Exploring the Potential of Nonclassical Crystallization Pathways to Advance Cementitious Materials.

Understanding the crystallization of cement-binding phases, from basic units to macroscopic structures, can enhance cement performance, reduce clinker use, and lower CO2 emissions in the construction sector. This review examines the crystallization pathways of C-S-H (the main phase in PC cement) and other alternative binding phases, particularly as cement formulations evolve toward increasing SCMs and alternative binders as clinker replacements. We adopt a nonclassical crystallization perspective, which recognizes the existence of critical intermediate steps between ions in solution and the final crystalline phases, such as solute ion associates, dense liquid phases, amorphous intermediates, and nanoparticles. These multistep pathways uncover innovative strategies for controlling the crystallization of binding phases through additive use, potentially leading to highly optimized cement matrices. An outstanding example of additive-controlled crystallization in cementitious materials is the synthetically produced mesocrystalline C-S-H, renowned for its remarkable flexural strength. This highly ordered microstructure, which intercalates soft matter between inorganic and brittle C-S-H, was obtained by controlling the assembly of individual C-S-H subunits. While large-scale production of cementitious materials by a bottom-up self-assembly method is not yet feasible, the fundamental insights into the crystallization mechanism of cement binding phases presented here provide a foundation for developing advanced cement-based materials.

Organic Nucleation: Water Rearrangement Reveals the Pathway of Ibuprofen.

The organic nucleation of the pharmaceutical ibuprofen is investigated, as triggered by the protonation of ibuprofen sodium salt at elevated pH. The growth and aggregation of nanoscale solution species by Analytical Ultracentrifugation and Molecular Dynamics (MD) simulations is tracked. Both approaches reveal solvated molecules, oligomers, and prenucleation clusters, their size as well as their hydration at different reaction stages. By combining surface-specific vibrational spectroscopy and MD simulations, water interacting with ibuprofen at the air-water interface during nucleation is probed. The results show the structure of water changes upon ibuprofen protonation in response to the charge neutralization. Remarkably, the water structure continues to evolve despite the saturation of protonated ibuprofen at the hydrophobic interface. This further water rearrangement is associated with the formation of larger aggregates of ibuprofen molecules at a late prenucleation stage. The nucleation of ibuprofen involves ibuprofen protonation and their hydrophobic assembly. The results highlight that these processes are accompanied by substantial water reorganization. The critical role of water is possibly relevant for organic nucleation in aqueous environments in general.

The Structure, Preparation, Characterization, and Intercalation Mechanism of Layered Hydroxides Intercalated with Guest Anions.

Since the intercalation of anions into layered hydroxides (LHs) has a great impact not only on their nucleation and growth but also on their structure, composition, and size, the intercalation chemistry of LHs has aroused the strong interest of researchers. However, the progress in the fundamental understanding of LHs intercalated with guest anions have not been paralleled by a concomitant development of the preparation and performance improvement of such materials. Considering the guidance of a timely in-depth review for scientists in this area, a systematic introduction about the development that is made on the above-mentioned issues is highly needed but yet missing so far. Herein, recent advances in understanding the chemical composition and structure of LHs intercalated with guest anions are systematically summarized. Meanwhile, typical and emerging bottom-up synthesis methods of LHs intercalated with anions are reviewed, and the potential impact of external reaction parameters on the intercalation of anions into LHs are discussed . Besides, different analytical characterization techniques employed in the examination of guest anion-intercalated LHs are deliberated upon. Finally, although progress is slow in exploring the intercalation mechanism, as many examples as possible are included in this review and inferred the possible intercalation mechanism.

Silica-Functionalized Nanolimes for the Conservation of Stone Heritage.

The relatively recent development of nanolimes (i.e., alcoholic dispersions of Ca(OH)2 nanoparticles) has paved the way for new approaches to the conservation of important art works. Despite their many benefits, nanolimes have shown limited reactivity, back-migration, poor penetration, and lack of proper bonding to silicate substrates. In this work a novel solvothermal synthesis process is presented by which extremely reactive nanostructured Ca(OH)2 particles are obtained using calcium ethoxide as the main precursor species. Moreover, it is demonstrated that this material can be easily functionalized with silica-gel derivatives under mild synthesis conditions, thereby preventing particle growth, increasing total specific surface area, enhancing reactivity, modifying colloidal behavior, and functioning as self-integrated coupling agents. Additionally, the formation of calcium silicate hydrate (CSH) nanocement is promoted by the presence of water, resulting in optimal bonding when applied to silicate substrates, as evidenced by the higher reinforcement effect produced on treated Prague sandstone specimens as compared to those consolidated with nonfunctionalized commercial nanolime. The functionalization of nanolimes is not only a promising strategy for the design of optimized consolidation treatments for the cultural heritage, but may also have important implications for the development of advanced nanomaterials for building, environmental, or biomedical applications.

