TY - JOUR A1 - Wolf, S. E. A1 - Lieberwirth, I. A1 - Natalio, F. A1 - Bardeau, J.-F. A1 - Delorme, N. A1 - Emmerling, Franziska A1 - Barrea, R. A1 - Kappl, M. A1 - Marin, F. T1 - Merging models of biomineralisation with concepts of nonclassical crystallisation: is a liquid amorphous precursor involved in the formation of the prismatic layer of the Mediterranean Fan Mussel Pinna nobilis? N2 - The calcitic prisms of Pinna nobilis (Pinnidae, Linnaeus 1758) are shown to be perfect examples of a mesocrystalline material. Based on their ultrastructure and on the occurrence of an amorphous transient precursor during the early stages of prism formation, we provide evidence for the pathway of mesocrystallisation proposed by Seto et al. (2012), which proceeds not by self-organized oriented attachment of crystalline nano-bricks but by aggregation of initially amorphous nanogranules which later transform by epitaxial nucleation to a three-dimensional array of well aligned nanocrystals. We further fathom the role of a liquid amorphous calcium carbonate in biomineralisation processes and provide strong evidence for the occurrence of PILP-like intermediates during prism formation. We develop a new scenario of prism formation based on the presented findings presented findings and discuss the implications of a speculative liquid amorphous calcium carbonate (LACC) intermediate in vivo. PY - 2012 DO - https://doi.org/10.1039/c2fd20045g SN - 1359-6640 SN - 1364-5498 VL - 159 IS - 0 SP - 433 EP - 448 PB - Soc. CY - Cambridge [u.a.] AN - OPUS4-27122 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wolf, S. E. A1 - Müller, L. A1 - Barrea, R. A1 - Kampf, C.J. A1 - Leiterer, Jork A1 - Panne, Ulrich A1 - Hoffmann, T. A1 - Emmerling, Franziska A1 - Tremel, W. T1 - Carbonate-coordinated metal complexes precede the formation of liquid amorphous mineral emulsions of divalent metal carbonates N2 - During the mineralisation of metal carbonates MCO3 (M = Ca, Sr, Ba, Mn, Cd, Pb) liquid-like amorphous intermediates emerge. These intermediates that form via a liquid/liquid phase separation behave like a classical emulsion and are stabilized electrostatically. The occurrence of these intermediates is attributed to the formation of highly hydrated networks whose stability is mainly based on weak interactions and the variability of the metal-containing pre-critical clusters. Their existence and compositional freedom are evidenced by electrospray ionization mass spectrometry (ESI-MS). Liquid intermediates in non-classical crystallisation pathways seem to be more common than assumed. PY - 2011 DO - https://doi.org/10.1039/c0nr00761g SN - 2040-3364 SN - 2040-3372 IS - 3 SP - 1158 EP - 1165 PB - RSC Publ. CY - Cambridge AN - OPUS4-23355 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wu, D. A1 - Descalzo López, Ana Belén A1 - Weik, F. A1 - Emmerling, Franziska A1 - Shen, Z. A1 - You, X.-Z. A1 - Rurack, Knut T1 - Ein kernmodifiziertes Rubyrin mit meso-Aryl-Subsituenten und Phenanthren-anellierten Pyrrolringen als hoch konjugierter NIR-Farbstoff und Hg2+-Sonde KW - Fluoreszenz KW - NIR-Farbstoffe KW - Porphyrinoide KW - Quecksilber KW - Sensoren PY - 2008 DO - https://doi.org/10.1002/ange.200702854 SN - 0044-8249 SN - 0932-2140 SN - 1521-3757 VL - 120 IS - 1 SP - 199 EP - 203 PB - Wiley-VCH CY - Weinheim AN - OPUS4-16447 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wu, D. A1 - Descalzo López, Ana Belén A1 - Weik, F. A1 - Emmerling, Franziska A1 - Shen, Z. A1 - You, X.-Z. A1 - Rurack, Knut T1 - A core-modified Rubyrin with meso-aryl substituents and phenanthrene-fused pyrrole rings: a highly conjugated near-infrared dye and Hg2+ probe KW - Fluorescence KW - Mercury KW - NIR dyes KW - Porphyrinoids KW - Sensors PY - 2008 DO - https://doi.org/10.1002/Anie.200702854 SN - 1433-7851 SN - 1521-3773 SN - 0570-0833 VL - 47 IS - 1 SP - 193 EP - 197 PB - Wiley-VCH CY - Weinheim AN - OPUS4-16448 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wuithschick, M. A1 - Paul, B. A1 - Bienert, Ralf A1 - Sarfraz, A. A1 - Vainio, U. A1 - Sztucki, M. A1 - Kraehnert, R. A1 - Strasser, P. A1 - Rademann, K. A1 - Emmerling, Franziska A1 - Polte, J. T1 - Size-controlled synthesis of colloidal silver nanoparticles based on mechanistic understanding N2 - Metal nanoparticles have attracted much attention due to their unique properties. Size control provides an effective key to an accurate adjustment of colloidal