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We present a comparison of common electron microscopy sample preparation methods for studying crystallisation processes from solution using both scanning and transmission electron microscopy (SEM and TEM). We focus on two widely studied inorganic systems: calcium sulphate, gypsum (CaSO4·2H2O) and calcium carbonate (CaCO3). We find significant differences in crystallisation kinetics and polymorph selection between the different sample preparation methods, which indicate that drying and chemical quenching can induce severe artefacts that are capable of masking the true native state of the crystallising solution. Overall, these results highlight the importance of cryogenic (cryo)-quenching crystallising solutions and the use of full cryo-TEM as the most reliable method for studying the early stages of crystallisation.
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The nucleation of ice crystals in clouds is poorly understood, despite being of critical importance for our planet's climate. Nucleation occurs largely at rare "active sites" present on airborne particles such as mineral dust, but the nucleation pathway is distinct under different meteorological conditions. These give rise to two key nucleation pathways where a particle is either immersed in a supercooled liquid water droplet (immersion freezing mode) or suspended in a supersaturated vapor (deposition mode). However, it is unclear if the same active sites are responsible for nucleation in these two modes. Here, we directly compare the sites that are active in these two modes by performing immersion freezing and deposition experiments on the same thin sections of two atmospherically important minerals (feldspar and quartz). For both substrates, we confirm that nucleation is dominated by a limited number of sites and show that there is little correlation between the two sets of sites operating in each experimental method: across both materials, only six out of 73 sites active for immersion freezing nucleation were also active for deposition nucleation. Clearly, different properties determine the activity of nucleation sites for each mode, and we use the pore condensation and freezing concept to argue that effective deposition sites have size and/or geometry requirements not of relevance to effective immersion freezing sites. Hence, the ability to nucleate is pathway dependent, and the mode of nucleation has to be explicitly considered when applying experimental data in cloud models.
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Incorporating additives within host single crystals is an effective strategy for producing composite materials with tunable mechanical, magnetic and optical properties. The type of guest materials that can be occluded can be limited, however, as incorporation is a complex process depending on many factors including binding of the additive to the crystal surface, the rate of crystal growth and the stability of the additives in the crystallisation solution. In particular, the size of occluded guests has been restricted to a few angstroms - as for single molecules - to a few hundred nanometers - as for polymer vesicles and particles. Here, we present a synthetic approach for occluding micrometer-scale objects, including high-complexity unicellular organisms and synthetic hollow calcite spheres within calcite single crystals. Both of these objects can transport functional additives, including organic molecules and nanoparticles that would not otherwise occlude within calcite. Therefore, this method constitutes a generic approach using calcite as a delivery system for active compounds, while providing them with effective protection against environmental factors that could cause degradation.
Assuntos
Minerais , Nanopartículas , Carbonato de Cálcio/química , Cristalização , Polímeros/químicaRESUMO
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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Understanding the transitions between polymorphs is essential in the development of strategies for manufacturing and maximizing the efficiency of pharmaceuticals. However, this can be extremely challenging: crystallization can be influenced by subtle changes in environment, such as temperature and mixing intensity or even imperfections in the crystallizer walls. Here, we highlight the importance of in situ measurements in understanding crystallization mechanisms, where a segmented flow crystallizer was used to study the crystallization of the pharmaceuticals urea: barbituric acid (UBA) and carbamazepine (CBZ). The reactor provides highly reproducible reaction conditions, while in situ synchrotron powder X-ray diffraction (PXRD) enables us to monitor the evolution of this system. UBA has two polymorphs of almost equivalent free-energy and so is typically obtained as a polymorphic mixture. In situ PXRD analysis uncovered a progression of polymorphs from UBA III to the thermodynamic polymorph UBA I, where different positions along the length of the tubular flow crystallizer correspond to different reaction times. Addition of UBA I seed crystals modified this pathway such that only UBA I was observed throughout, while transformation from UBA III into UBA I still occurred in the presence of UBA III seeds. Information regarding the mixing-dependent kinetics of the CBZ form II to III transformation was also uncovered in a series of seeded and unseeded flow crystallization runs, despite atypical habit expression. These results illustrate the importance of coupling controlled reaction environments with in situ XRD to study the phase relationships in polymorphic materials.
