@phdthesis{Giordano2014, author = {Giordano, Cristina}, title = {A neglected world: transition metal nitride and metal carbide based nanostructures}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-75375}, school = {Universit{\"a}t Potsdam}, pages = {191}, year = {2014}, abstract = {Potentiality of nanosized materials has been largely proved but a closer look shows that a significant percentage of this research is related to oxides and metals, while the number drastically drops for metallic ceramics, namely transition metal nitrides and metal carbides. The lack of related publications do not reflect their potential but rather the difficulties related to their synthesis as dense and defect-free structures, fundamental prerequisites for advanced mechanical applications. The present habilitation work aims to close the gap between preparation and processing, indicating novel synthetic pathways for a simpler and sustainable synthesis of transition metal nitride (MN) and carbide (MC) based nanostructures and easier processing thereafter. In spite of simplicity and reliability, the designed synthetic processes allow the production of functional materials, with the demanded size and morphology. The goal was achieved exploiting classical and less-classical precursors, ranging from common metal salts and molecules (e.g. urea, gelatin, agar, etc), to more exotic materials, such as leafs, filter paper and even wood. It was found that the choice of precursors and reaction conditions makes it possible to control chemical composition (going for instance from metal oxides to metal oxy-nitrides to metal nitrides, or from metal nitrides to metal carbides, up to quaternary systems), size (from 5 to 50 nm) and morphology (going from mere spherical nanoparticles to rod-like shapes, fibers, layers, meso-porous and hierarchical structures, etc). The nature of the mixed precursors also allows the preparation of metal nitrides/carbides based nanocomposites, thus leading to multifunctional materials (e.g. MN/MC@C, MN/MC@PILs, etc) but also allowing dispersion in liquid media. Control over composition, size and morphology is obtained with simple adjustment of the main route, but also coupling it with processes such as electrospin, aerosol spray, bio-templating, etc. Last but not least, the nature of the precursor materials also allows easy processing, including printing, coating, casting, film and thin layers preparation, etc). The designed routes are, concept-wise, similar and they all start by building up a secondary metal ion-N/C precursor network, which converts, upon heat treatment, into an intermediate "glass". This glass stabilizes the nascent nanoparticles during their nucleation and impairs their uncontrolled growth during the heat treatment (scheme 1). This way, one of the main problems related to the synthesis of MN/MC, i.e. the need of very high temperature, could also be overcome (from up to 2000°C, for classical synthesis, down to 700°C in the present cases). The designed synthetic pathways are also conceived to allow usage of non-toxic compounds and to minimize (or even avoid) post-synthesis purification, still bringing to phase pure and well-defined (crystalline) nanoparticles. This research aids to simplify the preparation of MN/MC, making these systems now readily available in suitable amounts both for fundamental and applied science. The prepared systems have been tested (in some cases for the first time) in many different fields, e.g. battery (MnN0.43@C shown a capacity stabilized at a value of 230 mAh/g, with coulombic efficiencies close to 100\%), as alternative magnetic materials (Fe3C nanoparticles were prepared with different size and therefore different magnetic behavior, superparamagnetic or ferromagnetic, showing a saturation magnetization value up to 130 emu/g, i.e. similar to the value expected for the bulk material), as filters and for the degradation of organic dyes (outmatching the performance of carbon), as catalysts (both as active phase but also as active support, leading to high turnover rate and, more interesting, to tunable selectivity). Furthermore, with this route, it was possible to prepare for the first time, to the best of our knowledge, well-defined and crystalline MnN0.43, Fe3C and Zn1.7GeN1.8O nanoparticles via bottom-up approaches. Once the synthesis of these materials can be made straightforward, any further modification, combination, manipulation, is in principle possible and new systems can be purposely conceived (e.g. hybrids, nanocomposites, ferrofluids, etc).