Jork Leiterer

Early Homogenous Amorphous Precursor Stages of Calcium Carbonate and Subsequent Crystal Growth in Levitated Droplets

An in situ study of the contact-free crystallization of calcium carbonate in acoustic levitated droplets is reported. The levitated droplet technique allows an in situ monitoring of the crystallization while avoiding any foreign phase boundaries that may influence the precipitation process by heterogeneous nucleation. The diffusion-controlled precipitation of CaCO3 at neutral pH starts in the initial step with the homogeneous formation of a stable, nanosized liquid-like amorphous calcium carbonate phase that undergoes in a subsequent step a solution-assisted transformation to calcite. Cryogenic scanning electron microscopy studies indicate that precipitation is not induced at the solution/air interface. Our findings demonstrate that a liquid-liquid phase separation occurs at the outset of the precipitation under diffusion-controlled conditions (typical for biomineral formation) with a slow increase of the supersaturation at neutral pH.

Carbonate-coordinated metal complexes precede the formation of liquid amorphous mineral emulsions of divalent metal carbonates

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.

Structure analysis using acoustically levitated droplets

Synchrotron diffraction with a micrometer-sized X-ray beam permits the efficient characterization of micrometer-sized samples, even in time-resolved experiments, which is important because often the amount of sample available is small and/or the sample is expensive. In this context, we will present acoustic levitation as a useful sample handling method for small solid and liquid samples, which are suspended in a gaseous environment (air) by means of a stationary ultrasonic field. A study of agglomeration and crystallization processes in situ was performed by continuously increasing the concentration of the samples by evaporating the solvent. Absorption and contamination processes on the sample container walls were suppressed strongly by this procedure, and parasitic scattering such as that observed when using glass capillaries was also absent. The samples investigated were either dissolved or dispersed in water droplets with diameters in the range of 1 micrometer to 2 millimeters. Initial results from time-resolved synchrotron small- and wide-angle X-ray scattering measurements of ascorbic acid, acetylsalicylic acid, apoferritin, and colloidal gold are presented.

Combined synchrotron XRD/Raman measurements: in situ identification of polymorphic transitions during crystallization processes.

A combination of two analytical methods, time-resolved X-ray diffraction (XRD) and Raman spectroscopy, is presented as a novel tool for crystallization studies. An acoustic levitator was employed as sample environment. This setup enables the acquisition of XRD and Raman data in situ simultaneously within a 20 s period and hence permits investigation of polymorphic phase transitions during the crystallization process in different solvents (methanol, ethanol, acetone, dichloromethane, acetonitrile). These real time measurements allow the determination of the phase content from the onset of the first crystalline molecular assemblies to the stable system. To evaluate the capability of this approach, the setup was applied to elucidate the crystallization process of the polymorphic compound nifedipine. The results indicate the existence of solvent-dependent transient phases during the crystallization process. The quality of the data allowed the assignment of the lattice constants of the hitherto unknown crystal structure of the beta-polymorph.

Acoustically Levitated Droplets

Acoustic levitation is used as a new tool to study concentration‐dependent processes in fluorescence spectroscopy. With this technique, small amounts of liquid and solid samples can be measured without the need for sample supports or containers, which often limits signal acquisition and can even alter sample properties due to interactions with the support material. We demonstrate that, because of the small sample volume, fluorescence measurements at high concentrations of an organic dye are possible without the limitation of inner‐filter effects, which hamper such experiments in conventional, cuvette‐based measurements. Furthermore, we show that acoustic levitation of liquid samples provides an experimentally simple way to study distance‐dependent fluorescence modulations in semiconductor nanocrystals. The evaporation of the solvent during levitation leads to a continuous increase of solute concentration and can easily be monitored by laser‐induced fluorescence.

Formation of α-helical nanofibers by mixing β-structured and α-helical coiled coil peptides.

The helical coiled coil is a well-studied folding motif that can be used for the design of nanometer-sized bioinspired fibrous structures with potential applications as functional materials. A two-component system of coiled coil based model peptides is investigated, which forms, under acidic conditions, uniform, hundreds of nanometers long, and ~2.6 nm thick trimeric α-helical fibers. In the absence of the other component and under the same solvent conditions, one model peptide forms β-sheet-rich amyloid fibrils and the other forms stable trimeric α-helical coiled coils, respectively. These observations reveal that the complementary interactions driving helical folding are much stronger here than those promoting the intermolecular β-sheet formation. The results of this study are important in the context of amyloid inhibition but also open up new avenues for the design of novel fibrous peptidic materials.

Container-less polymerization in acoustically levitated droplets: an analytical study by GPC and MALDI-TOF mass spectrometry

Molecular masses and end groups of polystyrene (PS) formed in a novel container-less polymerization strategy, based on levitated droplets in an acoustic trap, were determined by Gel Permeation Chromatography (GPC) and Matrix-assisted Laser Desorption/Ionization Time of Flight Mass spectrometry (MALDI-TOF MS).

The protofilament architecture of a de novo designed coiled coil-based amyloidogenic peptide

Amyloid fibrils are polymers formed by proteins under specific conditions and in many cases they are related to pathogenesis, such as Parkinsons and Alzheimers diseases. Their hallmark is the presence of a β-sheet structure. High resolution structural data on these systems as well as information gathered from multiple complementary analytical techniques is needed, from both a fundamental and a pharmaceutical perspective. Here, a previously reported de novo designed, pH-switchable coiled coil-based peptide that undergoes structural transitions resulting in fibril formation under physiological conditions has been exhaustively characterized by transmission electron microscopy (TEM), cryo-TEM, atomic force microscopy (AFM), wide-angle X-ray scattering (WAXS) and solid-state NMR (ssNMR). Overall, a unique 2-dimensional carpet-like assembly composed of large coexisiting ribbon-like, tubular and funnel-like structures with a clearly resolved protofilament substructure is observed. Whereas electron microscopy and scattering data point somewhat more to a hairpin model of β-fibrils, ssNMR data obtained from samples with selectively labelled peptides are in agreement with both, hairpin structures and linear arrangements.