Robustness of antiadhesion between nanofibers and surfaces covered with nanoripples of varying spatial period.

Since nanofibers have a high surface-to-volume ratio, van der Waals forces render them attracted to virtually any surface. The high ratio provides significant advantages for applications in drug delivery, wound healing, tissue regeneration, and filtration. Cribellate spiders integrate thousands of nanofibers into their capture threads as an adhesive to immobilize their prey. These spiders have antiadhesive nanoripples on the calamistrum, a comb-like structure on their hindmost legs, and are thus an ideal model for investigating how nanofiber adhesion can be reduced. We found that these nanoripples had similar spacing in the cribellate species Uloborus plumipes, Amaurobius similis, and Menneus superciliosus, independent of phylogenetic relation and size. Ripple spacing on other body parts (i.e., cuticle, claws, and spinnerets), however, was less homogeneous. To investigate whether a specific distance between the ripples determines antiadhesion, we fabricated nanorippled foils by nanosecond UV laser processing. We varied the spatial periods of the nanoripples in the range ~203-613 nm. Using two different pulse numbers resulted in ripples of different heights. The antiadhesion was measured for all surfaces, showing that the effect is robust against alterations across the whole range of spatial periods tested. Motivated by these results, we fabricated irregular surface nanoripples with spacing in the range ~130-480 nm, which showed the same antiadhesive behavior. The tested surfaces may be useful in tools for handling nanofibers such as spoolers for single nanofibers, conveyor belts for producing endless nanofiber nonwoven, and cylindrical tools for fabricating tubular nanofiber nonwoven. Engineered fibers such as carbon nanotubes represent a further candidate application area.

Integration of Inkjet Printed Graphene as a Hole Transport Layer in Organic Solar Cells.

This work demonstrates the green production of a graphene ink for inkjet printing and its use as a hole transport layer (HTL) in an organic solar cell. Graphene as an HTL improves the selective hole extraction at the anode and prevents charge recombination at the electronic interface and metal diffusion into the photoactive layer. Graphite was exfoliated in water, concentrated by iterative centrifugation, and characterized by Raman. The concentrated graphene ink was incorporated into inverted organic solar cells by inkjet printing on the active polymer in an ambient atmosphere. Argon plasma was used to enhance wetting of the polymer with the graphene ink during printing. The argon plasma treatment of the active polymer P3HT:PCBM was investigated by XPS, AFM and contact angle measurements. Efficiency and lifetime studies undertaken show that the device with graphene as HTL is fully functional and has good potential for an inkjet printable and flexible alternative to PEDOT:PSS.

Elucidating the Origins of High Preferential Crystal Orientation in Quasi-2D Perovskite Solar Cells.

Incorporating large organic cations to form 2D and mixed 2D/3D structures significantly increases the stability of perovskite solar cells. However, due to their low electron mobility, aligning the organic sheets to ensure unimpeded charge transport is critical to rival the high performances of pure 3D systems. While additives such as methylammonium chloride (MACl) can enable this preferential orientation, so far, no complete description exists explaining how they influence the nucleation process to grow highly aligned crystals. Here, by investigating the initial stages of the crystallization, as well as partially and fully formed perovskites grown using MACl, the origins underlying this favorable alignment are inferred. This mechanism is studied by employing 3-fluorobenzylammonium in quasi-2D perovskite solar cells. Upon assisting the crystallization with MACl, films with a degree of preferential orientation of 94%, capable of withstanding moisture levels of 97% relative humidity for 10 h without significant changes in the crystal structure are achieved. Finally, by combining macroscopic, microscopic, and spectroscopic studies, the nucleation process leading to highly oriented perovskite films is elucidated. Understanding this mechanism will aid in the rational design of future additives to achieve more defect tolerant and stable perovskite optoelectronics.

Data on production and characterization of melamine-furan-formaldehyde particles and reversible reactions thereof.

