Self assembled materials for solar cell application

In der vorliegenden Arbeit wurden Materialien und Aufbauten für Hybrid Solarzellen entwickelt und erforscht. rnDer Vergleich zweier bekannter Lochleitermaterialien für Solarzellen in einfachen Blend-Systemen brachte sowohl Einsicht zur unterschiedlichen Eignung der Materialien für optoelektronische Bauelemente als auch neue Erkenntnisse in Bereichen der Langzeitstabilität und Luftempfindlichkeit beider Materialien.rnWeiterhin wurde eine Methode entwickelt, um Hybrid Solarzelle auf möglichst unkomplizierte Weise aus kostengünstigen Materialien darzustellen. Die „Eintopf“-Synthese ermöglicht die unkomplizierte Darstellung eines funktionalen Hybridmaterials für die optoelektronische Anwendung. Mithilfe eines neu entwickelten amphiphilen Blockcopolymers, das als funktionelles Templat eingesetzt wurde, konnten mit einem TiO2-Precursor in einem Sol-Gel Ansatz verschiedene selbstorganisierte Morphologien des Hybridmaterials erhalten werden. Verschiedene Morphologien wurden auf ihre Eignung in Hybrid Solarzellen untersucht. Ob und warum die Morphologie des Hybridsystems die Effizienz der Solarzelle beeinflusst, konnte verdeutlicht werden. Mit der Weiterentwicklung der „Eintopf“-Synthese, durch den Austausch des TiO2-Precursors, konnte die Solarzelleneffizienz von 0.15 auf 0.4 % gesteigert werden. Weiterhin konnte die Übertragbarkeit des Systems durch den erfolgreichen Austausch des Halbleiters TiO¬2 mit ZnO bewiesen werden.rnNew materials and assemblies were designed and tested for hybrid solar cell application. A simple blending approach was used to prepare hybrid solar cells in a convenient, cheap and fast method. Nano crystalline TiO2 rods were blended with different hole conducting materials and tested in solar cell devices. Comparing their performance in photovoltaic devices, while experimental conditions are kept identical, showed that the choice of solvent and photovoltaic characterization conducted in inert atmosphere is of different influence for different hole conducting materials. External influences as long term stability were investigated.rnIn comparison to the blend approach a new one-pot approach was invented to prepare a nanostructured, multi-functional material with orthogonal properties. It consists of TiO2 as a functional metal oxide and a new amphiphilic block-copolymer poly(ethyleneoxide)-b-poly(triphenylamine) (PEO-b-PTPA) that was synthesized. The hybrid material was obtained within a single step via self assembly in solution. Therefore a method had to be found to obtain crystalline TiO2 under mild conditions. Within the materials synthesis the block-copolymer not only acts as a templating agent but also adds an electronic functionality to the resulting hybrid material. During the synthesis a variety of self assembled morphologies ranging from spheres to wires were created in a controlled fashion. The obtained morphology depends on the weight fraction of the polymer, solvent, TiO2 precursor and acid. Studying films on silicon wafers with scanning electron microscopy (SEM) and transmission electron microscopy (TEM) a ternary phase diagram could be mapped whereas the crystallinity of TiO2 could be proved by high resolution-TEM. Different morphologies of this self assembled hybrid material were tested for solar cell application. Even for devices with layer thicknesses of the active material below 10 nm power conversion efficiencies up to 0.15 % at 1 sun and 1.5 AM were observed. The solar cell efficiency was increased with further development of the one-pot approach by changing the precursor. A polyethyleneglycole modified titanate was used as precursor in combination with the functional block copolymer PEO-b-PTPA. Again self-assembled network morphologies were obtained and tested in solar cell devices. While the formation of percolating networks is of general importance the solar cell performance was found to depend on the morphological design of the hybrid material. With the aid of conductive scanning force microscopy, it was proven to preserve a percolating network despite an increase of the active layer thickness. In combination with a special functionalized Ti-precursor hybrid bulk heterojunction solar cells having a maximum power conversion efficiency of 0.4 % at 1 sun and 1.5 AM were obtained.r