}, language = {en} } @article{TaubertLerouxRabuetal.2019, author = {Taubert, Andreas and Leroux, Fabrice and Rabu, Pierre and de Zea Bermudez, Veronica}, title = {Advanced hybrid nanomaterials}, series = {Beilstein journal of nanotechnology}, volume = {10}, journal = {Beilstein journal of nanotechnology}, publisher = {Beilstein-Institut zur F{\"o}rderung der Chemischen Wissenschaften}, address = {Frankfurt am Main}, issn = {2190-4286}, doi = {10.3762/bjnano.10.247}, pages = {2563 -- 2567}, year = {2019}, language = {en} } @misc{OlejkoCywińskiBald2016, author = {Olejko, Lydia and Cywiński, P. J. and Bald, Ilko}, title = {An ion-controlled four-color fluorescent telomeric switch on DNA origami structures}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-95831}, pages = {10339 -- 10347}, year = {2016}, abstract = {The folding of single-stranded telomeric DNA into guanine (G) quadruplexes is a conformational change that plays a major role in sensing and drug targeting. The telomeric DNA can be placed on DNA origami nanostructures to make the folding process extremely selective for K+ ions even in the presence of high Na+ concentrations. Here, we demonstrate that the K+-selective G-quadruplex formation is reversible when using a cryptand to remove K+ from the G-quadruplex. We present a full characterization of the reversible switching between single-stranded telomeric DNA and G-quadruplex structures using F{\"o}rster resonance energy transfer (FRET) between the dyes fluorescein (FAM) and cyanine3 (Cy3). When attached to the DNA origami platform, the G-quadruplex switch can be incorporated into more complex photonic networks, which is demonstrated for a three-color and a four-color FRET cascade from FAM over Cy3 and Cy5 to IRDye700 with G-quadruplex-Cy3 acting as a switchable transmitter.}, language = {en} } @article{OlejkoCywińskiBald2016, author = {Olejko, Lydia and Cywiński, Piotr J. and Bald, Ilko}, title = {An ion-controlled four-color fluorescent telomeric switch on DNA origami structures}, series = {Nanoscale}, volume = {8}, journal = {Nanoscale}, publisher = {RSC Publ.}, address = {Cambridge}, issn = {2040-3372}, doi = {10.1039/C6NR00119J}, pages = {10339 -- 10347}, year = {2016}, abstract = {The folding of single-stranded telomeric DNA into guanine (G) quadruplexes is a conformational change that plays a major role in sensing and drug targeting. The telomeric DNA can be placed on DNA origami nanostructures to make the folding process extremely selective for K+ ions even in the presence of high Na+ concentrations. Here, we demonstrate that the K+-selective G-quadruplex formation is reversible when using a cryptand to remove K+ from the G-quadruplex. We present a full characterization of the reversible switching between single-stranded telomeric DNA and G-quadruplex structures using F{\"o}rster resonance energy transfer (FRET) between the dyes fluorescein (FAM) and cyanine3 (Cy3). When attached to the DNA origami platform, the G-quadruplex switch can be incorporated into more complex photonic networks, which is demonstrated for a three-color and a four-color FRET cascade from FAM over Cy3 and Cy5 to IRDye700 with G-quadruplex-Cy3 acting as a switchable transmitter.}, language = {en} } @article{XieMeiXuetal.2021, author = {Xie, Dongjiu and Mei, Shilin and Xu, Yaolin and Quan, Ting and Haerk, Eneli and Kochovski, Zdravko and Lu, Yan}, title = {Efficient sulfur host based on yolk-shell iron oxide/sulfide-carbon nanospindles for lithium-sulfur batteries}, series = {ChemSusChem : chemistry, sustainability, energy, materials}, volume = {14}, journal = {ChemSusChem : chemistry, sustainability, energy, materials}, number = {5}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1864-5631}, doi = {10.1002/cssc.202002731}, pages = {1404 -- 1413}, year = {2021}, abstract = {Numerous nanostructured materials have been reported as efficient sulfur hosts to suppress the problematic "shuttling" of lithium polysulfides (LiPSs) in lithium-sulfur (Li-S) batteries. However, direct comparison of these materials in their efficiency of suppressing LiPSs shuttling is challenging, owing to the structural and morphological differences between individual materials. This study introduces a simple route to synthesize a series of sulfur host materials with the same yolk-shell nanospindle morphology but tunable compositions (Fe3O4, FeS, or FeS2), which allows for a systematic investigation into the specific effect of chemical composition on the electrochemical performances of Li-S batteries. Among them, the S/FeS2-C electrode exhibits the best performance and delivers an initial capacity of 877.6 mAh g(-1) at 0.5 C with a retention ratio of 86.7 \% after 350 cycles. This approach can also be extended to the optimization of materials for other functionalities and applications.