The data present in this article affords insides in the characterization of a newly described bi-functional furan-melamine monomer, which is used for the production of monodisperse, furan-functionalized melamine-formaldehyde particles, as described in https://doi.org/10.1016/j.eurpolymj.2019.04.006 Urdl et al., 2019. In the related research article Urdl et al., 2019 data interpretations can be found. The furan-functionalization of particles is necessary to perform reversible Diels-Alder reactions with maleimide (BMI) crosslinker to form thermoreversible network systems. To understand the reaction conditions of Diels-Alder (DA) reaction with a Fu-Mel monomer and a maleimide crosslinker, model DA reaction were performed and evaluated using dynamic FT-IR measurements. During retro Diels-Alder (rDA) reactions of the monomer system, it was found out that some side reaction occurred at elevated temperatures. The data of evaluating the side reaction is described in one part of this manuscript. Additional high resolution SEM images of Fu-Mel particles are shown and thermoreversible particle networks with BMI2 are shown. The data of different Fu-Mel particle networks with maleimide crosslinker are presented. Therefore, the used maleimide crosslinker with different spacer lengths were synthesized and the resulting networks were analyzed by ATR-FT-IR, SEM and DSC.

Grinding of nano-graphite inkjet inks for application in organic solar cells.

The production of printable graphene flakes is not easy to scale up when produced by ultrasonication and purified by centrifugation. In this work, natural graphite flakes were exfoliated by wet ball milling in water supported by the addition of sodium deoxycholate as a surfactant and the dispersion was formulated for inkjet printing. By subsequent dilution and filtration of the milling paste, more than 45 l of a stable dispersion of nano-graphite particles in one batch process was obtained. The dispersion was characterized by thermogravimetric analysis and UV-vis spectroscopy to determine concentration, and experiments to measure long-term stability were conducted. The nano-graphite particles were analyzed by optical microscopy, scanning electron microscopy and Raman spectroscopy, revealing 300-400 nm sized particles. The dispersion was formulated into an inkjet ink and tested as interfacial hole transport layer between the anode and the photo-active bulk-heterojunction layer of an organic solar cell with inverted structure. The nano-graphite flakes are inkjet printable and conductive and therefore show potential as a low-cost alternative to polymer poly(3,4-ethylenedioxythiophene) polystyrene sulfonate.

Confining metal-halide perovskites in nanoporous thin films.

Controlling the size and shape of semiconducting nanocrystals advances nanoelectronics and photonics. Quantum-confined, inexpensive, solution-derived metal halide perovskites offer narrowband, color-pure emitters as integral parts of next-generation displays and optoelectronic devices. We use nanoporous silicon and alumina thin films as templates for the growth of perovskite nanocrystallites directly within device-relevant architectures without the use of colloidal stabilization. We find significantly blue-shifted photoluminescence emission by reducing the pore size; normally infrared-emitting materials become visibly red, and green-emitting materials become cyan and blue. Confining perovskite nanocrystals within porous oxide thin films drastically increases photoluminescence stability because the templates auspiciously serve as encapsulation. We quantify the template-induced size of the perovskite crystals in nanoporous silicon with microfocus high-energy x-ray depth profiling in transmission geometry, verifying the growth of perovskite nanocrystals throughout the entire thickness of the nanoporous films. Low-voltage electroluminescent diodes with narrow, blue-shifted emission fabricated from nanocrystalline perovskites grown in embedded nanoporous alumina thin films substantiate our general concept for next-generation photonic devices.

A stereochemical switch in the aDrs model system, a candidate for a functional amyloid.

