die Methoden zur Signalübertragung werden untersucht und linearisierte Darstellungen angegeben. Des Weiteren präsentieren wir eine neue Formulierung für die Ausführung mit fixierten Prioritäten, die zusätzlich Prozessantwortzeiten im schlimmsten anzunehmenden Fall berechnet, welche für Szenarien nötig sind, in denen zeitliche Bedingungen an Teilmengen von Prozessen und Signalen gegeben sind. Wir weisen die Anwendbarkeit unserer Methoden durch die Analyse von Instanzen nach, welche Prozessstrukturen aus realen Anwendungen enthalten. Unsere Ergebnisse zeigen, dass untere Schranken schnell berechnet werden können, um die Optimalität von heuristischen Lösungen zu beweisen. Wenn wir optimale Lösungen mit Antwortzeiten liefern, stellt sich unsere neue Formulierung in der Laufzeitanalyse vorteilhaft gegenüber anderen Ansätzen dar. Die besten Resultate werden mit einem hybriden Ansatz erzielt, der heuristische Startlösungen, eine Vorverarbeitung und eine heuristische mit einer kurzen nachfolgenden exakten Berechnungsphase verbindet.

Charge generation and recombination in solid-state dye-sensitized solar cells

Diese Doktorarbeit befasst sich mit Ladungsgeneration und – rekombination in Feststoff-Farbstoffsolarzellen, die spiro-OMeTAD als Lochleiter verwenden. Die vorliegende Arbeit ist in drei Fallstudien unterteilt: i.) Kern-erweiterte Rylen-Farbstoffe, ii.) ein Perylenmonoimid-Farbstoff und iii.) Donor-π verbrückte (Cyclopentadithiophen)-Akzeptor-Farbstoffe. Trotz ihres hohen molaren Extinktionskoeffizienten und der hohen Absorbanz der sensibilisierten Filme, zeigen einige dieser Farbstoffmoleküle nur geringe photovoltaischen Effizienzen. Um den Ursprung des geringen Wirkungsgrades herauszufinden, wurde breitbandige, ultraschnelle transiente Absorptionsspektroskopie an Solarzellen durchgeführt.rnInsbesondere die Auswirkungen verschiedender Ankergruppen, Dipolmomente, Photolumineszenzlebenszeiten, Lithium-Kationensensitivität und Ladungsträgerdynamik, die alle einen großen Einfluss auf den Wirkungsgrad der Solarzelle besitzen, wurden untersucht. In der ersten Fallstudie zeigte ein kurzer Rylen-Farbstoff aufgrund deutlich verlängerter Lebenszeiten die beste Effizienz im Vergleich zu größeren Kern-erweiterten Rylen-Farbstoffen. Die Lebenszeit wurde weiter reduziert, wenn Maleinsäure als Ankergruppe unter einer Ringöffnungsreaktion an die mesoporöse Oberfläche des Metalloxid-Halbleiters adsorbierte. Dies konnte mit Hilfe von Berechnungen mittels der Dichtefunktionaltheorie (DFT, B3LYP) auf die Differenz des Dipolmoments zwischen Grundzustand und angeregtem Zustand zurückgeführt werden. Die Berechnungen bekräftigen die unvorteilhafte Injektion von Ladungen durch die Änderung der Richtung des Dipolmoments, wenn eine Ringöffnung der Anhydridgruppe stattfindet. In der zweiten Studie zeigte das Perylenmonoimid-Derivat ID889 einen Wirkungsgrad von 4.5% in Feststoff-Farbstoffsolarzellen, wobei ID889 sogar ohne Zuhilfenahme eines Additivs in der Lage ist langlebige Farbstoffkationen zu bilden. Die Verwendung von Lithium-Kationen stabilisiert jedoch sowohl den Prozess der Ladungsgeneration als auch den der Ladungsregeneration. Des Weiteren wurde in ID889-sensitivierten Bauteilen kein reduktives Löschen beobachtet. Dabei wurde die Dynamik der Exzitonen mittels einer soft-modelling Methode Kurvenanalyse aus den Daten der transienten Absorptionsspektroskopie gewonnen. Zuletzt wurden Strukturen mit Cyclopentadithiophen(CPDT)-Baustein untersucht, die eine typische D-π-A Molekülstruktur bilden. FPH224 und 233 zeigten dabei eine bessere Effizienz als FPH231 und 303 aufgrund einer großen Injektionseffizienz (IE) und längerer Lebenszeit der angeregten Zustände. Dies kann auf reduktives Löschen in FPH231 und 303 zurückgeführt werden, wohingegen FPH224 und 233 einen moderaten Zerfall des Spirokationensignals zeigten.