307 research outputs found
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Biomolecular Modification of Inorganic Crystal Growth
The fascinating shapes and hierarchical designs of biomineralized structures are an inspiration to materials scientists because of the potential they suggest for biomolecular control over materials synthesis. Conversely, the failure to prevent or limit tissue mineralization in the vascular, skeletal, and urinary systems is a common source of disease. Understanding the mechanisms by which organisms direct or limit crystallization has long been a central challenge to the biomineralization community. One prevailing view is that mineral-associated macromolecules are responsible for either inhibiting crystallization or initiating and stabilizing non-equilibrium crystal polymorphs and morphologies through interactions between anionic moieties and cations in solution or at mineralizing surfaces. In particular, biomolecules that present carboxyl groups to the growing crystal have been implicated as primary modulators of growth. Here we review the results from a combination of in situ atomic force microscopy (AFM) and molecular modeling (MM) studies to investigate the effect of specific interactions between carboxylate-rich biomolecules and atomic steps on crystal surfaces during the growth of carbonates, oxalates and phosphates of calcium. Specifically, we how the growth kinetics and morphology depend on the concentration of additives that include citrate, simple amino acids, synthetic Asp-rich polypeptides, and naturally occurring Asp-rich proteins found in both functional and pathological mineral tissues. The results reveal a consistent picture of shape modification in which stereochemical matching of modifiers to specific atomic steps drives shape modification. Inhibition and other changes in growth kinetics are shown to be due to a range of mechanisms that depend on chemistry and molecular size. Some effects are well described by classic crystal growth theories, but others, such as step acceleration due to peptide charge and hydrophylicity, were previously unrealized. Finally, we show that the molecular scale observations are well correlated with macroscopic growth rate data
Structure and Stability of the Iodide Elpasolite, Cs2AgBiI6
Iodide elpasolites (or double perovskites, A2B'B"I6, B' = M+, B" = M3+) are
predicted to be promising alternatives to lead-based perovskite semiconductors
for photovoltaic and optoelectronic applications, but no iodide elpasolite has
ever been definitively prepared or structurally characterized. Iodide
elpasolites are widely predicted to be unstable due to favorable decomposition
to the competing A3B2I9 (B = M3+) phase. Here, we report the results of
synchrotron XRD and X-ray total scattering measurements on putative Cs2AgBiI6
nanocrystals made via anion exchange from parent Cs2AgBiBr6 nanocrystals.
Rietveld refinement of XRD and PDF data shows that these nanocrystals indeed
exhibit a tetragonal (I4-m) elpasolite structure, making them the first example
of a structurally characterized iodide elpasolite. A series of experiments
probing structural relaxation and the effects of surface ligation or grain size
all point to the critical role of surface free energy in stabilizing the iodide
elpasolite phase in these nanocrystals.Comment: 7 figures, 1 scheme, plus supporting information fil
Revisiting geochemical controls on patterns of carbonate deposition through the lens of multiple pathways to mineralization
The carbonate sedimentary record contains diverse compositions and textures that reflect the evolution of oceans and atmospheres through geological time. Efforts to reconstruct paleoenvironmental conditions from these deposits continue to be hindered by the need for process-based models that can explain observed shifts in carbonate chemistry and form. Traditional interpretations assume minerals precipitate and grow by classical ion-by-ion addition processes but are unable to reconcile a number of unusual features contained in Proterozoic carbonates. The realization that diverse organisms produce high Mg carbonate skeletal structures by non-classical pathways involving amorphous intermediates raises the question of whether similar processes are also active in sedimentary environments. This study examines the hypothesis that non-classical pathways to mineralization are the physical basis for some of the carbonate morphologies and compositions observed in natural and laboratory settings. We designed experiments with a series of different solution Mg : Ca ratios and saturation environments to investigate the effects on carbonate phase, Mg content, and morphology. Our observations of diverse carbonate mineral compositions and textures suggest geochemical conditions bias the mineralization pathway by a systematic relationship to Mg : Ca ratio and the abundance of carbonate ions. Environments with low Mg levels produce calcite crystallites with 0–12 mol% MgCO_3. In contrast, the combination of high initial Mg : Ca and rapidly increasing saturation opens a non-classical pathway that begins with extensive precipitation of an amorphous calcium carbonate (ACC). This phase slowly transforms to aggregates of very high Mg calcite nanoparticles whose structures and compositions are similar to natural disordered dolomites. The non-classical pathways are favored when the local environment contains sufficient Mg to inhibit calcite growth through increased solubility—a thermodynamic factor, and achieves saturation with respect to ACC on a timescale that is shorter than the rate of aragonite nucleation—a kinetic factor. Aragonite is produced when Mg levels are high but saturation is insufficient for ACC precipitation. The findings provide a physical basis for anecdotal claims that the interplay of kinetic and thermodynamic factors underlies patterns of carbonate precipitation and suggest the need to expand traditional interpretations of geological carbonate formation to include non-classical pathways to mineralization
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Fluctuations and Gibbs-Thomson Law - the Simple Physics.
