I13-2-Diamond Manchester Imaging
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Clara
Anduix-Canto
,
Mark A.
Levenstein
,
Yi-Yeoun
Kim
,
Jose R. A.
Godinho
,
Alexander N.
Kulak
,
Carlos
Gonzalez Nino
,
Philip J.
Withers
,
Jonathan P.
Wright
,
Nikil
Kapur
,
Hugo K.
Christenson
,
Fiona C.
Meldrum
Diamond Proposal Number(s):
[13578, 17314]
Open Access
Abstract: Characterizing the pathways by which crystals form remains a significant challenge, particularly when multiple pathways operate simultaneously. Here, an imaging-based strategy is introduced that exploits confinement effects to track the evolution of a population of crystals in 3D and to characterize crystallization pathways. Focusing on calcium sulfate formation in aqueous solution at room temperature, precipitation is carried out within nanoporous media, which ensures that the crystals are fixed in position and develop slowly. The evolution of their size, shape, and polymorph can then be tracked in situ using synchrotron X-ray computed tomography and diffraction computed tomography without isolating and potentially altering the crystals. The study shows that bassanite (CaSO4 0.5H2O) forms via an amorphous precursor phase and that it exhibits long-term stability in these nanoscale pores. Further, the thermodynamically stable phase gypsum (CaSO4 2H2O) can precipitate by different pathways according to the local physical environment. Insight into crystallization in nanoconfinement is also gained, and the crystals are seen to grow throughout the nanoporous network without causing structural damage. This work therefore offers a novel strategy for studying crystallization pathways and demonstrates the significant impact of confinement on calcium sulfate precipitation, which is relevant to its formation in many real-world environments.
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Sep 2021
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I11-High Resolution Powder Diffraction
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Mark A.
Levenstein
,
Yi-Yeoun
Kim
,
Liam
Hunter
,
Clara
Anduix-Canto
,
Carlos
Gonzalez Nino
,
Sarah J.
Day
,
Shunbo
Li
,
William J.
Marchant
,
Phillip A.
Lee
,
Chiu C.
Tang
,
Manfred
Burghammer
,
Fiona C.
Meldrum
,
Nikil
Kapur
Diamond Proposal Number(s):
[10425, 12352]
Open Access
Abstract: The clean and reproducible conditions provided by microfluidic devices are ideal sample environments for in situ analyses of chemical and biochemical reactions and assembly processes. However, the small size of microchannels makes investigating the crystallization of poorly soluble materials on-chip challenging due to crystal nucleation and growth that result in channel fouling and blockage. Here, we demonstrate a reusable insert-based microfluidic platform for serial X-ray diffraction analysis and examine scale formation in response to continuous and segmented flow configurations across a range of temperatures. Under continuous flow, scale formation on the reactor walls begins almost immediately on mixing of the crystallizing species, which over time results in occlusion of the channel. Depletion of ions at the start of the channel results in reduced crystallization towards the end of the channel. Conversely, segmented flow can control crystallization, so it occurs entirely within the droplet. Consequently, the spatial location within the channel represents a temporal point in the crystallization process. Whilst each method can provide useful crystallographic information, time-resolved information is lost when reactor fouling occurs and changes the solution conditions with time. The flow within a single device can be manipulated to give a broad range of information addressing surface interaction or solution crystallization.
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Jul 2020
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I22-Small angle scattering & Diffraction
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Open Access
Abstract: This work shows that highly uniform worm micelles formed by polymerisation induced self-assembly can be obtained via simple post-synthesis sonication. Importantly, this straightforward and versatile strategy yields exceptionally monodisperse worms with tunable aspect ratios ranging from 7.2 to 17.6 by simply changing the sonication time.
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May 2020
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I11-High Resolution Powder Diffraction
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Yi-Yeoun
Kim
,
Robert
Darkins
,
Alexander
Broad
,
Alexander N.
Kulak
,
Mark A.
Holden
,
Ouassef
Nahi
,
Steven P.
Armes
,
Chiu C.
