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Ordered assemblies of the peptide diphenylalanine (FF) are produced and deposited on planar substrates. The FF aggregate growth is achieved through precipitation from aqueous ammonia solutions induced by solvent evaporation. The applied dip-coating technique confines the FF assembly growth to a narrow zone near the three-phase contact. The growth was observed online by optical microscopy and was investigated systematically as a function of the process parameters. Depending on the external gas flow (to influence solvent evaporation), the withdrawal speed, the initial FF, and the initial ammonia concentrations, FF forms long, straight, and rigid microfibers and/or shorter, curved nanofibers. Under certain process conditions, the FF fibers can also aggregate into stripes. These can be deposited as large arrays of uniform stripes with regular widths and spacings. Scenarios leading to the various types of fibers and the stripe formation are presented and discussed in view of the experimental findings.

Considerable research efforts have been devoted to surface‐enhanced Raman spectroscopy (SERS), due to its excellent performance in biosensing and imaging. Here, a novel and facile strategy for the fabrication of well‐defined and uniform nanodimers as SERS substrates is presented. By the assistance of ultrasound, the violent polyol process for particle generation becomes controllable, enabling the self‐assembly of nanostars to nanodimers. Moreover, the aggregation of nanodimers can be easily tuned by post‐ultrasonic treatment, which gives a sensitive substrate for SERS., Made of nanostars: By the assistance of ultrasound, the violent polyol process for silver particle generation becomes controllable, enabling the self‐assembly of nanostars to nanodimers. Moreover, the aggregation of nanodimers can be easily tuned by post‐ultrasonic treatment, which gives a sensitive substrate for SERS.

Polymer modification plays an important role in the construction of devices, but the lack of fundamental understanding on polymer-surface adhesion limits the development of miniaturized devices. In this work, a thermoplastic polymer collection was established using the combinatorial laser-induced forward transfer technique as a research platform, to assess the adhesion of polymers to substrates of different wettability. Furthermore, it also revealed the influence of adhesion on dewetting phenomena during the laser transfer and relaxation process, resulting in polymer spots of various morphologies. This gives a general insight into polymer-surface adhesion and connects it with the generation of defined polymer microstructures, which can be a valuable reference for the rational use of polymers.

Multivalent ligand–protein interactions are a commonly employed approach by nature in many biological processes. Single glycan–protein interactions are often weak, but their affinity and specificity can be drastically enhanced by engaging multiple binding sites. Microarray technology allows for quick, parallel screening of such interactions. Yet, current glycan microarray methodologies usually neglect defined multivalent presentation. Our laser-based array technology allows for a flexible, cost-efficient, and rapid in situ chemical synthesis of peptide scaffolds directly on functionalized glass slides. Using copper(I)-catalyzed azide–alkyne cycloaddition, different monomer sugar azides were attached to the scaffolds, resulting in spatially defined multivalent glycopeptides on the solid support. Studying their interaction with several different lectins showed that not only the spatially defined sugar presentation, but also the surface functionalization and wettability, as well as accessibility and flexibility, play an essential role in such interactions. Therefore, different commercially available functionalized glass slides were equipped with a polyethylene glycol (PEG) linker to demonstrate its effect on glycan–lectin interactions. Moreover, different monomer sugar azides with and without an additional PEG-spacer were attached to the peptide scaffold to increase flexibility and thereby improve binding affinity. A variety of fluorescently labeled lectins were probed, indicating that different lectin–glycan pairs require different surface functionalization and spacers for enhanced binding. This approach allows for rapid screening and evaluation of spacing-, density-, ligand and surface-dependent parameters, to find optimal lectin binders.

Fabrication of hybrid photoelectrodes on a subsecond timescale with low energy consumption and possessing high photocurrent densities remains a centerpiece for successful implementation of photoelectrocatalytic synthesis of fuels and value-added chemicals. Here, we introduce a laser-driven technology to print sensitizers with desired morphologies and layer thickness onto different substrates, such as glass, carbon, or carbon nitride (CN). The specially designed process uses a thin polymer reactor impregnated with transition metal salts, confining the growth of transition metal oxide (TMO) nanostructures on the interface in milliseconds, while their morphology can be tuned by the laser. Multiple nano-p-n junctions at the interface increase the electron/hole lifetime by efficient charge trapping. A hybrid copper oxide/CN photoanode with optimal architecture reaches 10 times higher photocurrents than the pristine CN photoanode. This technology provides a modular approach to build a library of TMO-based composite films, enabling the creation of materials for diverse applications., Fabrication of hybrid photoelectrodes on a subsecond timescale with low energy consumption remains a challenge. Here, the authors report a modular approach, laser-driven transfer synthesis, to build a library of structurally defined transition metal oxide composite films, enabling the creation of materials for diverse applications.