properties. The common approach to size control is testing different sets of parameters via trial and error. The actual particle growth mechanisms, and in particular the influences of synthesis parameters on the growth process, remain a black box. As a result, precise size control is rarely achieved for most metal nanoparticles. This contribution presents an approach to size control that is based on mechanistic knowledge. It is exemplified for a common silver nanoparticle synthesis, namely, the reduction of AgClO4 with NaBH4. Conducting this approach allowed a well-directed modification of this synthesis that enables, for the first time, the size-controlled production of silver nanoparticles 4–8 nm in radius without addition of any stabilization agent. KW - Silver nanoparticles KW - Growth mechanism KW - SAXS KW - Size control KW - Sodium borohydride PY - 2013 DO - https://doi.org/10.1021/cm401851g SN - 0897-4756 SN - 1520-5002 VL - 25 IS - 23 SP - 4679 EP - 4689 PB - American Chemical Society CY - Washington, DC AN - OPUS4-30194 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yusenko, Kirill A1 - Kabelitz, Anke A1 - Schokel, Alexander A1 - Wagner, Ralf A1 - Prinz, Carsten A1 - Kemnitz, E A1 - Emmerling, Franziska A1 - Krahl, Thoralf A1 - de Oliveira Guilherme Buzanich, Ana T1 - Local Structure of Europium-Doped Luminescent Strontium Fluoride Nanoparticles: Comparative X-ray Absorption Spectroscopy and Diffraction Study N2 - Rare-earth based luminescent materials are key functional components for the rational design of light-conversion smart devices. Stable Eu3+-doped strontium fluoride (SrF2) nanoparticles were prepared at room temperature in ethylene glycol. Their luminescence depends on the Eu content and changes after heat treatment. The crystallinity of heat-treated material increases in comparison with as-synthesized samples. Particles were investigated in solution using X-ray diffraction, small-angle X-ray scattering, and X-ray spectroscopy. After heat treatment, the size of the disordered nanoparticles increases together with a change of their local structure. Interstitial fluoride ions can be localized near Eu3+ ions. Therefore, non-radiative relaxation from other mechanisms is decreased. Knowledge about the cation distribution is key information for understanding the luminescence properties of any material. KW - SrF2 KW - EXAFS KW - Eu PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-540094 DO - https://doi.org/10.1002/cnma.202100281 VL - 7 IS - 11 SP - 1221 EP - 1229 PB - Wiley Online Library AN - OPUS4-54009 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zauer, M. A1 - Prinz, Carsten A1 - Adolphs, J. A1 - Emmerling, Franziska A1 - Wagenführ, A. T1 - Sorption surfaces and energies of untreated and thermally modified wood evaluated by means of excess surface work (ESW) N2 - Water vapor sorption surface areas and sorption energies of untreated and thermally modified Norway spruce [Picea abies (L.) Karst.], sycamore maple (Acer pseudoplatanus L.) and European ash (Fraxinus excelcior L.) were investigated by means of dynamic vapor sorption (DVS) measurements and excess surface work (ESW) evaluation method, respectively. Adsorption and desorption experiments in the hygroscopic range and desorption tests from water saturation were conducted. Thermodynamically, ESW is the sum of the surface free energy and the isothermal isobaric work of sorption. From the amount adsorbed in the first Minimum a specific surface area similar to the BET surface area can be obtained. The results show that untreated spruce has a significantly higher specific water vapor Sorption surface and sorption energy compared to both hardwoods maple and ash. Thermal modification of the woods leads to a significant reduction of water vapor Sorption surface and sorption energy. The determined surface area and energy are higher in desorption direction than in adsorption direction, whereby the highest values in Desorption direction from water saturation, especially for maple and ash, were obtained. The surface areas calculated by means of the ESW method are similar to the surface areas calculated by means of the BET method, particularly in adsorption direction. KW - Excess surface work KW - Dynamic vapor sorption KW - Wood KW - BET PY - 2018 DO - https://doi.org/10.1007/s00226-018-1021-2 SN - 1432-5225 SN - 0043-7719 VL - 52 IS - 4 SP - 957 EP - 969 PB - Springer CY - Berlin Heidelberg