Scientific publications

2019
Enhancing optical re-orientation effect using external electric field in aluminum-doped zinc oxide nanocolloids

Koushki, E. | Esmaili, M. | Jafari Mohammadi, S. A. | Oliveira, Peter William de

DOI:

We propose a novel optical effect that involves switching the nonlinear refractive index of colloids and solutions by applying an external field. The third-order nonlinear optical properties of the colloidal aluminum-doped zinc oxide nanoparticles were studied using the z-scan technique by employing a polarized continuous-wave laser beam. To produce the anisotropic effect in the nanocolloids, an external electric field was applied. The nonlinear refraction index switches from minus values to positive ones as the magnitude of the electric field increases. Enhancement of linear and nonlinear absorption coefficients due to the amplitude of the electric field confirms potential application of the colloidal nanoparticles for optical switches. This phenomenon was described theoretically using the re-orientation effect and birefringence of the media. This effect could be interesting for application in nonlinear optical devices and sensors.

DOI:

Journal of the Optical Society of America B,
2019, 36 (8), 2148-2153.

Laser sintering of gravure printed indium tin oxide films on polyethylene terephthalate for flexible electronics

Serkov, A. A. | Snelling, H. V. | Heusing, Sabine | Amaral, T. Martins

DOI:

Tin doped indium oxide (ITO) thin films provide excellent transparency and conductivity for electrodes in displays and photovoltaic systems. Current advances in producing printable ITO inks are reducing the volume of wasted indium during thin film patterning. However, their applicability to flexible electronics is hindered by the need for high temperature processing that results in damage to conventional polymer substrates. Here, we detail the conditions under which laser heating can be used as a replacement for oven and furnace treatments. Measurements of the optical properties of both the printed ITO film and the polymer substrate (polyethylene terephthalate, PET) identify that in the 1.5–2.0 μm wavelength band there is absorption in the ITO film but good transparency in PET. Hence, laser light that is not absorbed in the film does not go on to add a deleterious energy loading to the substrate. Localization of the energy deposition in the film is further enhanced by using ultrashort laser pulses (~1 ps) thus limiting heat flow during the interaction. Under these conditions, laser processing of the printed ITO films results in an improvement of the conductivity without damage to the PET.

DOI:

Scientific Reports,
2019, 9 (1), 1773.

OPEN ACCESS
Solution combustion-derived ZnO nanoparticles for photoanode of solar cells

Shaat, S.K.K. | Musleh, H. | Zayed, H. | Tamous, H. | Issa, A. | Shurrab, N. | Asad, J. | Mousa, A. | Abu-Shawish, M. | Abu-Shawish, M. | Al-Dahoudi, Naji

DOI:

ZnO nanoparticles (NPs) were synthesized using solution combustion method with different urea percent (UP) i.e. U1, U2, U3 and U4. The obtained ZnO NPs were characterized using X-ray diffraction (XRD), high-resolution transmission electron microscope (HR-TEM), UV–Vis spectroscopy and photoluminescence spectroscopy (PL). XRD analysis confirmed the wurtzite structure of the prepared ZnO NPs and the estimated average crystallite size reduced from 28.03 nm to 17.33 nm with increasing of UP. HR-TEM image showed an irregular spherical shape for the prepared ZnO NPs. The absorption spectra analysis exhibited that the optical energy band gap (Eg) for the ZnO NPs increased with increasing of UP from 2.84 eV to 3.13 eV. Two groups (I and II) of dye sensitized solar cell (DSSCs) device based on the synthesized ZnO NPs were fabricated. In group I, 0.32 mM Eosin B (EB) used as photosensitizer for the samples U1, U2, U3 and U4, which showed that the overall conversion efficiency (η) increased from 0.09% to 0.13%, under a light intensity of 100 mW/cm2 due to the increasing of UP. Group II, different photosensitizer EB, Eosin Y (EY) and Rhodamine B (RB) used to sensitized the U4, where the EY exhibited the best all of them. The conversion efficiency presented a significant improvement from 0.13 to 1.26%. The combustion method can be considered as a promising method to produce good photoanode semiconductors such ZnO subsequently increase the efficiency of the solar cell.

DOI:

Materials Science and Engineering B-Solid State Materials for Advanced Technology,
2019, 241, 75-81.

Evaluation of novel organosilane modifications of paper spray mass spectrometry substrates for analyzing polar compounds

Bambauer, Thomas P. | Maurer, Hans H. | Weber, Armin A. | Hannig, Matthias | Pütz, Norbert | Koch, Marcus | Manier, Sascha K. | Schneider, Marc | Meyer, Markus R.

