title: 3D visualization of additive occlusion and tunable full-spectrum fluorescence in calcite.
abstract: From biomineralization to synthesis, organic additives provide an effective means of controlling crystallization processes. There is growing evidence that these additives are often occluded within the crystal lattice. This promises an elegant means of creating nanocomposites and tuning physical properties. Here we use the incorporation of sulfonated fluorescent dyes to gain new understanding of additive occlusion in calcite (CaCO3), and to link morphological changes to occlusion mechanisms. We demonstrate that these additives are incorporated within specific zones, as defined by the growth conditions, and show how occlusion can govern changes in crystal shape. Fluorescence spectroscopy and lifetime imaging microscopy also show that the dyes experience unique local environments within different zones. Our strategy is then extended to simultaneously incorporate mixtures of dyes, whose fluorescence cascade creates calcite nanoparticles that fluoresce white. This offers a simple strategy for generating biocompatible and stable fluorescent nanoparticles whose output can be tuned as required.
authors.affiliation: School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK.
authors.forename: David C
authors.identifier: 0000-0002-0578-2369
authors.initials: DC
authors.lastname: Green
authors.affiliation: School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK.
authors.forename: Johannes
authors.initials: J
authors.lastname: Ihli
authors.affiliation: School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK.
authors.forename: Paul D
authors.initials: PD
authors.lastname: Thornton
authors.affiliation: School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK.|School of Earth and Environment, University of Leeds, Leeds LS2 9JT, UK.
authors.forename: Mark A
authors.initials: MA
authors.lastname: Holden
authors.affiliation: School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK.
authors.forename: Bartosz
authors.initials: B
authors.lastname: Marzec
authors.affiliation: School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK.
authors.forename: Yi-Yeoun
authors.identifier: 0000-0002-8503-4554
authors.initials: YY
authors.lastname: Kim
authors.affiliation: School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK.
authors.forename: Alex N
authors.initials: AN
authors.lastname: Kulak
authors.affiliation: School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK.|School of Mechanical Engineering, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK.
authors.forename: Mark A
authors.identifier: 0000-0002-2309-3743
authors.initials: MA
authors.lastname: Levenstein
authors.affiliation: Diamond Light Source, Harwell Science and Innovation Campus, Didcot OX11 0DE, UK.
authors.forename: Chiu
authors.initials: C
authors.lastname: Tang
authors.affiliation: Central Laser Facility, Science and Technology Facilities Council, Research Complex at Harwell, Rutherford Appleton Laboratory, Didcot OX11 0QX, UK.|London Centre for Nanotechnology, UCL, London WC1H 0AJ, UK.
authors.forename: Christophe
authors.initials: C
authors.lastname: Lynch
authors.affiliation: Central Laser Facility, Science and Technology Facilities Council, Research Complex at Harwell, Rutherford Appleton Laboratory, Didcot OX11 0QX, UK.
authors.forename: Stephen E D
authors.initials: SE
authors.lastname: Webb
authors.affiliation: Central Laser Facility, Science and Technology Facilities Council, Research Complex at Harwell, Rutherford Appleton Laboratory, Didcot OX11 0QX, UK.
authors.forename: Christopher J
authors.initials: CJ
authors.lastname: Tynan
authors.affiliation: School of Chemistry, University of Leeds, Woodhouse Lane, Leeds LS2 9JT, UK.
authors.forename: Fiona C
authors.initials: FC
authors.lastname: Meldrum