Tang
,
Rebecca F.
Thompson
,
Frederic
Marin
,
Dorothy M.
Duffy
,
Fiona C.
Meldrum
Open Access
Abstract: Acidic macromolecules are traditionally considered key to calcium carbonate biomineralisation and have long been first choice in the bio-inspired synthesis of crystalline materials. Here, we challenge this view and demonstrate that low-charge macromolecules can vastly outperform their acidic counterparts in the synthesis of nanocomposites. Using gold nanoparticles functionalised with low charge, hydroxyl-rich proteins and homopolymers as growth additives, we show that extremely high concentrations of nanoparticles can be incorporated within calcite single crystals, while maintaining the continuity of the lattice and the original rhombohedral morphologies of the crystals. The nanoparticles are perfectly dispersed within the host crystal and at high concentrations are so closely apposed that they exhibit plasmon coupling and induce an unexpected contraction of the crystal lattice. The versatility of this strategy is then demonstrated by extension to alternative host crystals. This simple and scalable occlusion approach opens the door to a novel class of single crystal nanocomposites.
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Dec 2019
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I11-High Resolution Powder Diffraction
I22-Small angle scattering & Diffraction
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Mark A.
Levenstein
,
Clara
Anduix-Canto
,
Yi-Yeoun
Kim
,
Mark A.
Holden
,
Carlos
Gonzalez Nino
,
David C.
Green
,
Stephanie E.
Foster
,
Alexander N.
Kulak
,
Lata
Govada
,
Naomi E.
Chayen
,
Sarah J.
Day
,
Chiu C.
Tang
,
Britta
Weinhausen
,
Manfred
Burghammer
,
Nikil
Kapur
,
Fiona C.
Meldrum
Diamond Proposal Number(s):
[10425, 12352, 17729]
Abstract: The ability to control crystallization reactions is required in a vast range of processes including the production of functional inorganic materials and pharmaceuticals and the prevention of scale. However, it is currently limited by a lack of understanding of the mechanisms underlying crystal nucleation and growth. To address this challenge, it is necessary to carry out crystallization reactions in well‐defined environments, and ideally to perform in situ measurements. Here, a versatile microfluidic synchrotron‐based technique is presented to meet these demands. Droplet microfluidic‐coupled X‐ray diffraction (DMC‐XRD) enables the collection of time‐resolved, serial diffraction patterns from a stream of flowing droplets containing growing crystals. The droplets offer reproducible reaction environments, and radiation damage is effectively eliminated by the short residence time of each droplet in the beam. DMC‐XRD is then used to identify effective particulate nucleating agents for calcium carbonate and to study their influence on the crystallization pathway. Bioactive glasses and a model material for mineral dust are shown to significantly lower the induction time, highlighting the importance of both surface chemistry and topography on the nucleating efficiency of a surface. This technology is also extremely versatile, and could be used to study dynamic reactions with a wide range of synchrotron‐based techniques.
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Mar 2019
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I13-1-Coherence
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Diamond Proposal Number(s):
[7654, 7277]
Open Access
Abstract: Soluble additives provide a versatile strategy for controlling crystallization processes, enabling selection of properties including crystal sizes, morphologies, and structures. The additive species can also be incorporated within the crystal lattice, leading for example to enhanced mechanical properties. However, while many techniques are available for analyzing particle shape and structure, it remains challenging to characterize the structural inhomogeneities and defects introduced into individual crystals by these additives, where these govern many important material properties. Here, we exploit Bragg coherent diffraction imaging to visualize the effects of soluble additives on the internal structures of individual crystals on the nanoscale. Investigation of bio-inspired calcite crystals grown in the presence of lysine or magnesium ions reveals that while a single dislocation is observed in calcite crystals grown in the presence of lysine, magnesium ions generate complex strain patterns. Indeed, in addition to the expected homogeneous solid solution of Mg ions in the calcite lattice, we observe two zones comprising alternating lattice contractions and relaxation, where comparable alternating layers of high magnesium calcite have been observed in many magnesium calcite biominerals. Such insight into the structures of nanocomposite crystals will ultimately enable us to understand and control their properties.