AN - OPUS4-44975 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zink, N. A1 - Emmerling, Franziska A1 - Häger, T. A1 - Panthöfer, M. A1 - Tahir, M.N. A1 - Kolb, U. A1 - Tremel, W. T1 - Low temperature synthesis of monodisperse nanoscaled ZrO2 with a large specific surface area N2 - Thermal decomposition of Zr(C2O4)2·4H2O within an autoclave or in a conventional tube furnace at temperatures below 380 °C resulted in nano- and micron-sized ZrO2, respectively. Reactions under autogenic pressure yielded monodisperse monoclinic (m) and tetragonal (t) ZrO2 nanoparticles with an average diameter of ~8 nm and interconnected t-ZrO2 nanoparticles with diameters of ~4 nm, depending on the synthesis temperature. Samples were characterised by X-ray diffraction (XRD), small angle X-ray scattering (SAXS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) associated with energy dispersive X-ray spectroscopy (EDS), Raman microspectroscopy and photoluminescence spectroscopy (PL). Nanostructured zirconia materials exhibited high specific areas of 276–385 m2 g-1 which make them promising candidates as catalysts and catalyst supports. Co-existence of m- and t-ZrO2 nanoparticles with diameters of 6–9 nm, i.e. above the critical particle size of 6 nm for the formation of t-ZrO2, demonstrated that the particle size is not the only factor for stabilisation of the t-ZrO2 modification at room temperature. PY - 2013 DO - https://doi.org/10.1039/c2dt12496c SN - 1477-9226 SN - 1477-9234 SN - 1364-5447 VL - 42 SP - 432 EP - 440 PB - RSC CY - Cambridge AN - OPUS4-27733 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zuffa, Caterina A1 - Cappuccino, Chiara A1 - Casali, Lucia A1 - Emmerling, Franziska A1 - Maini, Lucia T1 - Liquid reagents are not enough for liquid assisted grinding in the synthesis of (AgBr)(n-pica) n N2 - This study investigates the mechanochemical reactions between AgBr 3-picolylamine and 4-picolylamine. The use of different stoichiometry ratios of the reagents allows [(AgBr)(n-pica)]n and [(AgBr)2(n-pica)]n to be obtained, and we report the new structures of [(AgBr)2(3-pica)]n and [(AgBr)2(4-pica)]n which are characterized by the presence of the following: (a) infinite inorganic chains, (b) silver atom coordinated only by bromide atoms and (c) argentophilic interactions. Furthermore, we studied the interconversion of [(AgBr)(n-pica)]n/[(AgBr)2(n-pica)]n by mechanochemical and thermal properties. The in situ experiments suggest that [(AgBr)(3-pica)]n is kinetically favoured while [(AgBr)2(3-pica)]n is converted into [(AgBr)(3-pica)]n only with a high excess of the ligand. Finally, the liquid nature of the ligands is not sufficient to assist the grinding process, and the complete reaction is observed with the addition of a small quantity of acetonitrile. KW - Mechanochemistry KW - Complex PY - 2024 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594755 DO - https://doi.org/10.1039/d3cp04791a SN - 1463-9076 SP - 1 EP - 10 PB - Royal Society of Chemistry (RSC) AN - OPUS4-59475 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Zänker, Steffen A1 - Scholz, G. A1 - Heise, M. A1 - Kemnitz, E. A1 - Emmerling, Franziska T1 - New 2D layered structures with direct fluorine-metal bonds: MF(CH3COO) (M: Sr, Ba, Pb) N2 - New coordination polymers with 2D network structures with fluorine directly coordinated to the metal ion were prepared both via mechanochemical synthesis and fluorolytic sol–gel synthesis. Depending on the synthesis route, the samples show different particle sizes, according to SEM imaging. The crystal structures of barium acetate fluoride, strontium acetate fluoride, and lead acetate fluoride (BaFIJCH3COO), SrFIJCH3COO) and PbFIJCH3COO)) were solved from X-ray powder diffraction data. The structure solution is backed by the results from 19F MAS NMR, FT IR data, and thermal analysis. The calculated chemical shifts of the 19F MAS NMR spectra coincide well with the measured ones. It turns out that the grinding conditions have a remarkable influence on the mechanochemical synthesis and its products. Our systematic study also indicates a strong influence of the atomic radii of Ca, Sr, Ba, and Pb on the success of the syntheses. KW - Mechanochemistry KW - Coordination polymers PY - 2020 DO - https://doi.org/10.1039/d0ce00287a VL - 22 IS - 16 SP - 2772 EP - 2780 PB - Royal Society of Chemistry AN - OPUS4-50789 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -