Nucleation of Minerals: Precursors, Intermediates and Their Use in Materials Chemistry

Nucleation is the key event in mineralisation, but a general molecular understanding of phase separation mechanisms is still missing, despite more than 100 years of research in this field. In recent years, many studies have highlighted the occurrence of precursors and intermediates, which seem to challenge the assumptions underlying classical theories of nucleation and growth. This is especially true for the field of biomineralisation, where bio-inspired strategies take advantage of the special properties of the precursors and intermediates for the generation of advanced materials. All of this has led to the development of "non-classical" frameworks, which, however, often lack quantitative expressions for the evaluation and prediction of phase separation, growth and ripening processes, and are under considerable debate. It is thus evident that there is a crucial need for research into the early stages of mineral nucleation and growth, designed for the testing, refinement, and expansion of the different existing notions. This Special Issue of Minerals aims to bring together corresponding studies from all these areas, dealing with precursors and intermediates in mineralisation with the hope that it may contribute to the achievement of a better understanding of nucleation precursors and intermediates, and their target-oriented use in materials chemistry

Generality of liquid precursor phases in gas diffusion-based calcium carbonate synthesis

The ammonia diffusion method (ADM) is one of the most widely used strategies for the bioinspired synthesis of minerals. Herein, we present investigations of the mineralization mechanism using an advanced ADM to solve the limitations of the conventional ADM. This allows us to confirm the presence of liquid calcium carbonate precursor species in additive-free and polymer-stabilized gas diffusion systems, indicating that liquid-liquid phase separated species exhibit sufficient kinetic stability to be detected. Time-dependent experiments reveal the role of these precursor phases during the early stages of the crystallization process, demonstrating that liquid calcium carbonate mineral precursors play an important role in the precipitation pathway and must be generally considered for the interpretation of gas diffusion experiments, with and without additives. This discovery poses an important step in the understanding of how minerals are formed, highlighting that nonclassical mineralization processes must be considered for material synthesis. Last but not least, the advanced ADM may be useful for the exploration of the formation mechanism of other minerals than calcium carbonate, which are also of broad interest in the materials chemistry community

Chemical trigger toward phase separation in the aqueous Al(III) system revealed

Although Al(III) hydrolysis, condensation, and nucleation play pivotal roles in the synthesis of Al-based compounds and determine their chemical behavior, we still lack experimental evidence regarding the chemistry of nucleation from solution. Here, by combining advanced titration assays, high-resolution transmission electron microscopy (HR-TEM), and 27Al–nuclear magnetic resonance spectroscopy, we show that highly dynamic solute prenucleation clusters (PNCs) are fundamental precursors of nanosolid formation. Chemical changes from olation to oxolation bridging within PNCs rely on the formation of tetrahedral AlO4 in solution and trigger phase separation at low driving force (supersaturation). This does not include the formation of Keggin-Al13 ions, at least during the earliest stages. The PNC pathway of the formation of Al(III) (oxy)(hydr)oxides offers new possibilities toward the development of strategies for controlling the entire crystallization process

Solvent-mediated isotope effects strongly influence the early stages of calcium carbonate formation: exploring D2O vs. H2O in a combined computational and experimental approach

In experimental studies, heavy water (D2O) is employed, e.g., so as to shift the spectroscopic solvent background, but any potential effects of this solvent exchange on reaction pathways are often neglected. While the important role of light water (H2O) during the early stages of calcium carbonate formation has been realized, studies into the actual effects of aqueous solvent exchanges are scarce. Here, we present a combined computational and experimental approach to start to fill this gap. We extended a suitable force field for molecular dynamics (MD) simulations. Experimentally, we utilised advanced titration assays and time-resolved attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. We find distinct effects in various mixtures of the two aqueous solvents, and in pure H2O or D2O. Disagreements between the computational results and experimental data regarding the stabilities of ion associates might be due to the unexplored role of HDO, or an unprobed complex phase behaviour of the solvent mixtures in the simulations. Altogether, however, our data suggest that calcium carbonate formation might proceed “more classically” in D2O. Also, there are indications for the formation of new structures in amorphous and crystalline calcium carbonates. There is huge potential towards further improving the understanding of mineralization mechanisms by studying solvent-mediated isotope effects, also beyond calcium carbonate. Last, it must be appreciated that H2O and D2O have significant, distinct effects on mineralization mechanisms, and that care has to be taken when experimental data from D2O studies are used, e.g., for the development of H2O-based computer models

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

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.Institute of Technical Sciences of SASA - Ministry of Education, Science and Technological Development of the Republic of Serbia (451-03-9/2021-14/200175)IAESTE Belgrade organization and DAA

Bottling Liquid-Like Minerals for Advanced Materials Synthesis

Materials synthesis via liquid-like mineral precursors has been studied since their discovery almost 25 years ago, because their properties offer several advantages, for example, the ability to infiltrate small pores, the production of non-equilibrium crystal morphologies or mimicking textures from biominerals, resulting in a vast range of possible applications. However, the potential of liquid-like precursors has never been fully tapped, and they have received limited attention in the materials chemistry community, largely due to the lack of efficient and scalable synthesis protocols. Herein, the “scalable controlled synthesis and utilization of liquid-like precursors for technological applications” (SCULPT) method is presented, allowing the isolation of the precursor phase on a gram scale, and its advantage in the synthesis of crystalline calcium carbonate materials and respective applications is demonstrated. The effects of different organic and inorganic additives, such as magnesium ions and concrete superplasticizers, on the stability of the precursor are investigated and allow optimizing the process for specific demands. The presented method is easily scalable and therefore allows synthesizing and utilizing the precursor on large scales. Thus, it can be employed for mineral formation during restoration and conservation applications but can also open up pathways toward calcium carbonate-based, CO2-neutral cements

