Publikationen am Institut für Chemie und Biotechnik

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Knauer, Andrea; Kuhfuss, Danja; Köhler, Michael;
Electrostatic control of Au nanorod formation in automated microsegmented flow synthesis. - In: ACS applied nano materials. - Washington, DC : ACS Publications, ISSN 2574-0970, Bd. 4 (2021), 2, S. 1411-1419

An automated flow rate program was applied for the synthesis of gold nanorods of different aspect ratios dependent on a two-dimensional concentration space of reducing agent and additional silver ions. It was found a regular redshift of the spectral position of the electromagnetic in-axis resonance of metal nanorods with decreasing concentration of reducing agent and increasing concentration of silver ions. The increase of resonance wavelength is strongly correlated with the aspect ratio of the formed nanorods. The experimental results agree with an electrostatic model of self-polarization due to positive excess charge of the nanorods in the presence of CTAB and confirm the crucial role of electrostatic control in the formation of nonspherical and composed nanoparticles in general.



https://doi.org/10.1021/acsanm.0c02941
Schumann, Peter; Kalensee, Franziska; Cao, Jialan; Criscuolo, Alexis; Clermont, Dominique; Köhler, Michael; Meier-Kolthoff, Jan Philipp; Neumann-Schaal, Meina; Tindall, Brian J.; Pukall, Rüdiger;
Reclassification of Haloactinobacterium glacieicola as Occultella glacieicola gen. nov., comb. nov., of Haloactinobacterium album as Ruania alba comb. nov, with an emended description of the genus Ruania, recognition that the genus names Haloactinobacterium and Ruania are heterotypic synonyms and description of Occultella aeris sp. nov., a halotolerant isolate from surface soil sampled at an ancient copper smelter. - In: International journal of systematic and evolutionary microbiology : IJSEM ; official publication of the International Committee on Systematic Bacteriology and the Bacteriology and Applied Microbiology Division of the International Union of Microbiological Societies.. - Reading : SGM, ISSN 1466-5034, Bd. 71 (2021), 4, S. 004769

In the course of screening the surface soils of ancient copper mines and smelters (East Harz, Germany) an aerobic, non-motile and halotolerant actinobacterium forming small rods or cocci was isolated. The strain designated F300T developed creamy to yellow colonies on tryptone soy agar and grew optimally at 28 ˚C, pH 7-8 and with 0.5-2% (m/v) NaCl. Its peptidoglycan was of type A4α l-Lys-l-Glu (A11.54). The menaquinone profile was dominated by MK-8(II, III-H4) and contained minor amounts of MK-8(H2), MK-8(H6) and MK-9(H4). The polar lipids comprised diphosphatidylglycerol, phosphatidylglycerol, phosphatidylinositol, mono and diacylated phosphatidylinositol dimannosides, and components that were not fully characterized, including two phospholipids, two glycolipids and an uncharacterized lipid. Major whole-cell sugars were rhamnose and ribose. The fatty acid profile contained mainly iso and anteiso branched fatty acids (anteiso-C15:0, iso-C14:0) and aldehydes/dimethylacetals (i.e. not fatty acids). Sequence analysis of its genomic DNA and subsequent analysis of the data placed the isolate in the group currently defined by members of the genera Ruania and Haloactinobacterium (family Ruaniaceae , order Micrococcales ) as a sister taxon to the previously described species Haloactinobacterium glacieicola , sharing an average nucleotide identity and average amino acid identity values of 85.3 and 85.7%, respectively. Genotypic and chemotaxonomic analyses support the view that strain F300T (=DSM 108350T=CIP 111667T) is the type strain of a new genus and new species for which the name Occultella aeris gen. nov., sp. nov. is proposed. Based on revised chemotaxonomic and additional genome based data, it is necessary to discuss and evaluate the results in the light of the classification and nomenclature of members of the family Ruaniaceae , i.e. the genera Haloactinobacterium and Ruania . Consequently, the reclassification of Haloactinobacterium glacieicola as Occultella glacieicola comb. nov. and Haloactinobacterium album as Ruania alba comb. nov., with an emended description of the genus Ruania are proposed.,



https://doi.org/10.1099/ijsem.0.004769
Visaveliya, Nikunjkumar R.; Köhler, Michael;
Hierarchical assemblies of polymer particles through tailored interfaces and controllable interfacial interactions. - In: Advanced functional materials. - Weinheim : Wiley-VCH, ISSN 1616-3028, Volume 31 (2021), issue 9, 2007407, Seite 1-22

