Amino Acid Assisted Incorporation of Dye Molecules within Calcite Crystals

Abstract

Biomineralisation processes invariably occur in the presence of multiple organic additives, which act in combination to give exceptional control over structures and properties. However, few synthetic studies have investigated the cooperative effects of soluble additives. This work addresses this challenge and focuses on the combined effects of amino acids and coloured dye molecules. The experiments demonstrate that strongly coloured calcite crystals only form in the presence of Brilliant Blue R (BBR) and four of the seventeen soluble amino acids, as compared with almost colourless crystals using the dye alone. The active amino acids are identified as those which themselves effectively occlude in calcite, suggesting a mechanism where they can act as chaperones for individual molecules or even aggregates of dyes molecules. These results provide new insight into crystal–additive interactions and suggest a novel strategy for generating materials with target properties.

Incorporation of nanogels within calcite single crystals for the storage, protection and controlled release of active compounds

“…71,72 For this purpose, considerable effort has been made to unravel the mechanisms by which additives become incorporated within calcite single crystals. 24,29,[73][74][75] These studies have demonstrated that occlusion is governed by the binding affinity of the additive to the surface of the growing crystal. Efficient occlusion is achieved when an additive binds strongly enough to binding sites on the crystal surface (i.e., kinks and step edges) such that the residence time on the crystal surface exceeds the time taken for steps to propagate around the particles, but not so strongly that crystal growth is inhibited.…”

Ptychographic X-ray tomography reveals additive zoning in nanocomposite single crystals

“…The occlusion of additives ranging from small molecules, 7 , 32 , 53 , 54 to polymers, 34 , 55 , 56 to organic and inorganic nanoparticles, 4 , 5 , 8 , 18 , 22 , 24 , 26 , 28 in single crystals provides a unique strategy for creating new materials with tailor-made properties. However, to fully profit from this approach, it is necessary to control the composition and structure of these nanocomposites.…”

“…Techniques such as confocal fluorescence microscopy or optical microscopy can provide information about the average distribution of fluorescent or colored additives within a crystal, but the resolution is frequently insufficient to identify the locations of individual nano-sized or molecular additives. 31 , 32 Serial sectioning and successive electron microscopy of samples can be carried out to build a tomographic image, but is both destructive and prone to artefacts. 23 While significant advances have been made in electron tomography, 33 , 34 this technique remains limited in the size of sample that can be studied, such that it is difficult to correlate the locations of the occlusions with the morphology of the host crystal.…”

Novel Multifunctional Porous Liquid Composite for Recyclable Sequestration, Storage and In-situ Catalytic Conversion of Carbon Dioxide

“…the characteristic SEM image of PoLi-bCA/CaCl 2 /CO 2 (i.e. after passing CO 2 ), whereby crystals having average dimensions of ≈ 115 × 103 nm and plausibly resembling rhombohedral calcite crystals could be observed [38][39][40][41][42][43]. A significant polydispersity in size was observed with the largest crystal dimensions being ca.…”