Amyloid fibrils are commonly observed to adopt multiple distinct morphologies, which eventually can have significantly different neurotoxicities, as e.g. demonstrated in case of the Alzheimer peptide. The architecture of amyloid deposits is apparently also determined by the stereochemistry of amino acids. Post-translational changes of the chirality of certain residues may thus be a factor in controlling the formation of functional or disease-related amyloids. Anionic dermaseptin (aDrs), an unusual peptide from the skin secretions of the frog Pachymedusa dacnicolor, assembles to amyloid-like fibrils in a pH-dependent manner, which could play a functional role in defense. aDrs can be enzymatically converted into the diastereomer [d-Leu2]-aDrs by an l/d-isomerase. EM and AFM on fibrils formed by these isomers have shown that their predominant morphology is controlled by the stereochemistry of residue 2, whereas kinetic and thermodynamic parameters of aggregation are barely affected. When fibrils were grown from preformed seeds, backbone stereochemistry rather than templating-effects apparently dominated the superstructural organization of the isomers. Interestingly, MD indicated small differences in the conformational propensities between the isomers. Our results demonstrate how d-amino acid substitutions could take active part in the formation of functional or disease-related amyloid. Moreover, these findings contribute to the development of amyloid-based nanomaterials.

Infrared emitting and photoconducting colloidal silver chalcogenide nanocrystal quantum dots from a silylamide-promoted synthesis.

Here, we present a hot injection synthesis of colloidal Ag chalcogenide nanocrystals (Ag(2)Se, Ag(2)Te, and Ag(2)S) that resulted in exceptionally small nanocrystal sizes in the range between 2 and 4 nm. Ag chalcogenide nanocrystals exhibit band gap energies within the near-infrared spectral region, making these materials promising as environmentally benign alternatives to established infrared active nanocrystals containing toxic metals such as Hg, Cd, and Pb. We present Ag(2)Se nanocrystals in detail, giving size-tunable luminescence with quantum yields above 1.7%. The luminescence, with a decay time on the order of 130 ns, was shown to improve due to the growth of a monolayer thick ZnSe shell. Photoconductivity with a quantum efficiency of 27% was achieved by blending the Ag(2)Se nanocrystals with a soluble fullerene derivative. The co-injection of lithium silylamide was found to be crucial to the synthesis of Ag chalcogenide nanocrystals, which drastically increased their nucleation rate even at relatively low growth temperatures. Because the same observation was made for the nucleation of Cd chalcogenide nanocrystals, we conclude that the addition of lithium silylamide might generally promote wet-chemical synthesis of metal chalcogenide nanocrystals, including in as-yet unexplored materials.

Organic-organic heteroepitaxy of red-, green-, and blue-emitting nanofibers.

Self-assembly processes and organic-organic heteroepitaxy are powerful techniques to obtain highly ordered molecular aggregates. Here we demonstrate that combining both methods allows not only to fabricate highly crystalline and uniaxially oriented self-assembled nanofibers but also to tune their polarized emission. We show that submonolayer coverage of sexithiophene on top of para-sexiphenyl nanofibers is sufficient to change their emission color from blue to green. Triband emission in the red, green, and blue is generated in nanofibers with thicker sexithiophene coverage, where layers of co-oriented crystals are separated by green-emitting molecular sheets.

Highly monodisperse bismuth nanoparticles and their three-dimensional superlattices.

A simple and reproducible synthesis of highly monodisperse and ligand-protected bismuth nanoparticles (Bi NPs) is reported. The size of the single-crystalline and spherically shaped NPs is controlled between 11 and 22 nm mainly by the reaction temperature. The high uniformity of the NPs allows their self-assembly into long-range-ordered two- and three-dimensional superstructures.

Large-area ordered superlattices from magnetic Wustite/cobalt ferrite core/shell nanocrystals by doctor blade casting.