Growth of organic crystals via attachment and transformation of nanoscopic precursors

A key requirement for the understanding of crystal growth is to detect how new layers form and grow at the nanoscale. Multistage crystallization pathways involving liquid-like, amorphous or metastable crystalline precursors have been predicted by theoretical work and have been observed experimentally. Nevertheless, there is no clear evidence that any of these precursors can also be relevant for the growth of crystals of organic compounds. Herein, we present a new growth mode for crystals of DL-glutamic acid monohydrate that proceeds through the attachment of preformed nanoscopic species from solution, their subsequent decrease in height at the surface and final transformation into crystalline 2D nuclei that eventually build new molecular layers by further monomer incorporation. This alternative mechanism provides a direct proof for the existence of multistage pathways in the crystallization of molecular compounds and the relevance of precursor units larger than the monomeric constituents in the actual stage of growth.publishe

Introducing the crystalline phase of dicalcium phosphate monohydrate

Calcium orthophosphates (CaPs) are important in geology, biomineralization, animal metabolism and biomedicine, and constitute a structurally and chemically diverse class of minerals. In the case of dicalcium phosphates, ever since brushite (CaHPO4·2H2O, dicalcium phosphate dihydrate, DCPD) and monetite (CaHPO4, dicalcium phosphate, DCP) were first described in 19th century, the form with intermediary chemical formula CaHPO4·H2O (dicalcium phosphate monohydrate, DCPM) has remained elusive. Here, we report the synthesis and crystal structure determination of DCPM. This form of CaP is found to crystallize from amorphous calcium hydrogen phosphate (ACHP) in water-poor environments. The crystal structure of DCPM is determined to show a layered structure with a monoclinic symmetry. DCPM is metastable in water, but can be stabilized by organics, and has a higher alkalinity than DCP and DCPD. This study serves as an inspiration for the future exploration of DCPM’s potential role in biomineralization, or biomedical applications

In Situ TEM Imaging of Solution‐Phase Chemical Reactions Using 2D‐Heterostructure Mixing Cells

From Wiley via Jisc Publications RouterHistory: received 2021-01-26, rev-recd 2021-03-31, pub-electronic 2021-06-09Article version: VoRPublication status: PublishedFunder: Engineering and Physical Sciences Research Council (UK) EPSRC; Grant(s): EP/M010619/1, EP/S021531/1, EP/P009050/1Funder: European Commission H2020 ERC Starter grant EvoluTEM; Grant(s): 715502Funder: Henry Royce Institute for Advanced MaterialsFunder: EPSRC; Id: http://dx.doi.org/10.13039/501100000266; Grant(s): EP/R00661X/1, EP/S019367/1, EP/P025021/1, EP/P025498/1Funder: Royal Society FellowshipAbstract: Liquid‐phase transmission electron microscopy is used to study a wide range of chemical processes, where its unique combination of spatial and temporal resolution provides countless insights into nanoscale reaction dynamics. However, achieving sub‐nanometer resolution has proved difficult due to limitations in the current liquid cell designs. Here, a novel experimental platform for in situ mixing using a specially developed 2D heterostructure‐based liquid cell is presented. The technique facilitates in situ atomic resolution imaging and elemental analysis, with mixing achieved within the immediate viewing area via controllable nanofracture of an atomically thin separation membrane. This novel technique is used to investigate the time evolution of calcium carbonate synthesis, from the earliest stages of nanodroplet precursors to crystalline calcite in a single experiment. The observations provide the first direct visual confirmation of the recently developed liquid‐liquid phase separation theory, while the technological advancements open an avenue for many other studies of early stage solution‐phase reactions of great interest for both the exploration of fundamental science and developing applications

Functional Prioritization and Hydrogel Regulation Phenomena Created by a Combinatorial Pearl-Associated Two-Protein Biomineralization Model System

In the nacre or aragonitic layer of an oyster pearl, there exists a 12-member proteome that regulates both the early stages of nucleation and nanoscale-to-mesoscale assembly of nacre tablets and calcitic crystals from mineral nanoparticle precursors. Several approaches to understanding protein-associated mechanisms of pearl nacre formation have been developed, yet we still lack insight into how protein ensembles or proteomes manage nucleation and crystal growth. To provide additional insights, we have created a proportionally defined combinatorial model consisting of two pearl nacre-associated proteins, PFMG1 and PFMG2 (shell oyster pearl nacre, Pinctada fucata) whose individual in vitro mineralization functionalities are distinct from one another. Using scanning electron microscopy, atomic force microscopy, Ca(II) potentiometric titrations, and quartz crystal microbalance with dissipation monitoring quantitative analyses, we find that at 1:1 molar ratios, rPFMG2 and rPFMG1 co-aggregate in specific molecular ratios to form hybrid hydrogels that affect both the early and later stages of in vitro calcium carbonate nucleation. Within these hybrid hydrogels, rPFMG2 plays a role in defining protein co-aggregation and hydrogel dimension, whereas rPFMG1 defines participation in nonclassical nucleation processes; both proteins exhibit synergy with regard to surface and subsurface modifications to existing crystals. The interactions between both proteins are enhanced by Ca(II) ions and may involve Ca(II)-induced conformational events within the EF-hand rPFMG1 protein, as well as putative interactions between the EF-hand domain of rPFMG1 and the calponin-like domain of rPFMG2. Thus, the pearl-associated PFMG1 and PFMG2 proteins interact and exhibit mineralization functionalities in specific ways, which may be relevant for pearl formation