(Oligo-)Thiophene Functionalized Tetraazaperopyrenes: Donor-Acceptor Dyes and Ambipolar Organic Semiconductors.

Tetraazaperopyrenes (TAPPs) have been functionalized with thiophene and terthiophene units of different architecture resulting in a variety of organic donor-acceptor (D-A) compounds. The influence of the connection of the thiophenes to the TAPP core on their structural, photophysical and electrochemical properties has been studied in detail by a combination of X-ray crystallography, UV-vis and fluorescence spectroscopy as well as cyclic voltammetry, which allowed the establishment of structure-property relationships. The HOMO-LUMO gap is significantly decreased upon substitution of the TAPP core with electron-donating thiophene units, the extent of which is strongly influenced by the orientation of the thiophene units. The latter also crucially directs the molecular packing in the solid. Linkage at the α-position allows both inter- and intramolecular N···S interaction, whereas linkage in the ß-position prevents intramolecular N···S interaction, resulting in a less pronounced conjugation of the TAPP core and the thiophene units. The new TAPP derivatives were processed as semiconductors in organic thin-film transistors (TFTs) that show ambipolar behavior. The insight into band gap and structure engineering may open up new possibilities to tailor the electronic properties of TAPP-based materials for certain desired applications.

A Water-Soluble Tetraazaperopyrene Dye as Strong G-Quadruplex DNA Binder.

The interactions of the water-soluble tetraazaperopyrene dye 1 with ct-DNA, duplex-[(dAdT)12 ⋅(dAdT)12 ], duplex-[(dGdC)12 ⋅(dGdC)12 ] as well as with two G-quadruplex-forming sequences, namely the human telomeric 22AG and the promotor sequence c-myc, were investigated by means of UV/visible and fluorescence spectroscopy, isothermal titration calorimetry (ITC) and molecular docking studies. Dye 1 exhibits a high affinity for G-quadruplex structures over duplex DNA structures. Furthermore, the ligand shows promising G-quadruplex discrimination, with an affinity towards c-myc of 2×10(7) m(-1) (i.e., Kd =50 nm), which is higher than for 22AG (4×10(6) m(-1) ). The ITC data reveal that compound 1 interacts with c-myc in a stoichiometric ratio of 1:1 but also indicate the presence of two identical lower affinity secondary binding sites per quadruplex. In 22AG, there are two high affinity binding sites per quadruplex, that is, one on each side, with a further four weaker binding sites. For both quadruplex structures, the high affinity interactions between compound 1 and the quadruplex-forming nucleic acid structures are weakly endothermic. Molecular docking studies suggest an end-stacking binding mode for compound 1 interacting with quadruplex structures, and a higher affinity for the parallel conformation of c-myc than for the mixed-hybrid conformation of 22AG. In addition, docking studies also suggest that the reduced affinity for duplex DNA structures is due to the non-viability of an intercalative binding mode.

Core Halogenation as a Construction Principle in Tuning the Material Properties of Tetraazaperopyrenes.

A detailed study on the effects of core halogenation of tetraazaperopyrene (TAPP) derivatives is presented. Its impact on the solid structure, as well as the photophysical and electrochemical properties, has been probed by the means of X-ray crystallography, UV/Vis and fluorescence spectroscopy, high-resolution electron energy loss spectroscopy (HREELS), cyclic voltammetry (CV), and DFT modeling. The aim was to assess the potential of this approach as a construction principle for organic electron-conducting materials of the type studied in this work. Although halogenation leads to a stabilization of the LUMOs compared to the unsubstituted parent compound, the nature of the halide barely affects the LUMO energy while strongly influencing the HOMO energies. In terms of band-gap engineering, it was demonstrated that the HOMO-LUMO gap is decreased by substitution of the TAPP core with halides, the effect being found to be most pronounced for the iodinated derivative. The performance of the recently reported core-fluorinated and core-iodinated TAPP derivatives in organic thin-film transistors (TFTs) was investigated on both a glass substrate, as well as on a flexible plastic substrate (PEN). Field-effect mobilities of up to 0.17 cm(2) Vs(-1) and on/off current ratio of >10(6) were established.

Introducing the trier univalence neutrality ambivalence (TUNA) database: A picture database differentiating complex attitudes.