Self-Assembly of Colloidal Nanocrystals into 3D Binary Mesocrystals.

Biominerals are unique materials found in many living organisms that often display outstanding functionalities attributed to their mesocrystalline structure. Mesocrystals are nanocrystal superstructures with mutual crystallographic alignment of the building units. One could thus imagine these optimized evolutionary systems as archetypes to fabricate advanced materials. The main advantage of such systems relies on their ability to combine the features of the nanocrystals with those of single crystalline microscopic structures, yielding assemblies with directional, enhanced, and potentially emergent properties. Moreover, fueled by the promises of multifunctional materials with unprecedented and tunable properties, the rational design of mesocrystals assembled from two distinct colloidal nanocrystal ensembles has become a recent focus of research. However, the combination of dissimilar nanocrystals into ordered binary superstructures is still a major scientific challenge due to the nature of the coassembly process.We focus this Account on the growth of tridimensional (3D) binary mesocrystals and the understanding of the self-assembly of two colloidal nanocrystal ensembles with the ultimate goal to serve as a basis for more rational mesocrystal syntheses in the future. The formation of mesocrystals demands nanocrystals with defined surface faceting, the primary factor influencing their oriented self-assembly. Notably, such a process cannot be successfully afforded without functionalized nanocrystals with high and, in many cases, tunable colloidal stability. Besides, the nature and solvation degree of the surface ligand shell influences the effective shape of the nanocrystals and the kinetics of self-assembly. If the assembly is triggered by reducing the colloidal stability with nonsolvents, 3D single-component mesocrystals are often grown. Here, the different magnitude of the van der Waals attraction forces between nanocrystals with differing compositions, dimensions, and morphologies generally favors the segregation and growth of single component mesocrystals. This phenomenon was illustrated during the successful preparation of 3D binary mesocrystals composed of iron oxide and platinum nanocubes. Although the building blocks possessed comparable sizes and were stabilized by similar ligands, the amount of the second component could only be arbitrarily tuned up to some extent, even when the assembly conditions were rationally optimized to achieve 3D binary mesocrystals. Only a small amount of it was effectively incorporated into the matrix of the initial mesocrystal. The 3D binary mesocrystal growth process demands a delicate control over the size, shape, and surface chemistry of the nanocrystals, the solvent nature, and the self-assembly process. Hence, the improvement of our ability to control the synthesis of 3D binary mesocrystalline materials is critical to exploit their potential toward technological applications in catalysis, energy storage, or structural materials.

Localized Crystallization of Calcium Phosphates by Light-Induced Processes.

Medical treatment options for bones and teeth can be significantly enhanced by taking control over the crystallization of biomaterials like hydroxyapatite in the healing process. Light-induced techniques are particularly interesting for this approach as they offer tremendous accuracy in spatial resolution. However, in the field of calcium phosphates, light-induced crystallization has not been investigated so far. Here, proof of principle is established to successfully induce carbonate-hydroxyapatite precipitation by light irradiation. Phosphoric acid is released by a photolabile molecule exclusively after irradiation, combining with calcium ions to form a calcium phosphate in the crystallization medium. 4-Nitrophenylphosphate (4NPP) is established as the photolabile molecule and the system is optimized and fully characterized. A calcium phosphate is crystallized exclusively by irradiation in aqueous solution and identified as carbonate apatite. Control over the localization and stabilization of the carbonate apatite is achieved by a pulsed laser, triggering precipitation in calcium and 4NPP-containing gel matrices. The results of this communication open up a wide range of new opportunities, both in the field of chemistry for more sophisticated reaction control in localized crystallization processes and in the field of medicine for enhanced treatment of calcium phosphate containing biomaterials.

How a Facet of a Nanocrystal Is Formed: The Concept of the Symmetry Based Kinematic Theory.

Conventional nanocrystal (NC) growth mechanisms have overwhelmingly focused on the final exposed facets to explain shape evolution. However, how the final facets are formed from the initial nuclei or seeds, has not been specifically interrogated. In this concept paper, we would like to concentrate on this specific topic, and introduce the symmetry based kinematic theory (SBKT) to explain the formation and evolution of crystal facets. It is a crystallographic theory based on the classical crystal growth concepts developed to illustrate the shape evolution during the NC growth. The most important principles connecting the basic NC growth processes and morphology evolution are the preferential growth directions and the properties of kinematic waves. On the contrary, the final facets are just indications of how the crystal growth terminates, and their formation and evolution rely on the NC growth processes: surface nucleation and layer advancement. Accordingly, the SBKT could even be applied to situations where non-faceted NCs such as spheres are formed.