DOI:

Paper spray mass spectrometry (PSMS) is currently used in different analytical fields, but less effort has been made so far to use PSMS for highly polar compounds. Such analytes usually show poor performance in PSMS due to their high affinity for common paper substrates in addition to high matrix effects. In this study, strategies for hydrophobic modifications of commercially available paper substrates using ten different organosilanes were developed. The modified substrates were generated, characterized, and applied for PSMS analysis of polar toxins. By using the modified paper, PSMS performance of some of the toxins could be considerably increased, especially for orellanine, showing a more than 80-fold signal enhancement when substrates modified with chlorotrimethylsilane were used. For other toxins like ricinine, only small beneficial effects could be shown on PSMS performance when using modified substrates. Statistical equivalence tests showed sufficient ruggedness of the developed procedures also compared to conventional substrates. Thus, further systematic development of paper substrates modified with organosilane derivatives based on the presented study for application in PSMS should be encouraged.

DOI:

Talanta,
2019, 204, 677-684.

Combining Soft Polysilazanes with Melt-Shear Organization of Core–Shell Particles: On the Road to Polymer-Templated Porous Ceramics

Boehm, Anna K. | Ionescu, Emanuel | Koch, Marcus | Gallei, Markus

DOI:

The preparation of ordered macroporous SiCN ceramics has attracted significant interest and is an attractive area for various applications, e.g., in the fields of catalysis, gas adsorption, or membranes. Non-oxidic ceramics, such as SiCN, own a great stability based on the covalent bonds between the containing elements, which leads to interesting properties concerning resistance and stability at high temperature. Their peculiar properties have become more and more important for a manifold of applications, like catalysis or separation processes, at high temperatures. Within this work, a feasible approach for the preparation of ordered porous materials by taking advantage of polymer-derived ceramics is presented. To gain access to free-standing films consisting of porous ceramic materials, the combination of monodisperse organic polymer-based colloids with diameters of 130 nm and 180 nm featuring a processable preceramic polymer is essential. For this purpose, the tailored design of hybrid organic/inorganic particles featuring anchoring sites for a preceramic polymer in the soft shell material is developed. Moreover, polymer-based core particles are used as sacrificial template for the generation of pores, while the preceramic shell polymer can be converted to the ceramic matrix after thermal treatment. Two different routes for the polymer particles, which can be obtained by emulsion polymerization, are followed for covalently linking the preceramic polysilazane Durazane1800 (Merck, Germany): (i) Free radical polymerization and (ii) atom transfer radical polymerization (ATRP) conditions. These hybrid hard core/soft shell particles can be processed via the so-called melt-shear organization for the one-step preparation of free-standing particle films. A major advantage of this technique is the absence of any solvent or dispersion medium, enabling the core particles to merge into ordered particle stacks based on the soft preceramic shell. Subsequent ceramization of the colloidal crystal films leads to core particle degradation and transformation into porous ceramics with ceramic yields of 18–54%.

DOI:

Molecules,
2019, 24 (19), 3553.

OPEN ACCESS
The synergistic effect of chlorotoxin-mApoE in boosting drug-loaded liposomes across the BBB

Formicola, Beatrice | Dal Magro, Roberta | Montefusco-Pereira, Carlos V. | Lehr, Claus-Michael | Koch, Marcus | Russo, Laura | Grasso, Gianvito | Deriu, Marco A. | Danani, Andrea | Bourdoulous, Sandrine | Re, Francesca

DOI:

We designed liposomes dually functionalized with ApoE-derived peptide (mApoE) and chlorotoxin (ClTx) to improve their blood–brain barrier (BBB) crossing. Our results demonstrated the synergistic activity of ClTx-mApoE in boosting doxorubicin-loaded liposomes across the BBB, keeping the anti-tumour activity of the drug loaded: mApoE acts promoting cellular uptake, while ClTx promotes exocytosis of liposomes.

DOI:

Journal of Nanobiotechnology,
2019, 17 (1), 115_1-7.

OPEN ACCESS
Effect of fluoride mouthrinses and stannous ions on the erosion protective properties of the in situ pellicle

Kensche, A. | Buschbeck, E. | König, B. | Koch, Marcus | Kirsch, J. | Hannig, C. | Hannig, M.

DOI:

The particular feature of this study is the investigation of effects of pure fluoride- or stannous ions based mouthrinses on the erosion protective properties and the ultrastructure of the in situ pellicle (12 volunteers). Experimental solutions were prepared either from 500 ppm NaF, SMFP, AmF or SnF2 or 1563 ppm SnCl2, respectively. After 1 min of in situ pellicle formation on bovine enamel slabs, rinses with one of the preparations were performed for 1 min and intraoral specimens’ exposure was continued for 28 min. Native enamel slabs and rinses with bidestilled water served as controls. After oral exposure, slabs were incubated in HCl (pH 2; 2.3; 3) for 120 s and kinetics of calcium- and phosphate release were measured photometrically; representative samples were analysed by TEM and EDX. All mouthrinses reduced mineral loss compared to the native 30-min pellicle. The effect was pH-dependent and significant at all pH values only for the tin-containing mouthrinses. No significant differences were observed between the SnF2- and the SnCl2-containing solutions. TEM/EDX confirmed ultrastructural pellicle modifications. SnF2 appears to be the most effective type of fluoride to prevent erosive enamel demineralisation. The observed effects primarily have to be attributed to the stannous ions’ content.

