Scientific publications

2015
Convective assembly of a particle monolayer

Fleck, Norman A. | McMeeking, Robert M. | Kraus, Tobias

DOI:

Recently, the steady-state process of convective assembly has emerged as a viable production route for colloidal monolayers. The present study models the regions of particle assembly: Region I comprises convective concentration of a particle suspension in a liquid below a meniscus, Region II comprises permeation of fluid through the dense particle monolayer, and Region III comprises capillary densification. For each region, the dominant physics and nondimensional groups are identified, and quantitative models are derived to describe the evolution of microstructure in terms of the main process parameters. The concentration profile within the assembly zone of Region I is predicted, including the role of a concentration-dependent diffusion constant and the shape of the meniscus. The fluid flow through the assembled monolayer is treated in Region II, along with a stability calculation to reveal that isolated particle clusters do not survive on top of the monolayer. The physics of capillary crystallization is addressed in Region III, with an emphasis on the density of cracks that emerge. The Peclet number and Capillary number both play important roles but in different regions of the assembly process.

DOI:

Langmuir,
2015, 31 (51), 13655-13663.

Indentation-induced two-way shape-memory effect in aged Ti-50.9 at.% Ni

Frensemeier, Mareike | Arzt, Eduard | Qin, Enwei | Frick, Carl P. | Schneider, Andreas S.

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In this study, Vickers indentation was used to investigate the two-way shape-memory effect (TWSME) in an austenitic Ti-50.9 at.% Ni alloy, exposed to different heat treatments. Three aging treatments were used to manipulate the size of Ti3Ni4 precipitates. All samples were Vickers indented, and the indent depth was investigated as function of thermal cycling. The TWSME was found only in the material aged at 400 °C, which contained coherent precipitates. Thermal cycling shows stable TWSME, however, heating well above the austenite finish temperature lead to permanent austenitic protrusions. The results indicate that stabilized martensite plays a critical role in creating TWSME surfaces.

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MRS Communications,
2015, 5 (1), 77-82.

Electrospinning of ultrafine metal oxide/carbon and metal carbide/carbon nanocomposite fibers

Atchison, Jennifer S. | Zeiger, Marco | Tolosa, Aura | Funke, Lena M. | Jäckel, Nicolas | Presser, Volker

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Electrospinning has emerged as a facile technology for the synthesis of ultrafine fibers and even nanofibers of various materials. While carbon nanofibers have been extensively investigated, there have also been studies reported on metal oxide and metal carbide fibers. Yet, comparative studies, especially following the same general synthesis approach, are lacking. In our comprehensive study, we use a sol gel process by which a carrier polymer (cellulose acetate or polyvinylpyrrolidone) is mixed with titanium butoxide, zirconium(iv) acetylacetonate, or niobium n-butoxide to yield nanotextured titania/carbon, zirconia/carbon, or niobia/carbon nonwoven textiles. Carbothermal reduction between 1300 °C and 1700 °C effectively transforms the metal oxide/carbon fibers to metal carbide/carbon nanocomposite while preserving the fiber integrity. As a beneficial effect, the fiber diameter decreases compared to the as-spun state and we obtained ultrafine fibers: 294 +/- 108 nm for ZrC/C, 122 +/- 28 nm for TiC/C, and 65 +/- 36 nm for NbC/C. The highly disordered and porous nature of the carbon matrix engulfing the metal carbide nanocrystals enables a high specific surface area of up to 450 m2g-1 (TiC/C) after carbothermal reduction.

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RSC Advances,
2015, 5 (45), 35683-35692.