Assuntos
Barbitúricos/química , Carbamazepina/química , Preparações Farmacêuticas/química , Ureia/química , Cristalização , Difração de PóRESUMO
Heterogeneous nucleation is vital to a wide range of areas as diverse as ice nucleation on atmospheric aerosols and the fabrication of high-performance thin films. There is excellent evidence that surface topography is a key factor in directing crystallization in real systems; however, the mechanisms by which nanoscale pits and pores promote nucleation remain unclear. Here, we use natural cleavage defects on Muscovite mica to investigate the activity of topographical features in the nucleation from vapor of ice and various organic crystals. Direct observation of crystallization within surface pockets using optical microscopy and also interferometry demonstrates that these sharply acute features provide extremely effective nucleation sites and allows us to determine the mechanism by which this occurs. A confined phase is first seen to form along the apex of the wedge and then grows out of the pocket opening to generate a bulk crystal after a threshold saturation has been achieved. Ice nucleation proceeds in a comparable manner, although our resolution is insufficient to directly observe a condensate before the growth of a bulk crystal. These results provide insight into the mechanism of crystal deposition from vapor on real surfaces, where this will ultimately enable us to use topography to control crystal deposition on surfaces. They are also particularly relevant to our understanding of processes such as cirrus cloud formation, where such topographical features are likely candidates for the "active sites" that make clay particles effective nucleants for ice in the atmosphere.
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Nanoparticle occlusion within growing crystals is of considerable interest because (i) it can enhance our understanding of biomineralization and (ii) it offers a straightforward route for the preparation of novel nanocomposites. However, robust design rules for efficient occlusion remain elusive. Herein, we report the rational synthesis of a series of silica-loaded poly(glycerol monomethacrylate)-poly(2-hydroxypropyl methacrylate)-poly(ethylene glycol dimethacrylate)-poly(methacrylic acid) tetrablock copolymer vesicles using polymerization-induced self-assembly. The overall vesicle dimensions remain essentially constant for this series; hence systematic variation of the mean degree of polymerization (DP) of the anionic poly(methacrylic acid) steric stabilizer chains provides an unprecedented opportunity to investigate the design rules for efficient nanoparticle occlusion within host inorganic crystals such as calcite. Indeed, the stabilizer DP plays a decisive role in dictating both the extent of occlusion and the calcite crystal morphology: sufficiently long stabilizer chains are required to achieve extents of vesicle occlusion of up to 41 vol %, but overly long stabilizer chains merely lead to significant changes in the crystal morphology, rather than promoting further occlusion. Furthermore, steric stabilizer chains comprising anionic carboxylate groups lead to superior occlusion performance compared to those composed of phosphate, sulfate, or sulfonate groups. Moreover, occluded vesicles are subjected to substantial deformation forces, as shown by the significant change in shape after their occlusion. It is also demonstrated that such vesicles can act as "Trojan horses", enabling the occlusion of non-functional silica nanoparticles within calcite. In summary, this study provides important new physical insights regarding the efficient incorporation of guest nanoparticles within host inorganic crystals.
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Crystallization is widely used by synthetic chemists as a purification technique because it usually involves the expulsion of impurities. In this context, the efficient occlusion of guest nanoparticles within growing host crystals can be regarded as a formidable technical challenge. Indeed, although there are various reports of successful nanoparticle occlusion within inorganic crystals in the literature, robust design rules remain elusive. Herein, we report the synthesis of two pairs of sterically stabilized diblock copolymer nanoparticles with identical compositions but varying particle size, morphology, stabilizer chain length, and stabilizer chain surface density via polymerization-induced self-assembly (PISA). The mean degree of polymerization of the stabilizer chains dictates the spatial distribution of these model anionic nanoparticles within calcite (CaCO3): relatively short stabilizer chains merely result in near-surface occlusion, whereas sufficiently long stabilizer chains are essential to achieve uniform occlusion. This study reconciles the various conflicting literature reports of occluded nanoparticles being either confined to surface layers or uniformly occluded throughout the host matrix and hence provides important new insights regarding the criteria required for efficient nanoparticle occlusion within inorganic crystals.
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Polymerization-induced self-assembly (PISA) mediated by reversible addition-fragmentation chain transfer (RAFT) polymerization offers a platform technology for the efficient and versatile synthesis of well-defined sterically stabilized block copolymer nanoparticles. Herein we synthesize a series of such nanoparticles with tunable anionic charge density within the stabilizer chains, which are prepared via statistical copolymerization of anionic 2-(phosphonooxy)ethyl methacrylate (P) with non-ionic glycerol monomethacrylate (G). Systematic variation of the P/G molar ratio enables elucidation of the minimum number of phosphate groups per copolymer chain required to promote nanoparticle occlusion within a model inorganic crystal (calcite). Moreover, the extent of nanoparticle occlusion correlates strongly with the phosphate content of the steric stabilizer chains. This study is the first to examine the effect of systemically varying the anionic charge density of nanoparticles on their occlusion efficiency and sheds new light on maximizing the loading of guest nanoparticles within calcite host crystals.
