Biogenic guanine crystals are solid solutions of guanine and other purine metabolites

Highly reflective crystals of the nucleotide base guanine are widely distributed in animal coloration and visual systems. Organisms precisely control the morphology and organization of the crystals to optimize different optical effects, but little is known about how this is achieved. Here we examine a fundamental question that has remained unanswered after over 100 years of research on guanine: what are the crystals made of? Using solution-state and solid-state chemical techniques coupled with structural analysis by powder XRD and solid-state NMR, we compare the purine compositions and the structures of seven biogenic guanine crystals with different crystal morphologies, testing the hypothesis that intracrystalline dopants influence the crystal shape. We find that biogenic “guanine” crystals are not pure crystals but molecular alloys (aka solid solutions and mixed crystals) of guanine, hypoxanthine, and sometimes xanthine. Guanine host crystals occlude homogeneous mixtures of other purines, sometimes in remarkably large amounts (up to 20% of hypoxanthine), without significantly altering the crystal structure of the guanine host. We find no correlation between the biogenic crystal morphology and dopant content and conclude that dopants do not dictate the crystal morphology of the guanine host. The ability of guanine crystals to host other molecules enables animals to build physiologically “cheaper” crystals from mixtures of metabolically available purines, without impeding optical functionality. The exceptional levels of doping in biogenic guanine offer inspiration for the design of mixed molecular crystals that incorporate multiple functionalities in a single material

Electrostatic interplay: The interaction triangle of polyamines, silicic acid, and phosphate studied through turbidity measurements, silicomolybdic acid test, and 29Si NMR spectroscopy

The discovery of long-chain polyamines as biomolecules that are tightly associated to biosilica in diatom cell walls has inspired numerous in vitro studies aiming to characterize polyamine–silica interactions. The determination of these interactions at the molecular level is of fundamental interest on one hand for the understanding of cell wall biogenesis in diatoms and on the other hand for designing bioinspired materials synthesis approaches. The present contribution deals with the influence of amines and polyamines upon the initial self-assembly processes taking place during polyamine-mediated silica formation in solution. The influence of phosphate upon these processes is studied. For this purpose, sodium metasilicate solutions containing additives such as polyallylamine, allylamine and others in the presence/absence of phosphate were investigated. The analyses are based mainly on turbidity measurements yielding information about the early aggregation steps which finally give rise to the formation and precipitation of silica

Mineralogical Imaging for Characterization of the Per Geijer Apatite Iron Ores in the Kiruna District, Northern Sweden: A Comparative Study of Mineral Liberation Analysis and Raman Imaging

The Per Geijer iron oxide apatite deposits are important potential future resources for Luossavaara-Kiirunavaara Aktiebolag (LKAB) which has been continuously mining magnetite/hematite ores in northern Sweden for over 125 years. Reliable and quantitative characterization of the mineralization is required as these ores inherit complex mineralogical and textural features. Scanning electron microscopy-based analyses software, such as mineral liberation analyzer (MLA) provide significant, time-efficient analyses. Similar elemental compositions of Fe-oxides and, therefore, almost identical backscattered electron (BSE) intensities complicate their discrimination. In this study, MLA and Raman imaging are compared to acquire mineralogical data for better characterization of magnetite and hematite-bearing ores. The different approaches demonstrate advantages and disadvantages in classification, imaging, discrimination of iron oxides, and time consumption of measurement and processing. The obtained precise mineralogical information improves the characterization of ore types and will benefit future processing strategies for this complex mineralization

Acidified water glass in the selective flotation of scheelite from calcite, part II: species in solution and related mechanism of the depressant

Sodium silicate is one of the main depressants against calcite and fluorite in the scheelite flotation industry. In the first part of this article, the authors acidified sodium silicate (AWG) with three acids (sulfuric, oxalic and hydrochloric) to improve its performance. Results showed that acidified water glass outperforms alkaline water glass in terms of selectivity: it increases mainly the grade by further depressing silicates and calcium-bearing minerals. In most cases, AWG requires lower dosages to do so. The effect of acidified water glass is evaluated through Mineral Liberation Analysis (MLA), froth analysis, Raman and Nuclear Magnetic Resonance (NMR) spectroscopy in order to hypothesize its mechanism. MLA shows that AWG affects silicates and sulfides more intensely than semi-soluble salttype minerals. Froth observations indicate other species in solution associated to the acid having an impact on the flotation results. Raman spectroscopy and NMR measurements indicate that the solution undergoes deep depolymerization when water glass is acidified. Lower molecular weight silica species, specifically Si-O monomers such as SiO(OH)3- will be responsible for the depression of the gangue minerals and are the drivers of the selectivity of AWG, more than orthosilicic acid. Depolymerization is more or less effective depending on the mass ratio of the acid to water glass and depending on the acid

Insight into the Supramolecular Architecture of Intact Diatom Biosilica from DNP-Supported Solid-State NMR Spectroscopy

Diatom biosilica is an inorganic/organic hybrid with interesting properties. The molecular architecture of the organic material at the atomic and nanometer scale has so far remained unknown, in particular for intact biosilica. A DNP-supported ssNMR approach assisted by microscopy, MS, and MD simulations was applied to study the structural organization of intact biosilica. For the first time, the secondary structure elements of tightly biosilica-associated native proteins in diatom biosilica were characterized in situ. Our data suggest that these proteins are rich in a limited set of amino acids and adopt a mixture of random-coil and β-strand conformations. Furthermore, biosilica-associated long-chain polyamines and carbohydrates were characterized, thereby leading to a model for the supramolecular organization of intact biosilica

Mesocrystalline Architecture in Hyaline Foraminifer Shells Indicates a Non-Classical Crystallisation Pathway

Calcareous foraminifer shells (tests) represent one of the most important archives for paleoenvironmental and paleoclimatic reconstruction. To develop a mechanistic understanding of the relationship between environmental parameters and proxy signals, knowledge of the fundamental processes operating during foraminiferal biomineralization is essential. Here, we apply microscopic and diffraction-based methods to address the crystallographic and hierarchical structure of the test wall of different hyaline foraminifer species. Our results show that the tests are constructed from micrometer-scale oriented mesocrystals built of nanometer-scale entities. Based on these observations, we propose a mechanistic extension to the biomineralization model for hyaline foraminifers, centered on the formation and assembly of units of metastable carbonate phases to the final mesocrystal via a non-classical particle attachment process, possibly facilitated by organic matter. This implies the presence of metastable precursors such as vaterite or amorphous calcium carbonate, along with phase transitions to calcite, which is relevant for the mechanistic understanding of proxy incorporation in the hyaline foraminifers.ISSN:1525-202