Effect of Nanoscale Confinement on the Crystallization of Potassium Ferrocyanide

Anduix‐Canto, Clara; Kim, Yi‐Yeoun; Wang, Yunwei; Kulak, Alexander N.; Meldrum, Fiona C.; Christenson, Hugo K.

doi:10.1021/acs.cgd.6b00894

Cited by 22 publications

(23 citation statements)

References 61 publications

(174 reference statements)

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“… is the molecular volume in m 3 mol -1 , and R is the gas constant. With a strong wettability of the nucleus or chemical affinity toward the confining walls, the nucleus would have concave edges 56 , 57 . Then, the Kelvin equation reads for negative curvature − r .…”

Section: Resultsmentioning

confidence: 99%

The role of confined collagen geometry in decreasing nucleation energy barriers to intrafibrillar mineralization

et al. 2018

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Mineralization of collagen is critical for the mechanical functions of bones and teeth. Calcium phosphate nucleation in collagenous structures follows distinctly different patterns in highly confined gap regions (nanoscale confinement) than in less confined extrafibrillar spaces (microscale confinement). Although the mechanism(s) driving these differences are still largely unknown, differences in the free energy for nucleation may explain these two mineralization behaviors. Here, we report on experimentally obtained nucleation energy barriers to intra- and extrafibrillar mineralization, using in situ X-ray scattering observations and classical nucleation theory. Polyaspartic acid, an extrafibrillar nucleation inhibitor, increases interfacial energies between nuclei and mineralization fluids. In contrast, the confined gap spaces inside collagen fibrils lower the energy barrier by reducing the reactive surface area of nuclei, decreasing the surface energy penalty. The confined gap geometry, therefore, guides the two-dimensional morphology and structure of bioapatite and changes the nucleation pathway by reducing the total energy barrier.

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Section: Resultsmentioning

confidence: 99%

The role of confined collagen geometry in decreasing nucleation energy barriers to intrafibrillar mineralization

et al. 2018

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“…Anhydrous KFC, which was never observed on precipitation in bulk aqueous solution, was the first phase to crystallize within the CPGs and was present for at least 1 day in 8, 48, and 362 nm pores. [ 301 ] Slow transformation to the metastable tetragonal polymorph of KFCT then occurred, where this polymorph was stable for a month in 8 nm pores. Finally, this converted to the thermodynamically stable monoclinic polymorph.…”

Section: Nanoscale Cylindrical Poresmentioning

confidence: 99%

Crystallization in Confinement

2020

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Many crystallization processes of great importance, including frost heave, biomineralization, the synthesis of nanomaterials, and scale formation, occur in small volumes rather than bulk solution. Here, the influence of confinement on crystallization processes is described, drawing together information from fields as diverse as bioinspired mineralization, templating, pharmaceuticals, colloidal crystallization, and geochemistry. Experiments are principally conducted within confining systems that offer well‐defined environments, varying from droplets in microfluidic devices, to cylindrical pores in filtration membranes, to nanoporous glasses and carbon nanotubes. Dramatic effects are observed, including a stabilization of metastable polymorphs, a depression of freezing points, and the formation of crystals with preferred orientations, modified morphologies, and even structures not seen in bulk. Confinement is also shown to influence crystallization processes over length scales ranging from the atomic to hundreds of micrometers, and to originate from a wide range of mechanisms. The development of an enhanced understanding of the influence of confinement on crystal nucleation and growth will not only provide superior insight into crystallization processes in many real‐world environments, but will also enable this phenomenon to be used to control crystallization in applications including nanomaterial synthesis, heavy metal remediation, and the prevention of weathering.

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“…This conclusively demonstrates that the high stability of bassanite within the CPGs therefore principally derives from confinement effects, as seen in many other systems. [7,13,14]…”

Section: Origin Of the Extended Stability Of Bassanitementioning

confidence: 99%

“…In situ synchrotron X-ray micro-computed tomography (µ-CT) and X-ray diffraction computed tomography (XRDCT) [12] can then be used to follow their spatial and structural development in 3D, where the extreme confinement offered by these environments significantly retards crystallization, such that intermediate phases that are short-lived and potentially overlooked in bulk solution are readily observed. [7,[13][14][15] Notably, the CPG rods exhibit uniform, low X-ray absorption, such that images of the developing particles can be recorded with exceptional definition. This system also offers a unique opportunity to study crystallization within porous media, where many important processes including weathering and frost heave, [16][17][18] the templating of inorganic nanostructures, [19] and biomineralization [20,21] arise from crystallization within porous media such as rocks, polymers or gels.…”

Section: Introductionmentioning

confidence: 99%

Exploiting Confinement to Study the Crystallization Pathway of Calcium Sulfate

Anduix‐Canto

Levenstein

Kim

et al. 2021

Adv Funct Materials

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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 (CaSO 4 0.5H 2 O) forms via an amorphous precursor phase and that it exhibits long-term stability in these nanoscale pores. Further, the thermodynamically stable phase gypsum (CaSO 4 2H 2 O) 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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Effect of Nanoscale Confinement on the Crystallization of Potassium Ferrocyanide

Cited by 22 publications

References 61 publications

The role of confined collagen geometry in decreasing nucleation energy barriers to intrafibrillar mineralization

The role of confined collagen geometry in decreasing nucleation energy barriers to intrafibrillar mineralization

Crystallization in Confinement

Exploiting Confinement to Study the Crystallization Pathway of Calcium Sulfate

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