2023, von Haugwitz, Gerlis, Donnelly, Kian, Di Filippo, Mara, Breite, Daniel, Phippard, Max, Schulze, Agnes, Wei, Ren, Baumann, Marcus, Bornscheuer, Uwe T.

Poly(vinyl alcohol) (PVA) is a water-soluble synthetic vinyl polymer with remarkable physical properties including thermostability and viscosity. Its biodegradability, however, is low even though a large amount of PVA is released into the environment. Established physical-chemical degradation methods for PVA have several disadvantages such as high price, low efficiency, and secondary pollution. Biodegradation of PVA by microorganisms is slow and frequently involves pyrroloquinoline quinone (PQQ)-dependent enzymes, making it expensive due to the costly cofactor and hence unattractive for industrial applications. In this study, we present a modified PVA film with improved properties as well as a PQQ-independent novel enzymatic cascade for the degradation of modified and unmodified PVA. The cascade consists of four steps catalyzed by three enzymes with in situ cofactor recycling technology making this cascade suitable for industrial applications.

2018, Liedtke, Susann, Grüner, Christoph, Gerlach, Jürgen W., Rauschenbach, Bernd

Metals with a wide range of melting points are deposited by electron beam evaporation under oblique deposition geometry on thermally oxidized Si substrates. During deposition the sample holder is cooled down to 77 K. It is observed that all obliquely deposited metals grow as tilted, high aspect ratio columns and hence with a similar morphology. A comparison of such columns with those deposited at room temperature (300 K) reveals that shadowing dominates the growth process for columns deposited at 77 K, while the impact of surface diffusion is significantly increased at elevated substrate temperatures. Furthermore, it is discussed how the incidence angle of the incoming particle flux and the substrate temperature affect the columnar tilt angles and the porosity of the sculptured thin films. Exemplarily for tilted Al columns deposited at 77 K and at 300 K, in-plane pole figure measurements are carried out. A tendency to form a biaxial texture as well as a change in the crystalline structure depending on the substrate temperature is found for those films.

2021, Urban, Raphael D., Fischer, Tillmann G., Charvat, Ales, Wink, Konstantin, Krafft, Benjamin, Ohla, Stefan, Zeitler, Kirsten, Abel, Bernd, Belder, Detlev

By the on-chip integration of a droplet generator in front of an emitter tip, droplets of non-polar solvents are generated in a free jet of an aqueous matrix. When an IR laser irradiates this free liquid jet consisting of water as the continuous phase and the non-polar solvent as the dispersed droplet phase, the solutes in the droplets are ionized. This ionization at atmospheric pressure enables the mass spectrometric analysis of non-polar compounds with the aid of a surrounding aqueous matrix that absorbs IR light. This works both for non-polar solvents such as n-heptane and for water non-miscible solvents like chloroform. In a proof of concept study, this approach is applied to monitor a photooxidation of N-phenyl-1,2,3,4-tetrahydroisoquinoline. By using water as an infrared absorbing matrix, analytes, dissolved in non-polar solvents from reactions carried out on a microchip, can be desorbed and ionized for investigation by mass spectrometry.

2022, Garmasukis, Rokas, Hackl, Claudia, Dusny, Christian, Elsner, Christian, Charvat, Ales, Schmid, Andreas, Abel, Bernd

This paper highlights an innovative, low-cost rapid-prototyping method for generating microfluidic chips with extraordinary short fabrication times of only a few minutes. Microchannels and inlet/outlet ports are created by controlled deposition of aqueous microdroplets on a cooled surface resulting in printed ice microstructures, which are in turn coated with a UV-curable acrylic cover layer. Thawing leaves an inverse imprint as a microchannel structure. For an exemplary case, we applied this technology for creating a microfluidic chip for cell-customized optical-cell analysis. The chip design includes containers for cell cultivation and analysis. Container shape, length, position, and angle relative to the main channel were iteratively optimized to cultivate and analyze different cell types. With the chip, we performed physiological analyses of morphologically distinct prokaryotic Corynebacterium glutamicum DM1919, eukaryotic Hansenula polymorpha RB11 MOX-GFP, and phototrophic Synechocystis sp. PCC 6803 cells via quantitative time-lapse fluorescence microscopy. The technology is not limited to rapid prototyping of complex biocompatible microfluidics. Further exploration may include printing with different materials other than water, printing on other substrates in-situ biofunctionalization, the inclusion of electrodes and many other applications.