Comparing thin-sheet models with 3-D multilayer models for continental collision

Various models have been proposed to explain tectonic deformations during continent collision. A frequently applied model is the thin viscous sheet model which is however not fully 3-D and assumes a priori diffuse thickening as the dominant deformation style. We compare a fully 3-D multilayer numerical model with a corresponding thin viscous sheet numerical model for the scenario of continent indentation. In our comparison we focus on the three basic viscous deformation styles thickening, buckling (folding) and lateral crustal flow. Both numerical models are based on the finite element method (FEM) and employ either a linear or power-law viscous rheology. The 3-D model consists of four layers representing a simplified continental lithosphere: strong upper crust, weak lower crust, strong upper mantle and weak lower mantle. The effective viscosity depth-profile in the 3-D model is used to calculate the depth-averaged effective viscosity used in the thin-sheet model allowing a direct comparison of both models. We quantify the differences in the strain rate and velocity fields, and investigate the evolution of crustal thickening, buckling and crustal flow resulting from the two models for two different phases of deformation: (1) indentation with a constant velocity and (2) gravitational collapse after a decrease of the indenting velocity by a factor of 5. The results indicate that thin-sheet models approximate well the overall large-scale lithospheric deformation, especially during indentation and for a linear viscous rheology. However, in the 3-D model, additional processes such as multilayer buckling and lower crustal flow emerge, which are ignored in the thin-sheet model but dominate the deformation style in the 3-D model within a range of a few hundreds of kilometres around the collision zone and indenter corner. Differences between the 3-D and thin-sheet model are considerably larger for a power-law viscous than for a linear viscous rheology. Buckling and lower crustal flow are significant in the 3-D model with power-law viscous rheology. For example, fibre strain rates due to buckling can be several hundred per cent different to the depth-averaged strain rate and the lateral mass flow of lower crustal material can be up to six times more than the flow of upper crustal material. Our results also show that the horizontal velocity fields of the upper crust and upper mantle remain nearly identical in the 3-D model during indentation despite their mechanical decoupling due to an intermediate weak lower crust. This result questions the validity of using similarities between velocities from the surface global positioning system (GPS) and mantle shear wave splitting data as evidence for a mechanically coupled lithosphere. 3-D multilayer models provide a more complete picture of continental collision than thin-sheet models as they enable studying the timing, locality and relative importance of different processes simultaneously which is especially important for the hundreds of kilometre scale around the collision zone and indenter corners. 3-D models are, however, still computationally challenging and we, therefore, also present results of a computational performance test of several solution algorithm

All-inorganic core-shell silica-titania mesoporous colloidal nanoparticles showing orthogonal functionality

Colloidal mesoporous silica (CMS) nanoparticles with a thin titania-enriched outer shell showing a spatially resolved functionality were synthesized by a delayed co-condensation approach. The titaniashell can serve as a selective nucleation site for the growth of nanocrystalline anatase clusters. These fully inorganic pure silica-core titania-enriched shell mesoporous nanoparticles show orthogonal functionality, demonstrated through the selective adsorption of a carboxylate-containing ruthenium N3-dye. UV-Vis and fluorescence spectroscopy indicate the strong interaction of the N3-dye with the titania-phase at the outer shell of the CMS nanoparticles. In particular, this interaction and thus the selective functionalization are greatly enhanced when anatase nanocrystallites are nucleated at the titania-enriched shell surface

Glycoform-resolved pharmacokinetic studies in a rat model employing glycoengineered variants of a therapeutic monoclonal antibody

Good pharmacokinetic (PK) behavior is a key prerequisite for sufficient efficacy of therapeutic monoclonal antibodies (mAbs). Fc glycosylation is a critical quality attribute (CQA) of mAbs, due to its impact on stability and effector functions. However, the effects of various IgG Fc glycoforms on antibody PK remain unclear. We used a combination of glycoengineering and glycoform-resolved PK measurements by mass spectrometry (MS) to assess glycoform effects on PK. Four differently glycoengineered mAbs, each still containing multiple glycoforms, were separately injected into rats. Rat models have been shown to be predictive of human PK. At different time points, blood was taken, from which the mAbs were purified and analyzed with a liquid chromatography-MS-based bottom-up glycoproteomics approach. This allowed us to follow changes in the glycosylation profiles of each glycoengineered mAb over time. Enzyme-linked immunosorbent assay measurements provided an absolute concentration in the form of a sum value for all glycoforms. Information from both readouts was then combined to calculate PK parameters per glycoform. Thereby, multiple glycoform kinetics were resolved within one mAb preparation. We confirmed increased clearance of high-mannose (Man5) and hybrid-type (Man5G0) glycoforms. Specifically, Man5 showed a 1.8 to 2.6-fold higher clearance than agalactosylated, complex glycans (G0F). Unexpectedly, clearance was even higher (4.7-fold) for the hybrid-type glycan Man5G0. In contrast, clearance of agalactosylated, monoantennary glycoforms (G0F-N) was only slightly increased over G0F (1.2 to 1.4-fold). Thus, monoantennary, hybrid-type and high-mannose glycoforms should be distinguished in CQA assessments. Strikingly, alpha 2,3-linked sialylation did not affect clearance, contradicting the involvement of the asialoglycoprotein receptor in mAb clearance.Proteomic

Bedrock sculpting under an active alpine glacier revealed from cosmic-ray muon radiography.