Using validated stimulus material is crucial for ensuring research comparability and replicability. However, many databases rely solely on bidimensional valence ratings, ranging from negative to positive. While this material might be appropriate for certain studies, it does not reflect the complexity of attitudes and therefore might hamper the unambiguous interpretation of some study results. In fact, most databases cannot differentiate between neutral (i.e., neither positive nor negative) and ambivalent (i.e., simultaneously positive and negative) attitudes. Consequently, even presumably univalent (only positive or negative) stimuli cannot be clearly distinguished from ambivalent ones when selected via bipolar rating scales. In the present research, we introduce the Trier Univalence Neutrality Ambivalence (TUNA) database, a database containing 304,262 validation ratings from heterogeneous samples of 3,232 participants and at least 20 (M = 27.3, SD = 4.84) ratings per self-report scale per picture for a variety of attitude objects on split semantic differential scales. As these scales measure positive and negative evaluations independently, the TUNA database allows to distinguish univalence, neutrality, and ambivalence (i.e., potential ambivalence). TUNA also goes beyond previous databases by validating the stimulus materials on affective outcomes such as experiences of conflict (i.e., felt ambivalence), arousal, anger, disgust, and empathy. The TUNA database consists of 796 pictures and is compatible with other popular databases. It sets a focus on food pictures in various forms (e.g., raw vs. cooked, non-processed vs. highly processed), but includes pictures of other objects that are typically used in research to study univalent (e.g., flowers) and ambivalent (e.g., money, cars) attitudes for comparison. Furthermore, to facilitate the stimulus selection the TUNA database has an accompanying desktop app that allows easy stimulus selection via a multitude of filter options.

Eleven strategies for making reproducible research and open science training the norm at research institutions.

Reproducible research and open science practices have the potential to accelerate scientific progress by allowing others to reuse research outputs, and by promoting rigorous research that is more likely to yield trustworthy results. However, these practices are uncommon in many fields, so there is a clear need for training that helps and encourages researchers to integrate reproducible research and open science practices into their daily work. Here, we outline eleven strategies for making training in these practices the norm at research institutions. The strategies, which emerged from a virtual brainstorming event organized in collaboration with the German Reproducibility Network, are concentrated in three areas: (i) adapting research assessment criteria and program requirements; (ii) training; (iii) building communities. We provide a brief overview of each strategy, offer tips for implementation, and provide links to resources. We also highlight the importance of allocating resources and monitoring impact. Our goal is to encourage researchers - in their roles as scientists, supervisors, mentors, instructors, and members of curriculum, hiring or evaluation committees - to think creatively about the many ways they can promote reproducible research and open science practices in their institutions.

A New Reactor Concept for Single-Chamber Microbial Fuel Cells and Possible Anti-Fouling Strategies for Long-Term Operation.

Microbial fuel cells are a promising technology for future wastewater treatment, as it allows cleaning and power generation simultaneously. The bottleneck of microbial fuel cells is often its cathodes because they determine the power output. Gas diffusion electrodes might overcome this bottleneck due to their low production costs and high oxygen reduction rates. However, biofilm formation on the gas diffusion electrodes reduces their performance over time. In this work, a new reactor design of the microbial fuel cell using rotating gas diffusion electrodes is presented. The biofilm growth on the electrode during operation was observed and its effect on the performance of the microbial fuel cell was examined. In addition, different antifouling strategies were investigated over a period of 80 days. It was found that already after 7 days of operation a complete biofilm had grown on an untreated gas diffusion electrode. However, this does not seem to affect the performance of the cells in the beginning. Differences in the performance of the reactors with and without an antifouling strategy only become apparent from day 15 onwards. The use of UV radiation and antibacterial membranes leads to the best results with maximum power densities of approx. 200 mW m-2 while the untreated microbial fuel cell only achieves a maximum power density of approx. 20 mW m-2.

Expression signatures of early-stage and advanced medaka melanomas.

Melanoma is one of the most aggressive tumors with a very low survival rate once metastasized. The incidence of newly detected cases increases every year suggesting the necessity of development and application of innovative treatment strategies. Human melanoma develops from melanocytes localized in the epidermis of the skin to malignant tumors because of deregulated effectors influencing several molecular pathways. Despite many advances in describing the molecular changes accompanying melanoma formation, many critical and clinically relevant molecular features of the transformed pigment cells and the underlying mechanisms are largely unknown. To contribute to a better understanding of the molecular processes of melanoma formation, we use a transgenic medaka melanoma model that is well suited for the investigation of melanoma tumor development because fish and human melanocytes are both localized in the epidermis. The purpose of our study was to gain insights into melanoma development from the first steps of tumor formation up to melanoma progression and to identify gene expression patterns that will be useful for monitoring treatment effects in drug screening approaches. Comparing transcriptomes from juvenile fish at the tumor initiating stage with nevi and advanced melanoma of adults, we identified stage specific expression signatures and pathways that are characteristic for the development of medaka melanoma, and are also found in human malignancies.

Tetralithiated tetraazaperopyrene as a key intermediate for the synthesis of functionalized derivatives.

A new synthetic approach to core-functionalized tetraazaperopyrenes (TAPP) is reported. In-situ reaction of 4-fold lithiated TAPP with electrophiles results in the formation of various unprecedented TAPP derivatives, which are highly emissive fluorophores, show promising photophysical and electrochemical properties and act as valuable starting materials. Thus, lithiation of the TAPP core opens up a facile way for developing new organic materials.

Highly emissive water-soluble tetraazaperopyrenes as fluorescent markers.

Water-soluble tetraazaperopyrene (TAPP) derivatives have been synthesized, which show both high photostability and high fluorescence quantum yields (>80%) in water. Furthermore delivery of the dye into cells demonstrated selective staining of the nucleus.