2021, Kapprell, Uta, Friebe, Sabrina, Grüner, Susann, Grüner, Christoph, Kupferer, Astrid, Rauschenbach, Bernd, Mayr, Stefan G.

Cells are established to sense and respond to the properties, including nano- and microscale morphology, of the substrate they adhere to, which opens up the possibility to tailor bioactivity. With this background, the potential of tilted TiO2 nanostructures grown by oblique angle sputtering to affect fibroblasts with particular focus on inducing anisotropy in cell behavior is explored. By depositing TiO2 at different oblique angles relative to the substrate normal, morphologies, columnar tilt angle, roughness, and distances between neighbored nanocolumns can be adjusted. To assess bioactivity of the resulting structures, L929-mouse fibroblasts are seeded in vitro on TiO2 nanostructured substrates. Angle-dependent movement and velocity distributions of the cells on differently tilted columns and a smooth reference sample are studied. Cell proliferation rates and cell areas are additional factors which provide information about viability and the well-being of cells. It could be shown that the local topography of the surface has an influence on the directed movement of the cells. © 2021 The Authors. Advanced Materials Interfaces published by Wiley-VCH GmbH

2017, Börner, Martin, Blömer, Laura, Kischel, Marcus, Richter, Peter, Salvan, Georgeta, Zahn, Dietrich R. T., Siles, Pablo F., Fuentes, Maria E. N., Bufon, Carlos C. B., Grimm, Daniel, Schmidt, Oliver G., Breite, Daniel, Abel, Bernd, Kersting, Berthold

The chemisorption of magnetically bistable transition metal complexes on planar surfaces has recently attracted increased scientific interest due to its potential application in various fields, including molecular spintronics. In this work, the synthesis of mixed-ligand complexes of the type [NiII2L(L’)](ClO4), where L represents a 24-membered macrocyclic hexaazadithiophenolate ligand and L’ is a ω-mercapto-carboxylato ligand (L’ = HS(CH2)5CO2− (6), HS(CH2)10CO2− (7), or HS(C6H4)2CO2− (8)), and their ability to adsorb on gold surfaces is reported. Besides elemental analysis, IR spectroscopy, electrospray ionization mass spectrometry (ESIMS), UV–vis spectroscopy, and X-ray crystallography (for 6 and 7), the compounds were also studied by temperature-dependent magnetic susceptibility measurements (for 7 and 8) and (broken symmetry) density functional theory (DFT) calculations. An S = 2 ground state is demonstrated by temperature-dependent susceptibility and magnetization measurements, achieved by ferromagnetic coupling between the spins of the Ni(II) ions in 7 (J = +22.3 cm−1) and 8 (J = +20.8 cm−1; H = −2JS1S2). The reactivity of complexes 6–8 is reminiscent of that of pure thiolato ligands, which readily chemisorb on Au surfaces as verified by contact angle, atomic force microscopy (AFM) and spectroscopic ellipsometry measurements. The large [Ni2L] tail groups, however, prevent the packing and self-assembly of the hydrocarbon chains. The smaller film thickness of 7 is attributed to the specific coordination mode of the coligand. Results of preliminary transport measurements utilizing rolled-up devices are also reported.

2018-9-5, Fischer, Kristina, Schulz, Paulina, Atanasov, Igor, Abdul Latif, Amira, Thomas, Isabell, Kühnert, Mathias, Prager, Andrea, Griebel, Jan, Schulze, Agnes

Titanium dioxide (TiO2) is described as an established material to remove pollutants from water. However, TiO2 is still not applied on a large scale due to issues concerning, for example, the form of use or low photocatalytic activity. We present an easily upscalable method to synthesize high active TiO2 nanoparticles on a polyethersulfone microfiltration membrane to remove pollutants in a continuous way. For this purpose, titanium(IV) isopropoxide was mixed with water and hydrochloric acid and treated up to 210 °C. After cooling, the membrane was simply dip-coated into the TiO2 nanoparticle dispersion. Standard characterization was undertaken (i.e., X-ray powder diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, water permeance, contact angle). Degradation of carbamazepine and methylene blue was executed. By increasing synthesis temperature crystallinity and photocatalytic activity elevates. Both ultrasound modification of nanoparticles and membrane pre-modification with carboxyl groups led to fine distribution of nanoparticles. The ultrasound-treated nanoparticles gave the highest photocatalytic activity in degrading carbamazepine and showed no decrease in degradation after nine times of repetition. The TiO2 nanoparticles were strongly bound to the membrane. Photocatalytic TiO2 nanoparticles with high activity were synthesized. The innovative method enables a fast and easy nanoparticle production, which could enable the use in large-scale water cleaning.