Mountain glaciers form landscapes with U-shaped valleys, roche moutonées and overdeepenings through bedrock erosion. However, little evidence for active glacial carving has been provided particularly for areas above the Equilibrium Line Altitude (ELA) where glaciers originate. This is mainly due to our lack of information about the shape of the bedrock underneath active glaciers in highly elevated areas. In the past years, the bedrock morphology underneath active glaciers has been studied by geophysical methods in order to infer the subglacial mechanisms of bedrock erosion. However, these comprise surveys on the glaciers' surface, from where it has been difficult to investigate the lateral boundary between the ice and the bedrock with sufficient resolution. Here we perform a muon-radiographic inspection of the Eiger glacier (Switzerland, European Alps) with the aid of cosmic-ray muon attenuation. We find a reach (600 × 300 m) within the accumulation area where strong lateral glacial erosion has cut nearly vertically into the underlying bedrock. This suggests that the Eiger glacier has profoundly sculpted its bedrock in its accumulation area. This also reveals that the cosmic-ray muon radiography is an ideal technology to reconstruct the shape of the bedrock underneath an active glacier

CD83 Modulates B Cell Function In Vitro: Increased IL-10 and Reduced Ig Secretion by CD83Tg B Cells

The murine transmembrane glycoprotein CD83 is an important regulator for both thymic T cell maturation and peripheral T cell responses. Recently, we reported that CD83 also has a function on B cells: Ubiquitous transgenic (Tg) expression of CD83 interfered with the immunoglobulin (Ig) response to infectious agents and to T cell dependent as well as T cell independent model antigen immunization. Here we compare the function of CD83Tg B cells that overexpress CD83 and CD83 mutant (CD83mu) B cells that display a drastically reduced CD83 expression. Correlating with CD83 expression, the basic as well as the lipopolysaccharide (LPS) induced expression of the activation markers CD86 and MHC-II are significantly increased in CD83Tg B cells and reciprocally decreased in CD83mu B cells. Wild-type B cells rapidly upregulate CD83 within three hours post BCR or TLR engagement by de novo protein synthesis. The forced premature overexpression of CD83 on the CD83Tg B cells results in reduced calcium signaling, reduced Ig secretion and a reciprocally increased IL-10 production upon in vitro activation. This altered phenotype is mediated by CD83 expressed on the B cells themselves, since it is observed in the absence of accessory cells. In line with this finding, purified CD83mu B cells displayed a reduced IL-10 production and slightly increased Ig secretion upon LPS stimulation in vitro. Taken together, our data strongly suggest that CD83 is expressed by B cells upon activation and contributes to the regulation of B cell function

Altered maturation of peripheral blood dendritic cells in patients with breast cancer

Tumours have at least two mechanisms that can alter dendritic cell (DC) maturation and function. The first affects the ability of haematopoietic progenitors to differentiate into functional DCs; the second affects their differentiation from CD14+ monocytes, promoting an early but dysfunctional maturation. The aim of this study was to evaluate the in vivo relevance of these pathways in breast cancer patients. For this purpose, 53 patients with invasive breast cancer were compared to 68 healthy controls. To avoid isolation or culture procedures for enrichment of DCs, analyses were directly performed by flow cytometry on whole-blood samples. The expression of surface antigens and intracellular accumulation of regulatory cytokines upon LPS stimulation were evaluated. The number of DCs, and in particular of the myeloid subpopulation, was markedly reduced in cancer patients (P < 0.001). Patient DCs were characterized by a more mature phenotype compared with controls (P = 0.016), and had impaired production of IL-12 (P < 0.001), These alterations were reverted by surgical resection of the tumour. To investigate the possible role of some tumour-related immunoactive soluble factors, we measured the plasmatic levels of vascular endothelial growth factor, IL-10 and spermine. A significant inverse correlation between spermine concentration and the percentage of DCs expressing IL-12 was found. Evidence was also obtained that in vitro exposure of monocyte-derived DCs to spermine promoted their activation and maturation, and impaired their function. Taken together, our results suggest that both the above-described mechanisms could concomitantly act in breast cancer to affect DC differentiation, and that spermine could be a mediator of dysfunctional maturation of DCs

