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.
28 October 2015 in Angewandte Chemie International Edition
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.