We present and analyze comprehensive measurements of the evaporation behavior, E, of a thinning liquid film during a hydrodynamic‐evaporative spin coating experiment. E, ω (the rotation speed), and ν (the liquid viscosity) are the main control parameters of the process. The entire film thinning process can be described theoretically quite well if these parameters are known. Values of ν are easily accessible in advance (calculations, literature values, measurements). Values for E can essentially not be found in the literature. They are hard to measure and specific for the experimental conditions. There is also no generally accepted strategy to calculate E. Our experimental results are compared with a theoretical prediction for E based on ideas by Bornside, Macosco, and Scriven, which were presented long ago. Their approach was never tested experimentally. Theory and experiment agree well for many solvents and different ω. This approach permits in advance the quantitative calculation of the evolution of the entire hydrodynamic‐evaporative film thinning process. We also derive a general formula to predict ab initio, with literature data only, the amount of final deposit (film thickness) of solute in the case of spin coating mixtures of volatile solvents and nonvolatile solutes.

Short-lived micro-sized thermal gradients are challenging to measure. Especially, in thin film processes and devices, it is important to know the exact temperature profile to assure process parameters and the stability of sensitive materials. Many theoretical models try to describe the occurring temperatures, but still lack in profound experimental data. Here, a facile approach is presented, which allows to measure confined temperature gradients with millisecond and micrometer precision. By casting a thin alkane film onto a substrate of interest, it is possible to reconstruct local temperature gradients by imaging the phase behavior and morphology of the alkane film with a simple optical microscope setup. Alkanes are inert and their melting and boiling temperatures depend on the chain length. This allows to measure temperatures between 37 and 522 °C on any surface. Furthermore, after thorough characterization of laser-induced temperature gradients, this approach can be used to measure the phase transition behavior of complex thin film polymer mixtures.

Single glycan–protein interactions are often weak, such that glycan binding partners commonly utilize multiple, spatially defined binding sites to enhance binding avidity and specificity. Current array technologies usually neglect defined multivalent display. Laser‐based array synthesis technology allows for flexible and rapid on‐surface synthesis of different peptides. By combining this technique with click chemistry, neo‐glycopeptides were produced directly on a functionalized glass slide in the microarray format. Density and spatial distribution of carbohydrates can be tuned, resulting in well‐defined glycan structures for multivalent display. The two lectins concanavalin A and langerin were probed with different glycans on multivalent scaffolds, revealing strong spacing‐, density‐, and ligand‐dependent binding. In addition, we could also measure the surface dissociation constant. This approach allows for a rapid generation, screening, and optimization of a multitude of multivalent scaffolds for glycan binding., Interactions of proteins with glycans rely on multivalency, where multiple adjacent binding events are involved. To study this glycan density‐dependent binding, a facile technique to synthesize peptide‐based multivalent carbohydrate scaffolds in parallel, directly on‐chip, in the microarray format, was developed. This allows to rapidly generate arrays of multivalent glycan structures, without the need for individual multistep syntheses per compound.

In this work, we present a qualitative and quantitative experimental analysis, as well as a numerical model, of a novel variant of the laser-induced forward transfer, which uses millisecond laser pulses. In this process, soft material nanolayer spots are transferred from a donor slide, which is coated with the soft material layer, to an acceptor slide via laser irradiation. This method offers a highly flexible material transfer to perform high-throughput combinatorial chemistry for the generation of biomolecule arrays. For the first time, we show visual evidence that the main transfer mechanism is contact-based, due to thermal surface expansion of the donor layer. Thus, the process is different from the many known variants of laser-induced forward transfer. We characterize the maximum axial surface expansion in relation to laser power and pulse duration. On this basis, we derive a numerical model that approximates the axial surface expansion within measurement tolerances. Finally, we analyze the topology of the transferred soft material nanolayer spots by fluorescence imaging and vertical scanning interferometry to determine width, height, and shape of the transferred material. Concluding from this experimental and numerical data, we can now predict the amount of transferred material in this process.

Controlled growth of one-dimensional nanostructures is playing a key role in creating types of materials for functional devices. Here, we report procedures for controlled assembly of the dipeptide diphenylalanine (FF) into aligned and ultralong single crystals in a capillary. With the evaporation of solvent, nucleation of the crystal occurred in the confined region, and the crystal grew continuously with a supply of molecules from the concentration gradient system inside the capillary. Based on the "Knudsen regime", an ultralong aligned individual FF single crystal possessing an active optical waveguide property at macroscopic length scale could be obtained. Moreover, capillary is also an effective microdevice to investigate the disassembly process of the FF single crystals. This strategy has potentials to broaden the range of applications of aligned organic nanomaterials.