Functional Characterization of the HuR:CD83 mRNA Interaction

Maturation of dendritic cells (DC) is characterized by expression of CD83, a surface protein that appears to be necessary for the effective activation of naïve T-cells and T-helper cells by DC. Lately it was shown that CD83 expression is regulated on the posttranscriptional level by interaction of the shuttle protein HuR with a novel posttranscriptional regulatory RNA element (PRE), which is located in the coding region of the CD83 transcript. Interestingly, this interaction commits the CD83 mRNA to efficient nuclear export via the CRM1 pathway. To date, however, the structural basis of this interaction, which potentially involves three distinct RNA recognition motifs (RRM1–3) in HuR and a complex three-pronged RNA stem-loop element in CD83 mRNA, has not been investigated in detail. In the present work we analyzed this interaction in vitro and in vivo using various HuR- and CD83 mRNA mutants. We are able to demonstrate that both, RRM1 and RRM2 are crucial for binding, whereas RRM3 as well as the HuR hinge region contributed only marginally to this protein∶RNA interaction. Furthermore, mutation of uridine rich patches within the PRE did not disturb HuR:CD83 mRNA complex formation while, in contrast, the deletion of specific PRE subfragments from the CD83 mRNA prevented HuR binding in vitro and in vivo. Interestingly, the observed inhibition of HuR binding to CD83 mRNA does not lead to a nuclear trapping of the transcript but rather redirected this transcript from the CRM1- towards the NXF1/TAP-specific nuclear export pathway. Thus, the presence of a functional PRE permits nucleocytoplasmic trafficking of the CD83 transcript via the CRM1 pathway

Risk factors for hepatitis C virus infection among blood donors in southern Brazil: a case-control study

BACKGROUND: In Brazil, it is estimated that between 2.5 and 4.9% of the general population present anti-hepatitis C virus (HCV) antibodies, which corresponds to as many as 3.9 to 7.6 million chronic carriers. Chronic liver disease is associated with HCV infection in 20% to 58% of the Brazilian patients. The objective of this case-control study was to investigate the risk factors for presence of anti-HCV antibody in blood donors in southern Brazil. METHODS: One hundred and seventy eight blood donors with two positive ELISA results for anti-HCV were cases, and 356 controls tested negative. A standardized questionnaire was used to collect data concerning demographic and socioeconomic aspects, history of previous hepatitis infection, social and sexual behaviors, and number of donations. Variables were grouped into sets of hierarchical categories. Cases and controls were compared using logistic regression, odds ratios, and 95% confidence intervals. The statistical significance of the associations was assessed through likelihood ratio tests based on a P value < 0.05. RESULTS: The prevalence of anti-HCV among blood donors was 1.1%. Most of the donors were white and males. In the multivariate analysis, independent predictors of anti-HCV positivity were: intravenous drug use, blood transfusion >10 years earlier, having had two to four sexually transmitted diseases, incarceration, tattooing, sex with a hepatitis B or C virus carrier or with intravenous drug users. CONCLUSION: Intravenous drug use, blood transfusion, and tattooing were the main risk factors for anti-HCV positivity among blood donors from southern Brazil, but sexual HCV transmission should also be considered

Simian virus 40 inhibits differentiation and maturation of rhesus macaque DC-SIGN+-dendritic cells

Dendritic cells (DC) are the initiators and modulators of the immune responses. Some species of pathogenic microorganisms have developed immune evasion strategies by controlling antigen presentation function of DC. Simian virus 40 (SV40) is a DNA tumor virus of rhesus monkey origin. It can induce cell transformation and tumorigenesis in many vertebrate species, but often causes no visible effects and persists as a latent infection in rhesus monkeys under natural conditions. To investigate the interaction between SV40 and rhesus monkey DC, rhesus monkey peripheral blood monocyte-derived DC were induced using recombinant human Interleukin-4 (rhIL-4) and infective SV40, the phenotype and function of DC-specific intracellular adhesion molecule-3 grabbing nonintegrin (DC-SIGN)+ DC were analyzed by flow cytometry (FCM) and mixed lymphocyte reaction (MLR). Results showed that SV40 can down-regulate the expression of CD83 and CD86 on DC and impair DC-induced activation of T cell proliferation. These findings suggest that SV40 might also cause immune suppression by influencing differentiation and maturation of DC