A Nanoparticle-Based Model System for the Study of Heterogeneous Nucleation Phenomena.

Heterogeneous nucleation processes are involved in many important phenomena in nature, including devastating human diseases caused by amyloid structures or the harmful frost formed on fruits. However, understanding them is challenging due to the difficulties of characterizing the initial stages of the process occurring at the interface between the nucleation medium and the substrate surfaces. This work implements a model system based on gold nanoparticles to investigate the effect of particle surface chemistry and substrate properties on heterogeneous nucleation processes. Using widely available techniques such as UV-vis-NIR spectroscopy and light microscopy, gold nanoparticle-based superstructure formation was studied in the presence of substrates with different hydrophilicity and electrostatic charges. The results were evaluated on grounds of classical nucleation theory (CNT) to reveal kinetic and thermodynamic contributions of the heterogeneous nucleation process. In contrast to nucleation from ions, the kinetic contributions toward nucleation turned out to be larger than the thermodynamic contributions for the nanoparticle building blocks. Electrostatic interactions between substrates and nanoparticles with opposite charges were crucial to enhancing the nucleation rates and decreasing the nucleation barrier of superstructure formation. Thereby, the described strategy is demonstrated advantageous for characterizing physicochemical aspects of heterogeneous nucleation processes in a simple and accessible manner, which could be potentially explored to study more complex nucleation phenomena.

Toward Understanding the Formation Mechanism and OER Catalytic Mechanism of Hydroxides by In Situ and Operando Techniques.

Developing efficient and affordable electrocatalysts for the sluggish oxygen evolution reaction (OER) remains a significant barrier that needs to be overcome for the practical applications of hydrogen production via water electrolysis, transforming CO2 to value-added chemicals, and metal-air batteries. Recently, hydroxides have shown promise as electrocatalysts for OER. In situ or operando techniques are particularly indispensable for monitoring the key intermediates together with understanding the reaction process, which is extremely important for revealing the formation/OER catalytic mechanism of hydroxides and preparing cost-effective electrocatalysts for OER. However, there is a lack of comprehensive discussion on the current status and challenges of studying these mechanisms using in situ or operando techniques, which hinders our ability to identify and address the obstacles present in this field. This review offers an overview of in situ or operando techniques, outlining their capabilities, advantages, and disadvantages. Recent findings related to the formation mechanism and OER catalytic mechanism of hydroxides revealed by in situ or operando techniques are also discussed in detail. Additionally, some current challenges in this field are concluded and appropriate solution strategies are provided.

Revealing the Formation Mechanism and Optimizing the Synthesis Conditions of Layered Double Hydroxides for the Oxygen Evolution Reaction.

Layered double hydroxides (LDHs), whose formation is strongly related to OH- concentration, have attracted significant interest in various fields. However, the effect of the real-time change of OH- concentration on LDHs' formation has not been fully explored due to the unsuitability of the existing synthesis methods for in situ characterization. Here, the deliberately designed combination of NH3 gas diffusion and in situ pH measurement provides a solution to the above problem. The obtained results revealed the formation mechanism and also guided us to synthesize a library of LDHs with the desired attributes in water at room temperature without using any additives. After evaluating their oxygen evolution reaction performance, we found that FeNi-LDH with a Fe/Ni ratio of 25/75 exhibits one of the best performances so far reported.

Crystal Nucleation and Growth of Inorganic Ionic Materials from Aqueous Solution: Selected Recent Developments, and Implications.

In this review article, selected, latest theoretical, and experimental developments in the field of nucleation and crystal growth of inorganic materials from aqueous solution are highlighted, with a focus on literature after 2015 and on non-classical pathways. A key point is to emphasize the so far underappreciated role of water and solvent entropy in crystallization at all stages from solution speciation through to the final crystal. While drawing on examples from current inorganic materials where non-classical behavior has been proposed, the potential of these approaches to be adapted to a wide-range of systems is also discussed, while considering the broader implications of the current re-assessment of pathways for crystallization. Various techniques that are suitable for the exploration of crystallization pathways in aqueous solution, from nucleation to crystal growth are summarized, and a flow chart for the assignment of specific theories based on experimental observations is proposed.

Influence of anisotropy on heterogeneous nucleation of gold nanorod assemblies.