2021, Moors, Marco, An, Yun, Kuc, Agnieszka, Monakhov, Kirill Yu

Highly ordered titanium oxide films grown on a Pt3Ti(111) alloy surface were utilized for the controlled immobilization and tip-induced electric field-triggered electronic manipulation of nanoscopic W3O9 clusters. Depending on the operating conditions, two different stable oxide phases, z'-TiO x and w'-TiO x , were produced. These phases show a strong effect on the adsorption characteristics and reactivity of W3O9 clusters, which are formed as a result of thermal evaporation of WO3 powder on the complex TiO x /Pt3Ti(111) surfaces under ultra-high vacuum conditions. The physisorbed tritungsten nano-oxides were found as isolated single units located on the metallic attraction points or as supramolecular self-assemblies with a W3O9-capped hexagonal scaffold of W3O9 units. By applying scanning tunneling microscopy to the W3O9-(W3O9)6 structures, individual units underwent a tip-induced reduction to W3O8. At elevated temperatures, agglomeration and growth of large WO3 islands, which thickness is strongly limited to a maximum of two unit cells, were observed. The findings boost progress toward template-directed nucleation, growth, networking, and charge state manipulation of functional molecular nanostructures on surfaces using operando techniques.

2021, Grau, Benedikt W., Dill, Maximilian, Hampel, Frank, Kahnt, Axel, Jux, Norbert, Tsogoeva, Svetlana B.

Hexaarylbenzene (HAB) derivatives are versatile aromatic systems playing a significant role as chromophores, liquid crystalline materials, molecular receptors, molecular-scale devices, organic light-emitting diodes and candidates for organic electronics. Statistical synthesis of simple symmetrical HABs is known via cyclotrimerization or Diels–Alder reactions. By contrast, the synthesis of more complex, asymmetrical systems, and without involvement of statistical steps, remains an unsolved problem. Here we present a generally applicable synthetic strategy to access asymmetrical HAB via an atom-economical and high-yielding metal-free four-step domino reaction using nitrostyrenes and α,α-dicyanoolefins as easily available starting materials. Resulting domino product—functionalized triarylbenzene (TAB)—can be used as a key starting compound to furnish asymmetrically substituted hexaarylbenzenes in high overall yield and without involvement of statistical steps. This straightforward domino process represents a distinct approach to create diverse and still unexplored HAB scaffolds, containing six different aromatic rings around central benzene core. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH

2021, Lorenz, Oliver, Kühne, Alexander, Rudolph, Martin, Diyatmika, Wahyu, Prager, Andrea, Gerlach, Jürgen W., Griebel, Jan, Winkler, Sara, Lotnyk, Andriy, Anders, André, Abel, Bernd

Understanding the reaction pathways for the hydrogen oxidation reaction (HOR) and the oxygen reduction reaction (ORR) is the key to design electrodes for solid acid fuel cells (SAFCs). In general, electrochemical reactions of a fuel cell are considered to occur at the triple-phase boundary where an electrocatalyst, electrolyte and gas phase are in contact. In this concept, diffusion processes of reaction intermediates from the catalyst to the electrolyte remain unconsidered. Here, we unravel the reaction pathways for open-structured Pt electrodes with various electrode thicknesses from 15 to 240 nm. These electrodes are characterized by a triple-phase boundary length and a thickness-depending double-phase boundary area. We reveal that the double-phase boundary is the active catalytic interface for the HOR. For Pt layers ≤ 60 nm, the HOR rate is rate-limited by the processes at the gas/catalyst and/or the catalyst/electrolyte interface while the hydrogen surface diffusion step is fast. For thicker layers (>60 nm), the diffusion of reaction intermediates on the surface of Pt be-comes the limiting process. For the ORR, the predominant reaction pathway is via the triple-phase boundary. The double-phase boundary contributes additionally with a diffusion length of a few nanometers. Based on our results, we propose that the molecular reaction mechanism at the electrode interfaces based upon the triple-phase boundary concept may need to be extended to an effective area near the triple-phase boundary length to include all catalytically relevant diffusion processes of the reaction intermediates. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.