OPEN ACCESS
Formation mechanism for stable hybrid clusters of proteins and nanoparticles

Moerz, Sebastian T. | Kraegeloh, Annette | Chanana, Munish | Kraus, Tobias

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Citrate-stabilized gold nanoparticles (AuNP) agglomerate in the presence of hemoglobin (Hb) at acidic pH. The extent of agglomeration strongly depends on the concentration ratio [Hb]/[AuNP]. Negligible agglomeration occurs at very low and very high [Hb]/[AuNP]. Full agglomeration and precipitation occurs at [Hb]/[AuNP] corresponding to a Hb monolayer on the AuNP. Ratios just above and below this value lead to the formation of an unexpected phase: stable, microscopic AuNP-Hb agglomerates. We investigated the kinetics of agglomeration with dynamic light scattering and the adsorption kinetics of Hb on planar gold with surface acoustic wave phase measurements. Comparing agglomeration and adsorption kinetics leads to an explanation of the complex behavior of this nanoparticle-protein mixture. Agglomeration is initiated either when Hb bridges AuNP or when the electrostatic repulsion between AuNP is neutralized by Hb. It is terminated when Hb has been depleted or when Hb forms multilayers on the agglomerates that stabilize microscopic clusters indefinitely.

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ACS Nano,
2015, 9 (7), 6696-6705.

OPEN ACCESS
Dense arrays of uniform submicron pores in silicon and their applications

Brodoceanu, Daniel | Elnathan, Roey | Prieto-Simón, Beatriz | Delalat, Bahman | Guinan, Taryn M. | Kroner, Elmar Karsten | Voelcker, Nicolas H. | Kraus, Tobias

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We report a versatile particle-based route to dense arrays of parallel submicron pores with high aspect ratio in silicon, and explore the application of these arrays in sensors, optics, and polymer micropatterning. Polystyrene (PS) spheres are convectively assembled on gold-coated silicon wafers and sputter-etched, resulting in well-defined gold disc arrays with excellent long-range order. The gold discs act as catalysts in Metal-Assisted Chemical Etching (MACE), yielding uniform pores with straight walls, flat bottoms and high aspect ratio. The resulting pore arrays can be used as robust antireflective surfaces, in biosensing applications, and as templates for polymer replica molding.

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ACS Applied Materials & Interfaces,
2015, 7 (2), 1160-1169.

Biomineralization in ciliates

Lemloh, Marie-Louise

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From a biomineralization point of view, the protist world is far less investigated than its metazoan counterpart. However, eukaryotic single-celled organisms offer a very unique access to discover biomineralization mechanisms in vivo. With respect to intracellular mechanisms involved in ion enrichment, mineral transport or vesicle formation ciliates represent a good model system. One important group of protists, the ciliates, is very common and numerous studies have been performed on their ecology, cell biology, morphology or genetics. Ciliates are also known for their formation of diverse mineralized intracellular and extracellular structures. However, only limited numbers of detailed studies on the kind of minerals, their properties or their formation mechanisms have been reported so far. This article reviews older and more recent literature on biomineralization in ciliates.

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Key Engineering Materials,
2015, 672, 40-46.

Sulphur-containing compounds as a response in sea urchins exposed to alkylated silicon nanocrystals and SiO2-coated iron oxide nanoparticles

Šiller, Lidija | Piticharoenphun, Sunthon | Lemloh, Marie-Louise | Horrocks, Benjamin R. | Kaulich, Burkhard | Gianoncelli, Alessandra | Hunt, Michael R. C. | Brümmer, Franz | Medakovi

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We report the effects of exposure to alkylated silicon nanocrystals ('alkyl-SiNCs' at concentration ~ 7.2 mg/L) and gamma-Fe2O3 nanoparticles coated with ultra-thin silica ('SiO2-coated IONPs' at concentration ~ 150 mg/L) on sea urchins Paracentrotus lividus and Arbacia lixula, respectively, studied with X-ray fluorescence (XRF) and Fourier transform infrared (FTIR) spectroscpoies using excitation from a synchrotron light source. A remarkably low mortality and low incidence of skeletal deformation is observed for exposure to both types of nanoparticles studied, despite the high concentrations employed in this work. XRF mapping demonstrates that both types of nanoparticle are found to agglomerate in the body of the sea urchins. FTIR spectra indicates that alkyl-SiNCs remain intact after ingestion and corresponding XRF maps show increased an oxygen throughout the organisms, possibly related to oxidation products arising from reactive oxygen species generated in the presence of the nanoparticles. Exposure to SiO2-coated IONPs is found to produce sulphur-containing species, which may be the result of a biological response in order to reduce the toxicity of the nanomaterial.