Crystals of slightly soluble materials should be subject of relatively weak attachment/detachment fluctuations on their faces so that steps on that faces have low kink density. These steps are parallel to the most close packed lattice rows and form polygons on a crystal surface. The process responsible for implementation of the classical Gibbs-Thomson law (GTL) for the polygonal step (in two dimensions, 2D) is kink exchange between the step corners. For the 3D crystallites, this mechanism includes step exchange. If these mechanisms do not operate because of slow fluctuations the GTL is not applicable. Physics of these processes and conditions for the GTL applicability are discussed on a simple qualitative level
Microscopic evidence for liquid-liquid separation in supersaturated CaCO3 solutions
Recent experimental observations of the onset of calcium carbonate (CaCO3) mineralization suggest the emergence of a population of clusters that are stable rather than unstable as predicted by classical nucleation theory. This study uses molecular dynamics simulations to probe the structure, dynamics, and energetics of hydrated CaCO3 clusters and lattice gas simulations to explore the behavior of cluster populations before nucleation. Our results predict formation of a dense liquid phase through liquid-liquid separation within the concentration range in which clusters are observed. Coalescence and solidification of nanoscale droplets results in formation of a solid phase, the structure of which is consistent with amorphous CaCO3. The presence of a liquid-liquid binodal enables a diverse set of experimental observations to be reconciled within the context of established phase-separation mechanisms
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The Effect of Ring Substitution Position on the Structural Conformation of Mercaptobenzoic Acid Self-Assembled Monolayers on Au(111)
Near edge X-ray absorption fine structure (NEX-AFS) spectroscopy, photoemission spectroscopy (PES) and contact angle measurements have been used to examine the structure and bonding of self-assembled monolayers (SAMs) prepared on Au(111) from the positional isomers of mercaptobenzoic acid (MBA). The isomer of MBA and solvent chosen in SAM preparation has considerable bearing upon film morphology. Carbon K-edge NEXAFS measurements indicate that the monomers of 2-, 3- and 4-MBA have well-defined orientations within their respective SAMs. Monomers of 3- and 4-MBA assume an upright orientation on the Au substrates in monolayers prepared using an acetic acid in ethanol solvent. The aryl ring and carboxyl group of these molecules are tilted from the surface normal by a colatitudal angle of {approx} 30{sup o}. Preparation of 4-MBA SAMs using pure ethanol solvent, a more traditional means of synthesis, had no appreciable effect upon the monomer orientation. Nonetheless, S(2p) PES measurements illustrate that it results in extensive bilayer formation via carboxyl group hydrogen-bonding between 4-MBA monomers. In 2-MBA monolayers prepared using acetic acid/ethanol solvent, the monomers adopt a more prostrate orientation on the Au substrates, in which the aryl ring and carboxyl group of the molecules are tilted {approx} 50{sup o} from the surface normal. This configuration is consistent with an interaction between both the mercaptan sulfur and carboxyl group of 2-MBA with the underlying substrate. S(2p) and C(1s) PES experiments provide supporting evidence for a bidentate interaction between 2-MBA and Au(111)
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Observation of photoexcited emission clusters in the bulk of KDP and laser conditioning under 355-nm irradiation
Defect clusters in the bulk of large KDP crystals are revealed using a microscopic fluorescence imaging system and CW laser illumination. Exposure of the crystal to high power 355-nm, 3-ns laser irradiation leads to a significant reduction of the number of observed optically active centers. The initially observed defect cluster concentration is approximately 104-106 per mm3 depending on the crystal growth method and sector of the crystal. The number of defect clusters can be reduced by a factor of 102 or more under exposure to 355-nm laser irradiation while their average intensities also decreases. Spectroscopic measurements provide information on the electronic structure of the defects
A classical view on nonclassical nucleation
Understanding and controlling nucleation is important for many crystallization applications. Calcium carbonate (CaCO_{3}) is often used as a model system to investigate nucleation mechanisms. Despite its great importance in geology, biology, and many industrial applications, CaCO_{3} nucleation is still a topic of intense discussion, with new pathways for its growth from ions in solution proposed in recent years. These new pathways include the so-called nonclassical nucleation mechanism via the assembly of thermodynamically stable prenucleation clusters, as well as the formation of a dense liquid precursor phase via liquid–liquid phase separation. Here, we present results from a combined experimental and computational investigation on the precipitation of CaCO_{3} in dilute aqueous solutions. We propose that a dense liquid phase (containing 4–7 H_{2}O per CaCO_{3} unit) forms in supersaturated solutions through the association of ions and ion pairs without significant participation of larger ion clusters. This liquid acts as the precursor for the formation of solid CaCO_{3} in the form of vaterite, which grows via a net transfer of ions from solution according to z Ca^{2+} + zCO_{3}^{2−} → z CaCO_{3}. The results show that all steps in this process can be explained according to classical concepts of crystal nucleation and growth, and that long-standing physical concepts of nucleation can describe multistep, multiphase growth mechanisms
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Scatter Loss From Environmental Degradation of KDP Crystals
Severe scattering losses from KDP crystals have been correlated with the exposure of porous sol AR coated crystals to ambient humidity. The scattering is attributed to formation of etch pits which develop under the coating on the KDP surface along crystallographic axes. This high angle scattering can in turn produce laser damage of downstream optics either through modulation of the beam or by optic contamination from ablation of adjacent metal structures. We have developed a simple tool to characterize the evolution of scatter from sol-coated KDP surfaces. We have measured the rate of etch pit formation as a function of relative humidity and surface treatment using both microscopy and scattering. We will discuss various surface treatments which can be utilized to retard or eliminate the environmental degradation of KDP crystals
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