Although a large diversity of single-component and binary superlattices from colloidal nanocrystals have been demonstrated, applications of such ordered nanocrystal assemblies are still hampered due to a lack of control over the self-assembly processes over large areas. A reel-to-reel compatible large-area coating technique for solutions is given by doctor blade casting, which is applied here to deposit colloidal nanocrystals onto various substrates. The self-assembly process is demonstrated for magnetic nanocrystals, having a high potential for applications in magnetic memory devices. Shape-controlled (spherical and cubic) and monodisperse nanocrystals with a Wustite core and a cobalt ferrite shell are used in particular. Doctor blade casting of these colloidal nanocrystals results in films exhibiting hexagonally closely packed arrangements, which are formed by a top-down growth, as is evidenced by cross sectional transmission electron microscopy. The ordering in the topmost layer extends over large areas, although some defects and irregularities are found. The degree and quality of self-assembly is quantified by analyzing plan view images of the assemblies by means of the decay of their autocorrelation function. This analysis reveals that the degree of ordering obtained by doctor blade casting outperforms those provided by alternative deposition techniques such as inkjet printing or drop casting. The results for the coherent lengths deduced from the autocorrelation analysis are shown to be consistent with those from grazing-incidence small-angle X-ray scattering, giving coherence length on the order of 1000 nm.

An orphan dermaseptin from frog skin reversibly assembles to amyloid-like aggregates in a pH-dependent fashion.

Dermaseptin PD-3-7 (aDrs) from frog skin contains three aspartic acid residues resulting in a negative net charge at neutral pH, as opposed to numerous other dermaseptins which are cationic helical antimicrobial peptides. Still, this peptide can be fitted into an amphipathic alpha helix by an Edmundson wheel projection. However, folding to the proposed helix was induced to only a low extent by zwitterionic vesicles or even detergents. Furthermore, no evidence of antibacterial or cytotoxic activity from soluble aDrs could be obtained. The peptide has an inherent propensity to an extended conformation in aqueous solution and self-assembles into amyloid fibrils in a reversible pH-controlled fashion, which was studied in some detail; above pH 5, the amyloid fibrils disassemble in a cooperative manner. This is probably caused by deprotonation of both side chain and terminal carboxyl groups, which results in intermolecular electrostatic repulsion. At neutral pH, this process proceeds instantaneously to the soluble form. Within the transition interval (pH 5-6.5), however, 'backward' granular aggregates, 10-500 nm in size, are formed. Such metastable amorphous aggregates, which are quickly released from an amyloid depot by a shift in pH, can mediate a strong cytotoxic effect. This activity does not involve lysis or interference with the cellular redox status, but apparently acts via an as yet unidentified mechanism. In this study, we present a new member of an emerging class of self-assembling frog skin peptides with extraordinary self-aggregation properties, which may potentially be relevant for biological processes. Structured digital abstract: * MINT-7256467: Dermaseptin (uniprotkb:O93455) and Dermaseptin (uniprotkb:O93455) bind (MI:0407) by circular dichroism (MI:0016) * MINT-7255686: Dermaseptin (uniprotkb:O93455) and Dermaseptin (uniprotkb:O93455) bind (MI:0407) by biophysical (MI:0013) * MINT-7256439: Dermaseptin (uniprotkb:O93455) and Dermaseptin (uniprotkb:O93455) bind (MI:0407) by fluorescence microscopy (MI:0416) * MINT-7256449: Dermaseptin (uniprotkb:O93455) and Dermaseptin (uniprotkb:O93455) bind (MI:0407) by electron microscopy (MI:0040) * MINT-7256430: Dermaseptin (uniprotkb:O93455) and Dermaseptin (uniprotkb:O93455) bind (MI:0407) by fluorescence technologies (MI:0051).

Colloidal HgTe nanocrystals with widely tunable narrow band gap energies: from telecommunications to molecular vibrations.

A convenient, aqueous-based synthesis of stable HgTe nanocrystals with widely size-tunable room temperature emission between wavelengths of 1.2 to 3.7 mum is demonstrated. By the choice of the thiols, applied as stabilizers, we optimized the growth dynamics, the luminescence quantum yields (up to 40%), and a ligand-exchange procedure, required to transfer the nanocrystals from water to nonpolar organic solvents. The latter is greatly improved and facilitated by the use of mercaptoethylamine as initial stabilizer. The possibility to tune the HgTe nanocrystal sizes from 3 to 12 nm and to control their surface functionalities (hydrophobic and hydrophilic) makes them very promising for the development of infrared optical devices, emitting in the wavelength region between the telecommunications and the molecular vibrations.