We developed a next-generation method for chemical in–situ combinatorial biomolecule array synthesis. This allows for an unprecedented combinatorial freedom in the automated chemical synthesis of molecule arrays with very high spot densities. Key feature of this new method is an automated positioning and laser transfer process: Small solid material spots are rapidly transferred from a donor film to an acceptor surface, requiring only minute amounts of materials. The transfer is performed with different and easy-to-produce donor slides. Each donor slide bears a thin polymer film, embedding one type of monomer. The coupling reaction occurs in a separate heating step, where the matrix becomes viscous and building blocks can diffuse within the material and couple to the acceptor surface. Since these transferred material spots are only several nanometers thin, this method allows for a consecutive multi-layer material deposition of e.g. activation reagents and amino acids. Subsequent heat-induced mixing facilitates an in–situ activation and coupling of the monomers. Positioning several of such resin spots, containing different chemical reagents, on top of each other, will enable for the first time in such small dimensions unique chemical synthesis strategies for each spot. Amount and concentration of the deposited materials can be adjusted with the laser parameters. Employing similar arrays, we can analyze the human immune response towards the proteome of different pathogens. We screened several peptide array replicas with different patient sera. The screenings resulted in significant hits in several proteins with interesting implications for future diagnostics and vaccine development.

On-line optical imaging of continuously thinning planar films in a spin cast configuration reveals the rupture behavior of ultra-thin films of binary mixtures of a volatile solvent and a nonvolatile solute. The pure solvents completely wet the silica substrates whereas the solution films rupture at certain film thicknesses, hrupture, which depend on, c0, the initial weighing in solute concentrations. With small c0, hrupture increases proportional to c0. With high c0, all films rupture at hrupture≈50nm, independent of c0. The findings can be explained by the solute enrichment during the evaporative thinning. Solute crystallization at the liquid/substrate interface upon reaching solute supersaturation leads to locally different wetting properties. This induces locally the rupture of the film as soon as it is sufficiently thin. A proper data rescaling based on this scenario yields a universal rupture behavior of various different solvent/solute mixtures.

Individual nanoparticles embedded in molecularly thin films at planar substrates and the resulting film surface distortion (meniscus) adjacent to the nanoparticles are investigated by conventional optical reflection microscopy. Even for nanoparticles much smaller than the Rayleigh diffraction limit, the meniscus creates such a pronounced optical footprint that the location of the nanoparticles can be identified. This is because the decay length (lateral extension) of the meniscus exceeds the size of the nanoparticle by orders of magnitude. Therefore, for the first time, the exact shape of the meniscus of the liquid adjacent to a nanosize object could be measured and analyzed. The meniscus has a zero curvature shape (cosine hyperbolic). The liquid in the meniscus is in pressure equilibrium with the far-field planar film. The decay length decreases with the decreasing nanoparticle size. However, it is independent of the far-field film thickness. Supposedly, the decay length is determined by van der Waals interactions although it is unknown what determines its (unexpectedly large) absolute value. The presented technical approach may be used to investigate biological systems (for instance, surface distortions in supported membranes caused by proteins or protein aggregates).

Oriented arrangement of single crystals plays a key role in improving the performance of their functional devices. Herein we describe a method for the exceptionally fast fabrication (mm/min) of ultralong aligned dipeptide single crystals (several centimeters). It combines an induced nucleation step with a continuous withdrawal of substrate, leading to specific evaporation/composition conditions at a three-phase contact line, which makes the growth process controllable. These aligned dipeptide fibers possess a uniform cross section with active optical waveguiding properties that can be used as waveguiding materials. The approach provides guidance for the controlled arrangement of organic single crystals, a family of materials with considerable potential applications in large-scale functional devices.

A low-cost laser-based printing setup is presented, which allows for the spot-wise patterning of surfaces with defined polymer nanolayers. These nanolayer spots serve as a “solid solvent,” embedding different chemicals, chemical building blocks, materials, or precursors and can be stacked on top of each other. By melting the spot pattern, the polymer-embedded molecules are released for chemical reaction. This enables researchers to quickly pattern a surface with different molecules and materials, mixing them directly on the surface for high-throughput chemical synthesis to generate and screen diverse microarray libraries. In contrast to expensive ink-jet or contact printing, this approach does not require premixing of inks, which enables in situ combinatorial mixing. Easy access and versatility of this patterning approach are shown by generating microarrays of various biomolecules, such as glycans for the first time, to screen interactions of antibodies and lectins. In addition, a layer-by-layer solid-phase synthesis of peptides directly on the microarray is presented. Amino acid–containing nanolayers are repeatedly laser-transferred and reacted with the functionalized acceptor surface in defined patterns. This simple system enables a reproducible array production, down to spot-to-spot distances of 100 μm, and offers a flexible and cheap alternative to expensive spotting robot technology.