}, language = {en} } @misc{PacholskiAgarwalBalderasValadez2016, author = {Pacholski, Claudia and Agarwal, Vivechana and Balderas-Valadez, Ruth Fabiola}, title = {Fabrication of porous silicon-based optical sensors using metal-assisted chemical etching}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-394426}, pages = {21430 -- 21434}, year = {2016}, abstract = {Optical biosensors based on porous silicon were fabricated by metal assisted chemical etching. Thereby double layered porous silicon structures were obtained consisting of porous pillars with large pores on top of a porous silicon layer with smaller pores. These structures showed a similar sensing performance in comparison to electrochemically produced porous silicon interferometric sensors.}, language = {en} } @article{HenningLiebigPrietzeletal.2020, author = {Henning, Ricky and Liebig, Ferenc and Prietzel, Claudia Christina and Klemke, Bastian and Koetz, Joachim}, title = {Gold nanotriangles with magnetite satellites}, series = {Colloids and surfaces : an international journal devoted to the principles and applications of colloid and interface science ; A, Physicochemical and engineering aspects}, volume = {600}, journal = {Colloids and surfaces : an international journal devoted to the principles and applications of colloid and interface science ; A, Physicochemical and engineering aspects}, publisher = {Elsevier}, address = {Amsterdam}, issn = {0927-7757}, doi = {10.1016/j.colsurfa.2020.124913}, pages = {7}, year = {2020}, abstract = {This work describes the synthesis of hybrid particles of gold nanotriangles (AuNTs) with magnetite nanoparticles (MNPs) by using 1-mercaptopropyl-3-trimethoxysilan (MPTMS) and L-cysteine as linker molecules. Due to the combination of superparamagnetic properties of MNPs with optical properties of the AuNTs, nanoplatelet-satellite hybrid nanostructures with combined features become available. By using MPTMS with silan groups as linker molecule a magnetic "cloud" with embedded AuNTs can be separated. In presence of L-cysteine as linker molecule at pH > pH(iso) a more unordered aggregate structure of MNPs is obtained due to the dimerization of the L-cysteine. At pH < pH(iso) water soluble positively charged AuNTs with satellite MNPs can be synthesized. The time-dependent loading with MNP satellites under release of the extinction and magnetization offer a hybrid material, which is of special relevance for biomedical applications and plasmonic catalysis.}, language = {en} } @article{QuanGoubardBretescheHaerketal.2019, author = {Quan, Ting and Goubard-Bretesche, Nicolas and Haerk, Eneli and Kochovski, Zdravko and Mei, Shilin and Pinna, Nicola and Ballauff, Matthias and Lu, Yan}, title = {Highly Dispersible Hexagonal Carbon-MoS2-Carbon Nanoplates with Hollow Sandwich Structures for Supercapacitors}, series = {Chemistry - a European journal}, volume = {25}, journal = {Chemistry - a European journal}, number = {18}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0947-6539}, doi = {10.1002/chem.201806060}, pages = {4757 -- 4766}, year = {2019}, abstract = {MoS2, a typical layered transition-metal dichalcogenide, is promising as an electrode material in supercapacitors. However, its low electrical conductivity could lead to limited capacitance if applied in electrochemical devices. Herein, a new nanostructure composed of hollow carbon-MoS2-carbon was successfully synthesized through an L-cysteine-assisted hydrothermal method by using gibbsite as a template and polydopamine as a carbon precursor. After calcination and etching of the gibbsite template, uniform hollow platelets, which were made of a sandwich-like assembly of partial graphitic carbon and two-dimensional layered MoS2 flakes, were obtained. The platelets showed excellent dispersibility and stability in water, and good electrical conductivity due to carbon provided by the calcination of polydopamine coatings. The hollow nanoplate morphology of the material provided a high specific surface area of 543 m(2) g(-1), a total pore volume of 0.677 cm(3) g(-1), and fairly small mesopores (approximate to 5.3 nm). The material was applied in a symmetric supercapacitor and exhibited a specific capacitance of 248 F g(-1) (0.12 F cm(-2)) at a constant current density of 0.1 Ag-1; thus suggesting that hollow carbon-MoS2 carbon nanoplates are promising candidate materials for supercapacitors.