Aggregates of diketopyrrolopyrrole dimers in solution

Dimers based on diketopyrrolopyrrole (DPP) chromophores have gained tremendous interest as an excellent material building block for organic solar cells and photodiodes. However, a counterintuitive blue-shift in their solution absorption spectra occurs with an increasing number of thiophene units bridging the DPP moieties. We allocate this to aggregates in solution, which might hinder adequate mixing in blends, leading to poor film forming quality and reduced charge generation in solution processed devices. Hence, identification of such aggregates is crucial in order to find measures for device optimisation. In this study, we present synthesis and characterisation of three pyridyl end-capped DPP dimers of different conjugation length using thiophene linkers and compare their parent monomer to evidence the behaviours of aggregates in solution. We employ conventional and temperature dependent UV–Vis spectroscopy, fluorescence and excitation-emission spectroscopy as well as TD-DFT calculations to show that such DPP dimers predominantly form aggregates in solution even at low concentrations. By disentangling the spectroscopic behaviour of both aggregated and non-aggregated species, we refute literature's explanation that the apparent blue shift in absorption arises from a reduced conjugation length due to more molecular flexibility. Instead, absorption and emission signals of non-aggregated dimers are mostly masked by their aggregated species. This work provides a tool set using common laboratory spectroscopic equipment to identify and characterise solution aggregates—information particularly important towards optimisation of organic electronics processed from solution

Specific protein antigen delivery to human Langerhans cells in intact skin

Immune modulating therapies and vaccines are in high demand, not least to the recent global spread of SARS-CoV2. To achieve efficient activation of the immune system, professional antigen presenting cells have proven to be key coordinators of such responses. Especially targeted approaches, actively directing antigens to specialized dendritic cells, promise to be more effective and accompanied by reduced payload due to less off-target effects. Although antibody and glycan-based targeting of receptors on dendritic cells have been employed, these are often expensive and time-consuming to manufacture or lack sufficient specificity. Thus, we applied a small-molecule ligand that specifically binds Langerin, a hallmark receptor on Langerhans cells, conjugated to a model protein antigen. Via microneedle injection, this construct was intradermally administered into intact human skin explants, selectively loading Langerhans cells in the epidermis. The ligand-mediated cellular uptake outpaces protein degradation resulting in intact antigen delivery. Due to the pivotal role of Langerhans cells in induction of immune responses, this approach of antigen-targeting of tissue-resident immune cells offers a novel way to deliver highly effective vaccines with minimally invasive administration

Nano-Alignment in Semiconducting Polymer Films: A Path to Achieve High Current Density and Brightness in Organic Light Emitting Transistors

Organic light emitting field effect transistors (LEFETs) integrate light emission of a diode with logic functions of a transistor into a single device architecture. This integration has the potential to provide simplified displays at low costs and access to injection lasing. However, the charge carrier mobility in LEFETs is a limiting factor in realizing high current densities along with a trade-off between brightness and efficiency. Herein, we present a technique controlling the nanoscale morphology of semiconducting polymers using nanoscale grooved substrates and dip-coating deposition to achieve high current density. We then applied this approach to heterostructure LEFETs and demonstrated brightness exceeding 29000 cd m–2 at an EQE of 0.4% for a yellow emitter and 9600 cd m–2 at an EQE of 0.7% for a blue emitter. These results represent a significant advancement in organic optoelectronics and are an important milestone toward the realization of new applications in displays and electrically pumped lasing

A Remote Secondary Binding Pocket Promotes Heteromultivalent Targeting of DC-SIGN

Dendritic cells (DC) are antigen-presenting cells coordinating the interplay of the innate and the adaptive immune response. The endocytic C-type lectin receptors DC-SIGN and Langerin display expression profiles restricted to distinct DC subtypes and have emerged as prime targets for next-generation immunotherapies and anti-infectives. Using heteromultivalent liposomes copresenting mannosides bearing aromatic aglycones with natural glycan ligands, we serendipitously discovered striking cooperativity effects for DC-SIGN+ but not for Langerin+ cell lines. Mechanistic investigations combining NMR spectroscopy with molecular docking and molecular dynamics simulations led to the identification of a secondary binding pocket for the glycomimetics. This pocket, located remotely of DC-SIGN’s carbohydrate bindings site, can be leveraged by heteromultivalent avidity enhancement. We further present preliminary evidence that the aglycone allosterically activates glycan recognition and thereby contributes to DC-SIGN-specific cell targeting. Our findings have important implications for both translational and basic glycoscience, showcasing heteromultivalent targeting of DCs to improve specificity and supporting potential allosteric regulation of DC-SIGN and CLRs in general

Automated Laser‐Transfer Synthesis of High‐Density Microarrays for Infectious Disease Screening