Hierarchical assembly architectures of functional polymer particles are promising because of their physicochemical and surface properties for multi-labeling and sensing to catalysis and biomedical applications. While polymer nanoparticles' interior is mainly made up of the cross-linked network, their surface can be tailored with soft, flexible, and responsive molecules and macromolecules as potential support for the controlled particulate assemblies. Molecular surfactants and polyelectrolytes as interfacial agents improve the stability of the nanoparticles whereas swellable and soft shell-like cross-linked polymeric layer at the interface can significantly enhance the uptake of guest nano-constituents during assemblies. Besides, layer-by-layer surface-functionalization holds the ability to provide a high variability in assembly architectures of different interfacial properties. Considering these aspects, various assembly architectures of polymer nanoparticles of tunable size, shapes, morphology, and tailored interfaces together with controllable interfacial interactions are constructed here. The microfluidic-mediated platform has been used for the synthesis of constituents polymer nanoparticles of various structural and interfacial properties, and their assemblies are conducted in batch or flow conditions. The assemblies presented in this progress report is divided into three main categories: cross-linked polymeric network's fusion-based self-assembly, electrostatic-driven assemblies, and assembly formed by encapsulating smaller nanoparticles into larger microparticles.



https://doi.org/10.1002/adfm.202007407
Hasselmann, Sebastian; Kopittke, Caroline; Götz, Maria; Witzel, Patrick; Riffel, Jacqueline; Heinrich, Doris;
Tailored nanotopography of photocurable composites for control of cell migration. - In: RSC Advances : an international journal to further the chemical sciences.. - London : RSC Publishing, ISSN 2046-2069, Bd. 11 (2021), 8, S. 4286-4296

External mechanical stimuli represent elementary signals for living cells to adapt to their adjacent environment. These signals range from bulk material properties down to nanoscopic surface topography and trigger cell behaviour. Here, we present a novel approach to generate tailored surface roughnesses in the nanometer range to tune surface properties by particle size and volume ratio. Time-resolved local mean-squared displacement (LMSD) analysis of amoeboid cell migration reveals that nanorough surfaces alter effectively cell migration velocities and the active cell migration phases. Since the UV curable composite material is easy to fabricate and can be structured via different light based processes, it is possible to generate hierarchical 3D cell scaffolds for tissue engineering or lab-on-a-chip applications with adjustable surface roughness in the nanometre range.



https://doi.org/10.1039/D0RA06530G
Köhler, Michael; Kluitmann, Jonas;
In situ assembly of gold nanoparticles in the presence of poly-DADMAC resulting in hierarchical and highly fractal nanostructures. - In: Applied Sciences : open access journal.. - Basel : MDPI, ISSN 2076-3417, Volume 11 (2021), issue 3, 1191, Seite 1-13

The presence of the polycationic macromolecule poly(diallyldimethylammonium chloride) (poly-DADMAC) has a strong effect on the shape and size of colloidal gold nanoparticles formed by the reduction of tetrachloroauric acid with ascorbic acid in aqueous solution. It slows down nanoparticle growth and supports the formation of nonspherical, partially highly fractal and hierarchical nanoparticle shapes. Four structural levels have been recognized from the near-spherical gold nanoparticles in the lower nanometer range over compact aggregates in the midnanometer range and flower and star-like particles in the submicron range up to larger filamentous aggregates. High-contrast scanning electron microscope (SEM) images show that single gold nanoparticles and clusters of them are connected by bundles of macromolecules in large aggregates. The investigation showed that a large spectrum of different nanoparticle shapes and sizes can be accessed by tuning the poly-DADMAC concentrations and their ratio to other reactants. The nanoassemblies with a very high specific surface area might be of interest for SERS and heterogeneous catalysis.



https://doi.org/10.3390/app11031191
Täuscher, Eric;
Salpetersäure zum Rauchen bringen. - In: Nachrichten aus der Chemie : Zeitschrift der Gesellschaft Deutscher Chemiker.. - Weinheim : Wiley-VCH, ISSN 1868-0054, Bd. 68 (2020), 10, S. 20-22

Rauchende Salpetersäure ist im Handel nur hochrein zu kaufen und daher teuer - zu teuer für Hochschulpraktika. An der TU Ilmenau synthetisieren die Studierenden die HNO3 nun selbst als Praktikumsversuch und nutzen dafür historische Anleitungen.



https://doi.org/10.1002/nadc.20204101724
Miao, Qing; Zurlo, Enrico; Bruin, Donny; Wondergem, Joeri A. J.; Timmer, Monika; Blok, Anneloes; Heinrich, Doris; Overhand, Mark; Huber, Martina; Ubbink, Marcellus;
A two-armed probe for in-cell DEER measurements on proteins. - In: Chemistry - a European journal. - Weinheim : Wiley-VCH, ISSN 1521-3765, Bd. 26 (2020), 71, S. 17128-17133