}, language = {en} } @article{OlejkoCywinskiBald2015, author = {Olejko, Lydia and Cywinski, Piotr J. and Bald, Ilko}, title = {Ion-Selective formation of a guanine quadruplex on DNA origami structures}, series = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, volume = {54}, journal = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition}, number = {2}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1433-7851}, doi = {10.1002/anie.201409278}, pages = {673 -- 677}, year = {2015}, abstract = {DNA origami nanostructures are a versatile tool that can be used to arrange functionalities with high local control to study molecular processes at a single-molecule level. Here, we demonstrate that DNA origami substrates can be used to suppress the formation of specific guanine (G) quadruplex structures from telomeric DNA. The folding of telomeres into G-quadruplex structures in the presence of monovalent cations (e.g. Na+ and K+) is currently used for the detection of K+ ions, however, with insufficient selectivity towards Na+. By means of FRET between two suitable dyes attached to the 3- and 5-ends of telomeric DNA we demonstrate that the formation of G-quadruplexes on DNA origami templates in the presence of sodium ions is suppressed due to steric hindrance. Hence, telomeric DNA attached to DNA origami structures represents a highly sensitive and selective detection tool for potassium ions even in the presence of high concentrations of sodium ions.}, language = {en} } @article{ReinhardtKocLeitenbergeretal.2016, author = {Reinhardt, Matthias and Koc, Azize and Leitenberger, Wolfram and Gaal, Peter and Bargheer, Matias}, title = {Optimized spatial overlap in optical pump-X-ray probe experiments with high repetition rate using laser-induced surface distortions}, series = {Journal of synchrotron radiation}, volume = {23}, journal = {Journal of synchrotron radiation}, publisher = {International Union of Crystallography}, address = {Chester}, issn = {1600-5775}, doi = {10.1107/S1600577515024443}, pages = {474 -- 479}, year = {2016}, abstract = {Ultrafast X-ray diffraction experiments require careful adjustment of the spatial overlap between the optical excitation and the X-ray probe pulse. This is especially challenging at high laser repetition rates. Sample distortions caused by the large heat load on the sample and the relatively low optical energy per pulse lead to only tiny signal changes. In consequence, this results in small footprints of the optical excitation on the sample, which turns the adjustment of the overlap difficult. Here a method for reliable overlap adjustment based on reciprocal space mapping of a laser excited thin film is presented.}, language = {en} } @misc{HesseKlierSgarzietal.2018, author = {Hesse, Julia and Klier, Dennis Tobias and Sgarzi, Massimo and Nsubuga, Anne and Bauer, Christoph and Grenzer, J{\"o}rg and H{\"u}bner, Ren{\´e} and Wislicenus, Marcus and Joshi, Tanmaya and Kumke, Michael Uwe and Stephan, Holger}, title = {Rapid synthesis of sub-10 nm hexagonal NaYF4-based upconverting nanoparticles using Therminol® 66}, series = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe}, journal = {Postprints der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe}, number = {613}, issn = {1866-8372}, doi = {10.25932/publishup-42351}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-423515}, pages = {10}, year = {2018}, abstract = {We report a simple one-pot method for the rapid preparation of sub-10nm pure hexagonal (-phase) NaYF4-based upconverting nanoparticles (UCNPs). Using Therminol((R))66 as a co-solvent, monodisperse UCNPs could be obtained in unusually short reaction times. By varying the reaction time and reaction temperature, it was possible to control precisely the particle size and crystalline phase of the UCNPs. The upconversion (UC) luminescence properties of the nanocrystals were tuned by varying the concentrations of the dopants (Nd3+ and Yb3+ sensitizer ions and Er3+ activator ions). The size and phase-purity of the as-synthesized core and core-shell nanocrystals were assessed by using complementary transmission electron microscopy, dynamic light scattering, X-ray diffraction, and small-angle X-ray scattering studies. In-depth photophysical evaluation of the UCNPs was pursued by using steady-state and time-resolved luminescence spectroscopy. An enhancement in the UC intensity was observed if the nanocrystals, doped with optimized concentrations of lanthanide sensitizer/activator ions, were further coated with an inert/active shell. This was attributed to the suppression of surface-related luminescence quenching effects.