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Nov 2018
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B16-Test Beamline
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Diamond Proposal Number(s):
[14790]
Abstract: The topic of calcite and aragonite polymorphism attracts enormous interest from fields including biomineralization and paleogeochemistry. While aragonite is only slightly less thermodynamically stable than calcite under ambient conditions, it typically only forms as a minor product in additive-free solutions at room temperature. However, aragonite is an abundant biomineral, and certain organisms can selectively generate calcite and aragonite. This fascinating behavior has been the focus of decades of research, where this has been driven by a search for specific organic macromolecules that can generate these polymorphs. However, despite these efforts, we still have a poor understanding of how organisms achieve such selectivity. In this work, we consider an alternative possibility and explore whether the confined volumes in which all biomineralization occurs could also influence polymorph. Calcium carbonate was precipitated within the cylindrical pores of track-etched membranes, where these enabled us to systematically investigate the relationship between the membrane pore diameter and polymorph formation. Aragonite was obtained in increasing quantities as the pore size was reduced, such that oriented single crystals of aragonite were the sole product from additive-free solutions in 25-nm pores and significant quantities of aragonite formed in pores as large as 200 nm in the presence of low concentrations of magnesium and sulfate ions. This effect can be attributed to the effect of the pore size on the ion distribution, which becomes of increasing importance in small pores. These intriguing results suggest that organisms may exploit confinement effects to gain control over crystal polymorph.
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Jul 2018
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I11-High Resolution Powder Diffraction
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Bartosz
Marzec
,
David C.
Green
,
Mark A.
Holden
,
Alexander S.
Coté
,
Johannes
Ihli
,
Saba
Khalid
,
Alexander
Kulak
,
Daniel
Walker
,
Chiu
Tang
,
Dorothy M.
Duffy
,
Yi-Yeoun
Kim
,
Fiona C.
Meldrum
Diamond Proposal Number(s):
[10137]
Open Access
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.
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Jun 2018
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I11-High Resolution Powder Diffraction
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David C.
Green
,
Johannes
Ihli
,
Paul D.
Thornton
,
Mark A.
Holden
,
Bartosz
Marzec
,
Yi-Yeoun
Kim
,
Alex N.
Kulak
,
Mark A.
Levenstein
,
Chiu
Tang
,
Christophe
Lynch
,
Stephen E. D.
Webb
,
Christopher J.
Tynan
,
Fiona C.
Meldrum
Diamond Proposal Number(s):
[10137]
Open Access
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.
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Nov 2016
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I11-High Resolution Powder Diffraction
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Yi-Yeoun
Kim
,
Joseph D.
Carloni
,
Beatrice
Demarchi
,
David
Sparks
,
David G.
Reid
,
Miki. E.
Kunitake
,
Chiu
Tang
,
Melinda J.
Duer
,
Colin L.
Freeman
,
Boaz
Pokroy
,
Kirsty
Penkman
,
John H.
Harding
,
Lara A.
Estroff
,
Shefford P.
Baker
,
Fiona
Meldrum
Diamond Proposal Number(s):
[10137]
Abstract: Structural biominerals are inorganic/organic composites that exhibit remarkable mechanical properties. However, the structure–property relationships of even the simplest building unit—mineral single crystals containing embedded macromolecules—remain poorly understood. Here, by means of a model biomineral made from calcite single crystals containing glycine (0–7 mol%) or aspartic acid (0–4 mol%), we elucidate the origin of the superior hardness of biogenic calcite. We analysed lattice distortions in these model crystals by using X-ray diffraction and molecular dynamics simulations, and by means of solid-state nuclear magnetic resonance show that the amino acids are incorporated as individual molecules. We also demonstrate that nanoindentation hardness increased with amino acid content, reaching values equivalent to their biogenic counterparts. A dislocation pinning model reveals that the enhanced hardness is determined by the force required to cut covalent bonds in the molecules.
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May 2016
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