Laser-induced forward transfer (LIFT) is a rapid laser-patterning technique for high-throughput combinatorial synthesis directly on glass slides. A lack of automation and precision limits LIFT applications to simple proof-of-concept syntheses of fewer than 100 compounds. Here, an automated synthesis instrument is reported that combines laser transfer and robotics for parallel synthesis in a microarray format with up to 10 000 individual reactions cm−2. An optimized pipeline for amide bond formation is the basis for preparing complex peptide microarrays with thousands of different sequences in high yield with high reproducibility. The resulting peptide arrays are of higher quality than commercial peptide arrays. More than 4800 15-residue peptides resembling the entire Ebola virus proteome on a microarray are synthesized to study the antibody response of an Ebola virus infection survivor. Known and unknown epitopes that serve now as a basis for Ebola diagnostic development are identified. The versatility and precision of the synthesizer is demonstrated by in situ synthesis of fluorescent molecules via Schiff base reaction and multi-step patterning of precisely definable amounts of fluorophores. This automated laser transfer synthesis approach opens new avenues for high-throughput chemical synthesis and biological screening

Semitransparent and Low-Voltage Operating Organic Light-Emitting Field-Effect Transistors Processed at Low Temperatures

A see-through organic light emitting field-effect transistor (LEFET) is realized by using a highly transparent, high mobility material. Low voltage operated LEFETs with increased optical and electrical characteristics are shown

UV-Deep Blue-Visible Light-Emitting Organic Field Effect Transistors with High Charge Carrier Mobilities

Two non-single-crystal high-mobility single-layer light-emitting field-effect transistors (LEFETs) exhibiting narrow UV and deep-blue emission are described. The organic semiconductors are based on a [1]benzothieno[3,2-b][1]benzothiophene (BTBT) scaffold and achieve charge carrier mobilities of 2 and 6 cm2 V−1 s−1, respectively. The general applicability of BTBT-C10 as an excellent semiconductor for LEFETs is then demonstrated in conventional heterostructure LEFETs. Here it acts as a thin charge carrier layer underneath blue, yellow, and red organic light-emitting materials. This layout increases the emissive layers' optical and electrical characteristics by several orders of magnitude. Both device architectures give way toward novel display technologies and potentially injection lasers

Information transfer in mammalian glycan-based communication

Glycan-binding proteins, so-called lectins, are exposed on mammalian cell surfaces and decipher the information encoded within glycans translating it into biochemical signal transduction pathways in the cell. These glycan-lectin communication pathways are complex and difficult to analyze. However, quantitative data with single-cell resolution provide means to disentangle the associated signaling cascades. We chose C-type lectin receptors (CTLs) expressed on immune cells as a model system to study their capacity to transmit information encoded in glycans of incoming particles. In particular, we used nuclear factor kappa-B-reporter cell lines expressing DC-specific ICAM-3–grabbing nonintegrin (DC-SIGN), macrophage C-type lectin (MCL), dectin-1, dectin-2, and macrophage-inducible C-type lectin (MINCLE), as well as TNFαR and TLR-1&2 in monocytic cell lines and compared their transmission of glycan-encoded information. All receptors transmit information with similar signaling capacity, except dectin-2. This lectin was identified to be less efficient in information transmission compared to the other CTLs, and even when the sensitivity of the dectin-2 pathway was enhanced by overexpression of its co-receptor FcRγ, its transmitted information was not. Next, we expanded our investigation toward the integration of multiple signal transduction pathways including synergistic lectins, which is crucial during pathogen recognition. We show how the signaling capacity of lectin receptors using a similar signal transduction pathway (dectin-1 and dectin-2) is being integrated by compromising between the lectins. In contrast, co-expression of MCL synergistically enhanced the dectin-2 signaling capacity, particularly at low-glycan stimulant concentration. By using dectin-2 and other lectins as examples, we demonstrate how signaling capacity of dectin-2 is modulated in the presence of other lectins, and therefore, the findings provide insight into how immune cells translate glycan information using multivalent interactions

High performance p- and n-type light-emitting field-effect transistors employing thermally activated delayed fluorescence

Light-emitting field-effect transistors (LEFETs) are an emerging type of devices that combine light-emitting properties with logical switching function. One of the factors limiting their efficiency stems from the spin statistics of electrically generated excitons. Only 25% of them, short lived singlet states, are capable of light emission, with the other 75% being long lived triplet states that are wasted as heat due to spin-forbidden processes. Traditionally, the way to overcome this limitation is to use phosphorescent materials as additional emission channel harnessing the triplet excitons. Here, an alternative strategy for triplet usage in LEFETs in the form of thermally activated delayed fluorescence (TADF) is presented. Devices employing a TADF capable material, 4CzIPN (2,4,5,6-tetra[9H-carbazol-9-yl]isophthalonitrile), in both n-type and p-type configurations are shown. They manifest excellent electrical characteristics, consistent brightness in the range of 100-1,000 cd m and external quantum efficiency (EQE) of up to 0.1%, which is comparable to the equivalent organic light-emitting diode (OLED) based on the same materials. Simulation identifies the poor light out-coupling as the main reason for lower than expected EQEs. Transmission measurements show it can be partially alleviated using a more transparent top contact, however more structural optimization is needed to tap the full potential of the device

High-performance, fullerene-free organic photodiodes based on a solution-processable indigo

A solution-processable dibromoindigo with an alkyoxyphenyl solubilizing group is developed and used as a new electron acceptor in organic photodiodes. The solution-processed fullerene-free organic photodiodes show an almost spectrally flat response with a high responsivity (0.4 A W-1) and a high detectivity (1 x 10(12) Jones). These values are comparable to silicon-based photodiodes