}, language = {en} } @article{HesseKlierSgarzietal.2018, author = {Hesse, Julia and Klier, Dennis Tobias and Sgarzi, Massimo and Nsubuga, Anne and Bauer, Christoph and Grenzer, Joerg and H{\"u}bner, Rene and Wislicenus, Marcus and Joshi, Tanmaya and Kumke, Michael Uwe and Stephan, Holger}, title = {Rapid Synthesis of Sub-10nm Hexagonal NaYF4-Based Upconverting Nanoparticles using Therminol((R))66}, series = {ChemistryOpen : including thesis treasury}, volume = {7}, journal = {ChemistryOpen : including thesis treasury}, number = {2}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {2191-1363}, doi = {10.1002/open.201700186}, pages = {159 -- 168}, year = {2018}, abstract = {We report a simple one-pot method for the rapid preparation of sub-10nm pure hexagonal (-phase) NaYF4-based upconverting nanoparticles (UCNPs). Using Therminol((R))66 as a co-solvent, monodisperse UCNPs could be obtained in unusually short reaction times. By varying the reaction time and reaction temperature, it was possible to control precisely the particle size and crystalline phase of the UCNPs. The upconversion (UC) luminescence properties of the nanocrystals were tuned by varying the concentrations of the dopants (Nd3+ and Yb3+ sensitizer ions and Er3+ activator ions). The size and phase-purity of the as-synthesized core and core-shell nanocrystals were assessed by using complementary transmission electron microscopy, dynamic light scattering, X-ray diffraction, and small-angle X-ray scattering studies. In-depth photophysical evaluation of the UCNPs was pursued by using steady-state and time-resolved luminescence spectroscopy. An enhancement in the UC intensity was observed if the nanocrystals, doped with optimized concentrations of lanthanide sensitizer/activator ions, were further coated with an inert/active shell. This was attributed to the suppression of surface-related luminescence quenching effects.}, language = {en} } @phdthesis{FortesMartin2023, author = {Fortes Mart{\´i}n, Rebeca}, title = {Water-in-oil microemulsions as soft-templates to mediate nanoparticle interfacial assembly into hybrid nanostructures}, doi = {10.25932/publishup-57180}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-571801}, school = {Universit{\"a}t Potsdam}, pages = {119}, year = {2023}, abstract = {Hybrid nanomaterials offer the combination of individual properties of different types of nanoparticles. Some strategies for the development of new nanostructures in larger scale rely on the self-assembly of nanoparticles as a bottom-up approach. The use of templates provides ordered assemblies in defined patterns. In a typical soft-template, nanoparticles and other surface-active agents are incorporated into non-miscible liquids. The resulting self-organized dispersions will mediate nanoparticle interactions to control the subsequent self-assembly. Especially interactions between nanoparticles of very different dispersibility and functionality can be directed at a liquid-liquid interface. In this project, water-in-oil microemulsions were formulated from quasi-ternary mixtures with Aerosol-OT as surfactant. Oleyl-capped superparamagnetic iron oxide and/or silver nanoparticles were incorporated in the continuous organic phase, while polyethyleneimine-stabilized gold nanoparticles were confined in the dispersed water droplets. Each type of nanoparticle can modulate the surfactant film and the inter-droplet interactions in diverse ways, and their combination causes synergistic effects. Interfacial assemblies of nanoparticles resulted after phase-separation. On one hand, from a biphasic Winsor type II system at low surfactant concentration, drop-casting of the upper phase afforded thin films of ordered nanoparticles in filament-like networks. Detailed characterization proved that this templated assembly over a surface is based on the controlled clustering of nanoparticles and the elongation of the microemulsion droplets. This process offers versatility to use different nanoparticle compositions by keeping the surface functionalization, in different solvents and over different surfaces. On the other hand, a magnetic heterocoagulate was formed at higher surfactant concentration, whose phase-transfer from oleic acid to water was possible with another auxiliary surfactant in ethanol-water mixture. When the original components were initially mixed under heating, defined oil-in-water, magnetic-responsive nanostructures were obtained, consisting on water-dispersible nanoparticle domains embedded by a matrix-shell of oil-dispersible nanoparticles. Herein, two different approaches were demonstrated to form diverse hybrid nanostructures from reverse microemulsions as self-organized dispersions of the same components. This shows that microemulsions are versatile soft-templates not only for the synthesis of nanoparticles, but also for their self-assembly, which suggest new approaches towards the production of new sophisticated nanomaterials in larger scale.}, language = {en} }