The application of double electron-electron resonance (DEER) with site-directed spin labeling (SDSL) to measure distances in proteins and protein complexes in living cells puts rigorous restraints on the spin-label. The linkage and paramagnetic centers need to resist the reducing conditions of the cell. Rigid attachment of the probe to the protein improves precision of the measured distances. Here, three two-armed GdIII complexes, GdIII-CLaNP13a/b/c were synthesized. Rather than the disulfide linkage of most other CLaNP molecules, a thioether linkage was used to avoid reductive dissociation of the linker. The doubly GdIII labeled N55C/V57C/K147C/T151C variants of T4Lysozyme were measured by 95 GHz DEER. The constructs were measured in vitro, in cell lysate and in Dictyostelium discoideum cells. Measured distances were 4.5 nm, consistent with results from paramagnetic NMR. A narrow distance distribution and typical modulation depth, also in cell, indicate complete and durable labeling and probe rigidity due to the dual attachment sites.



https://doi.org/10.1002/chem.202002743
Sukhodub, Liudmyla B.; Sukhodub, Leonid F.; Prylutskyy, Yuriy I.; Kumeda, Mariya A.; Ritter, Uwe;
Graphene oxide influences on mechanical properties and drug release ability of hydroxyapatite based composite material. - In: Nanomaterials in biomedical application and bionsensors (NAP-2019). - Singapore : Springer, (2020), S. 139-149

Bioactive composite material based on hydroxyapatite (HA), sodium alginate (Alg) with different content of graphene oxide (GO) was synthesized by the wet chemistry method and characterized by TEM, XRD, FTIR, HPLC analysis. Introduced the GO nanoparticles, as well as Ca2+ ions, as cross-linker of Alg macromolecules by the beads formation, lead to enhancement of the composites mechanical properties. HA-Alg-GO10 sample with GO content of 0.004% in relation to the HA powder has a much higher Youngs modulus (1325 MPa) in comparison with GO-free HA-Alg composite (793 MPa), as well as steel sample of the same size (˜706 MPa). The addition of GO reduces the degree of the composites swelling in a phosphate buffered saline for 43% and enhances the beads shape stability. Chlorhexidine bigluconate release from GO containing samples lasts for 48 h longer according to HPLC study. The findings clear demonstrate the potential possibility of applications of the HA-Alg-GO composite material in bioengineering of bone tissue to fill bone defects of various geometries with the function of prolonged release of the drug. It is assumed that HA-Alg-GO composite material can be used in 3D modeling of areas of bone tissue that have to bear a mechanical load.



Mazétyté-Stasinskiené, Raminta; Köhler, Michael;
Sensor micro and nanoparticles for microfluidic application. - In: Applied Sciences : open access journal.. - Basel : MDPI, ISSN 2076-3417, Volume 10 (2020), issue 23, 8383, Seite 1-37

Micro and nanoparticles are not only understood as components of materials but as small functional units too. Particles can be designed for the primary transduction of physical and chemical signals and, therefore, become a valuable component in sensing systems. Due to their small size, they are particularly interesting for sensing in microfluidic systems, in microarray arrangements and in miniaturized biotechnological systems and microreactors, in general. Here, an overview of the recent development in the preparation of micro and nanoparticles for sensing purposes in microfluidics and application of particles in various microfluidic devices is presented. The concept of sensor particles is particularly useful for combining a direct contact between cells, biomolecules and media with a contactless optical readout. In addition to the construction and synthesis of micro and nanoparticles with transducer functions, examples of chemical and biological applications are reported.



https://doi.org/10.3390/app10238353
Visaveliya, Nikunjkumar R.; Köhler, Michael;
Emerging structural and interfacial features of particulate polymers at the nanoscale. - In: Langmuir : the ACS journal of surfaces and colloids.. - Washington, DC : ACS Publ., ISSN 1520-5827, Bd. 36 (2020), 44, S. 13125-13143

Particulate polymers at the nanoscale are exceedingly promising for diversified functional applications ranging from biomedical and energy to sensing, labeling, and catalysis. Tailored structural features (i.e., size, shape, morphology, internal softness, interior cross-linking, etc.) determine polymer nanoparticles' impact on the cargo loading capacity and controlled/sustained release, possibility of endocytosis, degradability, and photostability. The designed interfacial features, however (i.e., stimuli-responsive surfaces, wrinkling, surface porosity, shell-layer swellability, layer-by-layer surface functionalization, surface charge, etc.), regulate nanoparticles interfacial interactions, controlled assembly, movement and collision, and compatibility with the surroundings (e.g., solvent and biological environments). These features define nanoparticles' overall properties/functions on the basis of homogeneity, stability, interfacial tension, and minimization of the surface energy barrier. Lowering of the resultant outcomes is directly influenced by inhomogeneity in the structural and interfacial design through the structure-function relationship. Therefore, a key requirement is to produce well-defined polymer nanoparticles with controlled characteristics. Polymers are amorphous, flexible, and soft, and hence controlling their structural/interfacial features through the single-step process is a challenge. The microfluidics reaction strategy is very promising because of its wide range of advantages such as efficient reactant mixing and fast phase transfer. Overall, this feature article highlights the state-of-the-art synthetic features of polymer nanoparticles with perspectives on their advanced applications.



https://doi.org/10.1021/acs.langmuir.0c02566