Macroporous inorganic solids from a biomineral template

Yue, Wenbo; Park, Robert J.; Kulak, Alex N.; Meldrum, Fiona C.

doi:10.1016/j.jcrysgro.2006.05.028

Cited by 48 publications

(51 citation statements)

References 46 publications

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“…4,56 A perfect example of a process which occurs in confinement is biomineralization. 7,8 Despite this, with the exception of control over morphology, [9][10][11][12] the effects of confinement on the formation of biominerals, or indeed inorganic substances has received little attention, possibly partly due to the experimental challenges associated with carrying out systematic studies of the precipitation of poorly soluble compounds in small volumes. Recent work has provided strong evidence, however, that confinement can also have significant effects on the precipitation of compounds such as calcium carbonate 13 and calcium sulfate, sometimes at surprisingly large length scales.…”

Section: Introductionmentioning

confidence: 99%

Confinement Increases the Lifetimes of Hydroxyapatite Precursors

2014

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The mineral component of bone is a carbonated, non-stoichiometric hydroxyapatite (calcium phosphate) that forms in nanometer confinement within collagen fibrils, the principal organic constituent of bone. We here employ a model system to study the effect of confinement on hydroxyapatite precipitation from solution under physiological conditions. In common with earlier studies of calcium carbonate and calcium sulfate precipitation, we find that confinement significantly prolongs the lifetime of metastable phases, here amorphous calcium phosphate (ACP) and octacalcium phosphate (OCP). The effect occurs at surprisingly large separations of up to 1 m, and at 0.2 m the lifetime of ACP is extended by at least an order of magnitude. The soluble additive poly(aspartic acid), which in bulk stabilizes ACP, appears to act synergistically with confinement to give a greatly enhanced stability of ACP. The reason for the extended lifetime appears to be different from that found with CaCO 3 and CaSO 4 , and underscores both the variety of mechanisms whereby 2 confinement affects the growth and transformation of solid phases, and the necessity to study a wide range of crystalline systems to build a full understanding of confinement effects. We suggest that in the case of ACP and OCP the extended lifetime of these metastable phases is chiefly due to a slower transport of ions between a dissolving metastable phase, and the more stable, growing phase. These results highlight the potential importance of confinement on biomineralisation processes.3

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Section: Introductionmentioning

confidence: 99%

Confinement Increases the Lifetimes of Hydroxyapatite Precursors

2014

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“…1,2 Soluble additives can be particularly effective in defining crystal sizes, morphologies and polymorphs, 3 delivering for example, crystalline particles with complex hierarchical structures. [4][5][6][7][8] The encapsulation of additives within the crystal lattice can also change the textures, 9 mechanical properties, [10][11][12] and optical properties 13,14 of crystals. As an alternative to additive-directed crystallization, it is also becoming increasingly evident that the micro-environments in which crystals form can themselves define crystallization pathways and products.…”

Section: Introductionmentioning

confidence: 99%

“…18,20,21 Looking then at biologically-relevant solids such as calcium carbonate and calcium sulfate, confined volumes can provide environments that can control the formation of single crystals with complex morphologies. 7,[22][23][24] Using systems including a crossedcylinders apparatus, 19,25,26 arrays of picolitre droplets, 27 vesicles that offer confinement in the general range 50 nm -50 m, [28][29][30] and the pores of track-etched membranes, [31][32][33] it has also been demonstrated that the lifetimes of amorphous precursor phases and metastable crystalline polymorphs of calcium carbonate, calcium phosphate, calcium sulfate and calcium oxalate can be significantly extended, even in micron-scale environments. While this length scale is relevant to many biomineralization processes, crystallization in the environment (eg.…”

Section: Introductionmentioning

confidence: 99%

Effect of Nanoscale Confinement on the Crystallization of Potassium Ferrocyanide

Anduix‐Canto

Kim

Wang

et al. 2016

Crystal Growth & Design

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Many crystallization processes of great significance in nature and technology occur in small volumes rather than in bulk solution. This article describes an investigation into the effects of nanoscale confinement on the crystallization of the inorganic compound potassium ferrocyanide, K4Fe(CN)6 (KFC). Selected for study due to its high solubility, rich polymorphism and interesting physical properties, K4Fe(CN)6 was precipitated within controlled pore glasses (CPG) with pore diameters of 8, 48 and 362 nm. Remarkable effects were seen, such that although anhydrous potassium ferrocyanide was never observed on precipitation in bulk aqueous solution, it was the first phase to crystallize within the CPGs and was present for at least 1 day in all three pore sizes. Slow transformation to the metastable tetragonal polymorph of the trihydrate K4Fe(CN)6•3H2O (KFCT) then occurred, where this polymorph was stable for a month in 8 nm pores. Finally, conversion to the thermodynamically stable monoclinic polymorph of KFCT was observed, where this phase always found after a few minutes in bulk solution. As far as we are aware these retardation effects -by up to five orders of magnitude in the 8 nm pores -are far greater than any seen previously in inorganic systems, and provide strong evidence for the universal effects of confinement on crystallization.

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“…Thus, the materials will have promising prospects for industrial processes involving catalysis, adsorption, separation, chemical sensing, storage of fluids and gases in transportation [2][3][4], and enzyme immobilization [5]. Generally, hierarchical porous materials have been prepared by multiple template methods, including hard templates for macropores [6][7][8][9][10][11][12][13], and soft templates for preparation of meso-/micro-pores [14]. Constructing novel hierarchically porous materials with natural biological templates is an brand-new field.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of hierarchically porous bioactive glasses using natural plants as template for bone tissue regeneration

et al. 2012

J Sol-Gel Sci Technol

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A series of highly ordered hierarchically porous silica and bio-glasses materials with macropore size of 8-1,000 lm and mesopore size of 3.1-5.6 nm have been synthesized using six plant based materials as templates. However, the as-obtained porous structure was reported for the first time with interconnected 3D macropore up to 1,000 lm. The porous silica materials were used as the host for drug loading and release, which showed a good sustained delivery function. The as-synthesized bio-glasses materials indicated the highly bioactive capability in the bone regeneration. This method can be utilized to synthesize other multi-porous bioactive glasses using different plants as templates for bone tissue repairing.

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Macroporous inorganic solids from a biomineral template

Cited by 48 publications

References 46 publications

Confinement Increases the Lifetimes of Hydroxyapatite Precursors

Confinement Increases the Lifetimes of Hydroxyapatite Precursors

Effect of Nanoscale Confinement on the Crystallization of Potassium Ferrocyanide

Synthesis of hierarchically porous bioactive glasses using natural plants as template for bone tissue regeneration

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