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In principle, incorporating nanoparticles into growing crystals offers an attractive and highly convenient route for the production of a wide range of novel nanocomposites. Herein we describe an efficient aqueous route that enables the spatially controlled occlusion of gold nanoparticles (AuNPs) within ZnO crystals at up to 20 % by mass. Depending on the precise synthesis protocol, these AuNPs can be (i)â solely located within a central region, (ii)â uniformly distributed throughout the ZnO host crystal or (iii)â confined to a surface layer. Remarkably, such efficient occlusion is mediated by a non-ionic water-soluble polymer, poly(glycerol monomethacrylate)70 (G70 ), which is chemically grafted to the AuNPs; pendent cis-diol side groups on this steric stabilizer bind Zn2+ cations, which promotes nanoparticle interaction with the growing ZnO crystals. Finally, uniform occlusion of G70 -AuNPs within this inorganic host leads to faster UV-induced photodegradation of a model dye.
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With their potential to offer new properties, single crystals containing nanoparticles provide an attractive class of nanocomposite materials. However, to fully profit from these, it is essential that we can characterise their 3D structures, identifying the locations of individual nanoparticles, and the defects present within the host crystals. Using calcite crystals containing quantum dots as a model system, we here use 3D stochastic optical reconstruction microscopy (STORM) to locate the positions of the nanoparticles within the host crystal. The nanoparticles are shown to preferentially associate with dislocations in a manner previously recognised for atomic impurities, rendering these defects visible by STORM. Our images also demonstrate that the types of dislocations formed at the crystal/substrate interface vary according to the nucleation face, and dislocation loops are observed that have entirely different geometries to classic misfit dislocations. This approach offers a rapid, easily accessed, and non-destructive method for visualising the dislocations present within crystals, and gives insight into the mechanisms by which additives become occluded within crystals.
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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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Segmented flow microfluidic devices offer an attractive means of studying crystallization processes. However, while they are widely employed for protein crystallization, there are few examples of their use for sparingly soluble compounds due to problems with rapid device fouling and irreproducibility over longer run-times. This article presents a microfluidic device which overcomes these issues, as this is constructed around a novel design of "picoinjector" that facilitates direct injection into flowing droplets. Exploiting a Venturi junction to reduce the pressure within the droplet, it is shown that passive injection of solution from a side-capillary can be achieved in the absence of an applied electric field. The operation of this device is demonstrated for calcium carbonate, where highly reproducible results are obtained over long run-times at high supersaturations. This compares with conventional devices that use a Y-junction to achieve solution loading, where in-channel precipitation of calcium carbonate occurs even at low supersaturations. This work not only opens the door to the use of microfluidics to study the crystallization of low solubility compounds, but the simple design of a passive picoinjector will find wide utility in areas including multistep reactions and investigation of reaction dynamics.
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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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Our understanding of crystal nucleation is a limiting factor in many fields, not least in the atmospheric sciences. It was recently found that feldspar, a component of airborne desert dust, plays a dominant role in triggering ice formation in clouds, but the origin of this effect was unclear. By investigating the structure/property relationships of a wide range of feldspars, we demonstrate that alkali feldspars with certain microtextures, related to phase separation into Na and K-rich regions, show exceptional ice-nucleating abilities in supercooled water. We found no correlation between ice-nucleating efficiency and the crystal structures or the chemical compositions of these active feldspars, which suggests that specific topographical features associated with these microtextures are key in the activity of these feldspars. That topography likely acts to promote ice nucleation, improves our understanding of ice formation in clouds, and may also enable the design and manufacture of bespoke nucleating materials for uses such as cloud seeding and cryopreservation.
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As crystallization processes are often rapid, it can be difficult to monitor their growth mechanisms. In this study, we made use of the fact that crystallization proceeds more slowly in small volumes than in bulk solution to investigate the effects of the soluble additives Mg2+ and poly(styrene sulfonate) (PSS) on the early stages of growth of calcite crystals. Using a "Crystal Hotel" microfluidic device to provide well-defined, nanoliter volumes, we observed that calcite crystals form via an amorphous precursor phase. Surprisingly, the first calcite crystals formed are perfect rhombohedra, and the soluble additives have no influence on the morphology until the crystals reach sizes of 0.1-0.5â µm for Mg2+ and 1-2â µm for PSS. The crystals then continue to grow to develop morphologies characteristic of these additives. These results can be rationalized by considering additive binding to kink sites, which is consistent with crystal growth by a classical mechanism.