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Organisationseinheit der BAM
We present how mesoporosity can be engineered in transition metal phosphate (TMPs) materials in a template-free manner. The method involves the transformation of a precursor metal phosphate phase, called M-struvite (NH4MPO4·6H2O, M = Mg2+, Ni2+, Co2+, NixCo1−x2+). It relies on the thermal decomposition of crystalline M-struvite precursors to an amorphous and simultaneously mesoporous phase, which forms during degassing of NH3 and H2O. The temporal evolution of mesoporous frameworks and the response of the metal coordination environment were followed by in situ and ex situ scattering and diffraction, as well as X-ray spectroscopy. Despite sharing the same precursor struvite structure, different amorphous and mesoporous structures were obtained depending on the involved transition metal. We highlight the systematic differences in absolute surface area, pore shape, pore size, and phase transitions depending on the metal cation present in the analogous M-struvites. The amorphous structures of thermally decomposed Mg-, Ni- and NixCo1−x-struvites exhibit high surface areas and pore volumes (240 m2 g−1 and 0.32 cm−3 g−1 for Mg and 90 m2 g−1 and 0.13 cm−3 g−1 for Ni). We propose that the low-cost, environmentally friendly M-struvites could be obtained as recycling products from industrial and agricultural wastewaters. These waste products could be then upcycled into mesoporous TMPs through a simple thermal treatment for further application, for instance in (electro)catalysis.
Mechanochemistry is increasingly used as a ‘green alternative’ for synthesizing various materials including pharmaceutical cocrystals. Herein, we present the mechanochemical synthesis of three new cocrystals containing the API carbamazepine (cocrystals CBZ:Indometacin 1:1, CBZ:Benzamide 1:1, and CBZ:Nifedipine 1:1). The mechanochemical reaction was investigated in situ documenting a fast and complete reaction within one minute. Online NMR spectroscopy proved the direct influence of the dissolution behaviour of the coformers to the dissolution behaviour of the API carbamazepine. The dissolution behaviour of the organic cocrystals is compared to the behaviour of the pure drug indicating a general applicability of this approach for detailed cocrystal dissolution studies.
While polymorphism is a common phenomenon in the crystallization processes of organic compounds, polyamorphism has gained importance only recently. Using sophisticated sample environments and applying in situ scattering methods and vibrational spectroscopy, the complete crystallization process of organic compounds from solution can be traced and characterized. Diffuse scattering from amorphous intermediates can be investigated by analyzing the atomic pair distribution function (PDF) to gain further insights into molecular pre-orientation. The crystallization behavior of paracetamol was studied exemplarily under defined, surface-free conditions. Based on the choice of the solvent, the formation of different polymorphs is promoted. The thermodynamically stable form I and the metastable orthorhombic form II could be isolated in pure form directly from solution. For both polymorphs, the crystallization from solution proceeds via a distinct amorphous precursor phase. PDF analyses of these different amorphous states indicate a specific pre-orientation of the analyte molecules introduced by the solvent. The resulting crystalline polymorph is already imprinted in these proto-crystalline precursors. Direct experimental evidence for the polyamorphism of paracetamol is provided.
The absolute configuration of the title compound, C18H24O5·H2O, was not been determined by anomalous-dispersion effects, but has been assigned by reference to an unchanging chiral centre in the synthetic procedure. Intramolecular O—H···O hydrogen bonds stabilize the molecular conformation. In the crystal, O—H···O hydrogen bonds link the main molecules and the water molecules, forming an infinite three-dimensional network.
A systematic crystal morphology study on the pharmaceutical model compound caffeine has been conducted on different surfaces: silicon, silver, soda lime glass, and silver subsurface ion-exchanged soda-lime silicate (SIMO) glasses. The morphology of the solid caffeine deposits has been investigated using environmental scanning electron microscopy (ESEM), atomic force microscopy (AFM), and X-ray diffraction (XRD). Needle-shaped caffeine crystals have been observed by drop-casting and also by applying the rapid expansion of supercritical solutions (RESS) technique using supercritical carbon dioxide. The aspect ratio of the crystalline needles typically vary between 10 and 100, but have been observed as large as 500. The XRD data of the RESS products indicate unambiguously the presence of the thermodynamically most stable polymorph of caffeine known as the β-form. Under defined conditions we observe a unique, surface-mediated morphology for caffeine crystals with nearly perfect hexagonal shape. The relative fraction of the hexagons was seen to strongly increase especially when SIMO glasses were used. These hexagons have a distinct upper size limit depending on the solvent and substrate being used. The size distribution analysis of the hexagons yielded an average perimeter of typically 10 µm. The mechanism of the formation process of this new hexagonal motif is explained in terms of the spinodal dewetting of the thin film of caffeine solution on the surface.