DOI:

Scientific Reports,
2019, 9 (1), 5336.

OPEN ACCESS
Bioinspired Liposomes for Oral Delivery of Colistin to Combat Intracellular Infections by Salmonella enterica

Menina, Sara | Eisenbeis, Janina | Kamal, Mohamed Ashraf M. | Koch, Marcus | Bischoff, Markus | Gordon, Sarah | Loretz, Brigitta | Lehr, Claus-Michael

DOI:

Abstract Bacterial invasion into eukaryotic cells and the establishment of intracellular infection has proven to be an effective means of resisting antibiotic action, as anti-infective agents commonly exhibit a poor permeability across the host cell membrane. Encapsulation of anti-infectives into nanoscaled delivery systems, such as liposomes, is shown to result in an enhancement of intracellular delivery. The aim of the current work is, therefore, to formulate colistin, a poorly permeable anti-infective, into liposomes suitable for oral delivery, and to functionalize these carriers with a bacteria-derived invasive moiety to enhance their intracellular delivery. Different combinations of phospholipids and cholesterol are explored to optimize liposomal drug encapsulation and stability in biorelevant media. These liposomes are then surface-functionalized with extracellular adherence protein (Eap), derived from Staphylococcus aureus. Treatment of HEp-2 and Caco-2 cells infected with Salmonella enterica using colistin-containing, Eap-functionalized liposomes resulted in a significant reduction of intracellular bacteria, in comparison to treatment with nonfunctionalized liposomes as well as colistin alone. This indicates that such bio-invasive carriers are able to facilitate intracellular delivery of colistin, as necessary for intracellular anti-infective activity. The developed Eap-functionalized liposomes, therefore, present a promising strategy for improving the therapy of intracellular infections.

DOI:

Advanced Healthcare Materials,
2019, 8 (17), 1900564.

OPEN ACCESS
Strength of bacterial adhesion on nanostructured surfaces quantified by substrate morphometry

Spengler, Christian | Nolle, Friederike | Mischo, Johannes | Faidt, Thomas | Grandthyll, Samuel | Thewes, Nicolas | Koch, Marcus | Müller, Frank | Bischoff, Markus | Klatt, Michael Andreas | Jacobs, Karin

DOI:

Microbial adhesion and the subsequent formation of resilient biofilms at surfaces are decisively influenced by substrate properties, such as the topography. To date, studies that quantitatively link surface topography and bacterial adhesion are scarce, as both are not straightforward to quantify. To fill this gap, surface morphometry combined with single-cell force spectroscopy was performed on surfaces with irregular topographies on the nano-scale. As surfaces, hydrophobized silicon wafers were used that were etched to exhibit surface structures in the same size range as the bacterial cell wall molecules. The surface structures were characterized by a detailed morphometric analysis based on Minkowski functionals revealing both qualitatively similar features and quantitatively different extensions. We find that as the size of the nanostructures increases, the adhesion forces decrease in a way that can be quantified by the area of the surface that is available for the tethering of cell wall molecules. In addition, we observe a bactericidal effect, which is more pronounced on substrates with taller structures but does not influence adhesion. Our results can be used for a targeted development of 3D-structured materials for/against bio-adhesion. Moreover, the morphometric analysis can serve as a future gold standard for characterizing a broad spectrum of material structures.

DOI:

Nanoscale,
2019, 11 (42), 19713-19722.

OPEN ACCESS
Combining cryo-TEM and energy-filtered TEM for imaging organic core-shell nanoparticles and defining the polymer distribution

Weiss, Agnes-Valencia | Koch, Marcus | Schneider, Marc

DOI:

Nanoparticulate systems intended for the use in drug delivery are getting more and more complex. Composite nanoparticles, such as core-shell particles are designed in order to be used for co-delivery of drugs or a modified release profile. Often the structure can only be postulated by the preparation process, such as surface polymerization, but cannot be experimentally determined due to a lack of appropriate analytical methods. Here a core-shell particle system composed of two biodegradable and biocompatible materials, gelatin and PLGA, is developed. In order to reveal the actual polymer distribution, a combination of cryo-transmission electron microscopy and energy-filtered transmission electron microscopy was established. Using the occurrence of specific elements in combination with degradation kinetics induced by the electron beam allows to conclude on the nanoparticles’ architecture. Based on these methods and thus, the particle composition, the drug delivery system can be further developed.

DOI:

International Journal of Pharmaceutics,
2019, 570, 118650.