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Key Engineering Materials,
2015, 672, 312-327.

Iron and FER-LIKE IRON DEFICIENCY-INDUCED TRANSCRIPTION FACTOR-dependent regulation of proteins and genes in Arabidopsis thaliana roots

Mai, Hans-Jörg | Lindermayr, Christian | von Toerne, Christine | Fink-Straube, Claudia | Durner, Jörg | Bauer, Petra

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Iron is an essential micronutrient for plants, and iron deficiency requires a variety of physiological adaptations. FIT (FER-LIKE IRON DEFICIENCY-INDUCED TRANSCRIPTION FACTOR) is essential for the regulation of iron uptake in Arabidopsis thaliana roots. FIT is transcriptionally as well as posttranscriptionally regulated in response to iron supply. To investigate to which extent posttranscriptional regulation upon iron deficiency applies to proteins and to determine the dependency on FIT, we performed a parallel proteomic and transcriptomic study with wild-type, a fit knock-out mutant, and a FIT overexpressing Arabidopsis line. Among 92 proteins differentially regulated by iron and/or FIT, we identified 30 proteins, which displayed differential regulation at the transcriptional level. Eleven protein spots were regulated in at least one of the data points even contrary to the respective genes dependent on FIT. We found ten proteins in at least two forms. The analysis of functional classification showed enriched GO terms among the posttranscriptionally regulated genes and of proteins, that were downregulated or absent in the fit knock-out mutant. Taken together, we provide evidence for iron and FIT-dependent posttranscriptional regulation in iron homeostasis in A. thaliana.

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Proteomics,
2015, 15 (17), 3030-3047.

Analysis of fatty acids and triacylglycerides by Pd nanoparticle-assisted laser desorption/ionization mass spectrometry

Silina, Yuliya E. | Fink-Straube, Claudia | Hayen, Heiko | Volmer, Dietrich A.

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In this study, we propose a simple and rapid technique for characterization of free fatty acids and triacylglycerides (TAG) based on palladium nanoparticular (Pd-NP) surface-assisted laser desorption/ionization (SALDI) mass spectrometry (MS). The implemented Pd-NP material allowed detection of free fatty acids and TAGs exclusively as [M + K]+ ions in positive ion mode. Under negative ionization conditions, unusual trimetric structures were generated for free fatty acids, while TAGs underwent irreproducible degradation reactions. Importantly, the mass spectra obtained from Pd-NP targets in positive ion mode were very clean without interferences from matrix-derived ions in the low m/z range and readily enabled the detection of intact TAGs in vegetable oils without major fragmentation reactions as compared to conventional MALDI-MS, requiring only a minimal amount of sample preparation.

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Analytical Methods,
2015, 7 (9), 3701-3707.

OPEN ACCESS
Sorption of hydrophilic dyes on anodic aluminium oxide films and application to pH sensing

Silina, Yuliya E. | Kuchmenko, Tatyana A. | Volmer, Dietrich A.

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The sorption of selected hydrophilic pH-sensitive dyes (bromophenol blue, bromothymol blue, bromocresol purple, alizarin red, methyl orange, congo red, rhodamine 6G) on films of anodized aluminium oxide (AAO) was investigated in this study. Depth and pore structure of the AAO channels were adjusted by changing electrolysis time and current density during treatment of aluminium foil in oxalic acid, sulfosalycilic acid and sulfuric acid at concentration levels between 0.2 and 0.6 M. The dyes were immobilized on the AAO surface by direct saturation of the films in dye solutions. It was shown by scanning electron microscopy and X-ray spectral analysis that the dyes penetrated into the AAO channels by more than 1.5 [small mu ]m, even at static saturation conditions. The anionic dyes linked to the porous AAO surface exhibited differential shifts of the UV absorption bands in their acidic/basic forms. By combining several dyes, the films have an application range between pH = 0.5-9 in aqueous media. The dye-modified AAO film was a simple, portable, inexpensive and reusable pH sensor with very fast response time and clear colour transitions.

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Analyst,
2015, 140 (3), 771-778.