Self-similar mesocrystals form via interface-driven nucleation and assembly

Zhu, Guomin; Sushko, Maria L.; Loring, John S.; Legg, Benjamin A.; Song, Miao; Soltis, Jennifer A.; Huang, Xiaopeng; Rosso, Kevin M.; DeYoreo, James J.

doi:10.1038/s41586-021-03300-0

Cited by 105 publications

(123 citation statements)

References 61 publications

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“…S2 and S3) can be found and these large natural crystals of anhydrite AII contain a unique register of nanometers to macroscopic length-scales growth processes taking place over a period of millenia. We used a multitechnique approach to extract the growth history of an anhydrite single crystal from the Naica mine to better understand its internal structure at different length scales and correlate it with the particle-mediated crystallization model of calcium sulfate [22][23][24] .…”

Section: Introductionmentioning

confidence: 99%

Seeds of imperfection rule the mesocrystalline disorder in natural anhydrite single crystals

Stawski

Smales

Scoppola

et al. 2021

Proc. Natl. Acad. Sci. U.S.A.

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In recent years, we have come to appreciate the astounding intricacies associated with the formation of minerals from ions in aqueous solutions. In this context, a number of studies have revealed that the nucleation of calcium sulfate systems occurs nonclassically, involving the aggregation and reorganization of nanosized prenucleation species. In recent work, we have shown that this particle-mediated nucleation pathway is actually imprinted in the resultant micrometer-sized CaSO4 crystals. This property of CaSO4 minerals provides us with the unique opportunity to search for evidence of nonclassical nucleation pathways in geological environments. In particular, we focused on large anhydrite crystals extracted from the Naica Mine in Mexico. We were able to shed light on this mineral's growth history by mapping defects at different length scales. Based on this, we argue that the nanoscale misalignment of the structural subunits, observed in the initial calcium sulfate crystal seeds, propagates through different length scales both in morphological, as well as in strictly crystallographic aspects, eventually causing the formation of large mesostructured single crystals of anhydrite. Hence, the nonclassical nucleation mechanism introduces a “seed of imperfection,” which leads to a macroscopic “single” crystal whose fragments do not fit together at different length scales in a self-similar manner. Consequently, anisotropic voids of various sizes are formed with very well-defined walls/edges. However, at the same time, the material retains in part its single crystal nature.

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Section: Introductionmentioning

confidence: 99%

Seeds of imperfection rule the mesocrystalline disorder in natural anhydrite single crystals

Stawski

Smales

Scoppola

et al. 2021

Proc. Natl. Acad. Sci. U.S.A.

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“…The literature data on iron (oxy)(hydr)oxide nucleation is vast, and the formation of akagenéite, ferrihydrite, maghemite, and hematite has been extensively studied [6,7]. Recently, magnetite crystallization has been described as a colloidal assembly process [8], while the formation of hematite mesocrystals was proposed to proceed via interface-driven nucleation and assembly [9]. The influence of sodium oxalate on the formation of hematite mesocrystals was explained by a change in solution chemistry in the interfacial region of the solid [9].…”

Section: Introductionmentioning

confidence: 99%

“…Recently, magnetite crystallization has been described as a colloidal assembly process [8], while the formation of hematite mesocrystals was proposed to proceed via interface-driven nucleation and assembly [9]. The influence of sodium oxalate on the formation of hematite mesocrystals was explained by a change in solution chemistry in the interfacial region of the solid [9]. However, it is also important to study the changes that occur in the early, that is, the prenucleation stage, in a homogeneous solution, where Fe(III) prenucleation cluster (PNC) species and organic additives interact and may lead to the formation of distinct solids.…”

Section: Introductionmentioning

confidence: 99%

On the Role of Poly-Glutamic Acid in the Early Stages of Iron(III) (Oxy)(hydr)oxide Formation

et al. 2021

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Nucleation of minerals in the presence of additives is critical for achieving control over the formation of solids in biomineralization processes or during syntheses of advanced hybrid materials. Herein, we investigated the early stages of Fe(III) (oxy)(hydr)oxide formation with/without polyglutamic acid (pGlu) at low driving force for phase separation (pH 2.0 to 3.0). We employed an advanced pH-constant titration assay, X-ray diffraction, thermal analysis with mass spectrometry, Fourier Transform infrared spectroscopy, and scanning electron microscopy. Three stages were observed: initial binding, stabilization of Fe(III) pre-nucleation clusters (PNCs), and phase separation, yielding Fe(III) (oxy)(hydr)oxide. The data suggest that organic–inorganic interactions occurred via binding of olation Fe(III) PNC species. Fourier Transform Infrared Spectroscopy (FTIR) analyses revealed a plausible interaction motif and a conformational adaptation of the polypeptide. The stabilization of the aqueous Fe(III) system against nucleation by pGlu contrasts with the previously reported influence of poly-aspartic acid (pAsp). While this is difficult to explain based on classical nucleation theory, alternative notions such as the so-called PNC pathway provide a possible rationale. Developing a nucleation theory that successfully explains and predicts distinct influences for chemically similar additives like pAsp and pGlu is the Holy Grail toward advancing the knowledge of nucleation, early growth, and structure formation.

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“…Recent advances with in situ [ 1–18 ] and cryo‐TEM imaging [ 19–29 ] have enabled a wide range of new experimental capabilities for materials characterization. Conventional methods to refrigerate samples during in situ TEM measurements involve continuous evaporation of liquid nitrogen.…”

Section: Introductionmentioning

confidence: 99%

Hydrothermal Synthesis of Yb³⁺: LuLiF₄ Microcrystals and Laser Refrigeration of Yb³⁺: LuLiF₄/Silicon‐Nitride Composite Nanostructures

Dobretsova

Xia

Pant

et al. 2021

Laser & Photonics Reviews

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The hydrothermal synthesis and characterization of 10%Yb3+:LiLuF4 (LLF) microcrystals are reported. A combination of X‐ray diffraction (XRD) analysis, analytical transmission electron microscopy (TEM), scanning TEM (STEM), energy‐dispersive X‐ray (EDX) spectroscopy), temperature‐dependent Fourier‐transform infrared (FTIR) spectroscopy, and photoluminescence (PL) measurements confirm a scheelite (I41/a) phase and substitutional doping of Yb3+ within the microcrystals. Laser cooling to more than 20 K below room temperature in vacuum (10−3 torr) is demonstrated when irradiating individual microcrystals using a near‐infrared pumping wavelength (λ = 1020nm) at a laser power of 40 mW (irradiance of 0.85 MW cm−2). The use of these microcrystals is further demonstrated for solid‐state laser refrigeration of an electron‐transparent silicon‐nitride (Si3N4) TEM window. A combination of internal luminescence thermometry, heat‐transfer modeling, and control measurements on lithographically patterned Si3N4 optical cavities is used to demonstrate successful bulk laser cooling of Si3N4 TEM windows by ≈15 K below room temperature, opening new opportunities for contactless in situ TEM refrigeration.

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Self-similar mesocrystals form via interface-driven nucleation and assembly

Cited by 105 publications

References 61 publications

Seeds of imperfection rule the mesocrystalline disorder in natural anhydrite single crystals

Seeds of imperfection rule the mesocrystalline disorder in natural anhydrite single crystals

On the Role of Poly-Glutamic Acid in the Early Stages of Iron(III) (Oxy)(hydr)oxide Formation

Hydrothermal Synthesis of Yb³⁺: LuLiF₄ Microcrystals and Laser Refrigeration of Yb³⁺: LuLiF₄/Silicon‐Nitride Composite Nanostructures

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Self-similar mesocrystals form via interface-driven nucleation and assembly

Cited by 105 publications

References 61 publications

Seeds of imperfection rule the mesocrystalline disorder in natural anhydrite single crystals

Seeds of imperfection rule the mesocrystalline disorder in natural anhydrite single crystals

On the Role of Poly-Glutamic Acid in the Early Stages of Iron(III) (Oxy)(hydr)oxide Formation

Hydrothermal Synthesis of Yb3+: LuLiF4 Microcrystals and Laser Refrigeration of Yb3+: LuLiF4/Silicon‐Nitride Composite Nanostructures

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Product

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Hydrothermal Synthesis of Yb³⁺: LuLiF₄ Microcrystals and Laser Refrigeration of Yb³⁺: LuLiF₄/Silicon‐Nitride Composite Nanostructures