In this study, we analysed for the first time heterogeneous nucleation with anisotropic nanoparticles as a model system for non-spherical building units on the nanoscale. Gold nanorods were synthesised and assembled to investigate the phenomenon of heterogeneous nucleation. To determine the influence of the particle shape on heterogeneous nucleation, we utilised gold nanorods with varying aspect ratios, ranging from 3.00 and 2.25 to 1.75, while keeping the surface chemistry constant. First, the nucleation of the gold nanorod assemblies in solution and the process kinetics were analyzed with UV-vis-NIR spectroscopy followed by a microscopic examination of the gold nanorod-based superstructures formed heterogeneously on substrates. Here, positively charged cetyltrimethylammonium bromide (CTAB)-functionalized gold nanorods and negatively charged polystyrene sulfonate (PSS) functionalized substrates ensured the directed heterogeneous nucleation on the substrates. A combination of light microscopy with simultaneous UV-vis-NIR spectroscopy allowed us to observe the gold nanorod-based superstructure formation on the substrates in situ and to determine the nucleation rates of the process. We analysed the resulting data with the classical nucleation theory, which revealed a dominating kinetic term and a negligible thermodynamic term in contrast to ionic systems like calcium carbonate. Our studies consistently exhibit an influence of the aspect ratio on the nucleation behaviour resulting in faster nucleation of superstructures as the aspect ratio decreases. Hence our studies show unprecedented insight into the influence of particle anisotropy on the nucleation and growth of nanorod-based superstructures and reveal significant differences in the nucleation of nanoparticle building units compared to the nucleation of atoms or molecules as building units.

Turning Seashell Waste into Electrically Conductive Particles.

Biomaterials such as seashells are intriguing due to their remarkable properties, including their hierarchical structure from the nanometer to the micro- or even macroscopic scale. Transferring this nanostructure to generate nanostructured polymers can improve their electrical conductivity. Here, we present the synthesis of polypyrrole using waste seashell powder as a template to prepare a polypyrrole/CaCO3 composite material. Various synthesis parameters were optimized to produce a composite material with an electrical conductivity of 2.1 × 10-4 ± 3.2 × 10-5 S/cm. This work presents the transformation of waste seashells into sustainable, electronically conductive materials and their application as an antistatic agent in polymers. The requirements of an antistatic material were met for a safety shoe sole.

A Symmetry-Based Kinematic Theory for Nanocrystal Morphology Design.

The growth of crystalline nanoparticles (NPs) generally involves three processes: nucleation, growth, and shape evolution. Among them, the shape evolution is less understood, despite the importance of morphology for NP properties. Here, we propose a symmetry-based kinematic theory (SBKT) based on classical growth theories to illustrate the process. Based on the crystal lattice, nucleus (or seed) symmetry, and the preferential growth directions under the experimental conditions, the SBKT can illustrate the growth trajectories. The theory accommodates the conventional criteria of the major existing theories for crystal growth and provides tools to better understand the symmetry-breaking process during the growth of anisotropic structures. Furthermore, complex dendritic growth is theoretically and experimentally demonstrated. Thus, it provides a framework to explain the shape evolution, and extends the morphogenesis prediction to cases, which cannot be treated by other theories.

3D Binary Mesocrystals from Anisotropic Nanoparticles.

Binary mesocrystals offer the combination of nanocrystal properties in an ordered superstructure. Here, we demonstrate the simultaneous self-assembly of platinum and iron oxide nanocubes into micrometer-sized 3D mesocrystals using the gas-phase diffusion technique. By the addition of minor amounts of a secondary particle type tailored to nearly identical size, shape and surface chemistry, we were able to promote a random incorporation of foreign particles into a self-assembling host lattice. The random distribution of the binary particle types on the surface and within its bulk has been visualized using advanced transmission and scanning electron microscopy techniques. The 20-40 µm sized binary mesocrystals have been further characterized through wide and small angle scattering techniques to reveal a long-range ordering on the atomic scale throughout the crystal while showing clear evidence that the material consists of individual building blocks. Through careful adjustments of the crystallization parameters, we could further obtain a reverse superstructure, where incorporated particles and host lattice switch roles.

Role of Water in CaCO3 Biomineralization.

Biomineralization occurs in aqueous environments. Despite the ubiquity and relevance of CaCO3 biomineralization, the role of water in the biomineralization process has remained elusive. Here, we demonstrate that water reorganization accompanies CaCO3 biomineralization for sea urchin spine generation in a model system. Using surface-specific vibrational spectroscopy, we probe the water at the interface of the spine-associated protein during CaCO3 mineralization. Our results show that, while the protein structure remains unchanged, the structure of interfacial water is perturbed differently in the presence of both Ca2+ and CO32- compared to the addition of only Ca2+. This difference is attributed to the condensation of prenucleation mineral species. Our findings are consistent with a nonclassical mineralization pathway for sea urchin spine generation and highlight the importance of protein hydration in biomineralization.

Local Light-Controlled Generation of Calcium Carbonate and Barium Carbonate Biomorphs via Photochemical Stimulation.

Photochemical activation is proposed as a general method for controlling the crystallization of sparingly soluble carbonates in space and time. The photogeneration of carbonate in an alkaline environment is achieved upon photo-decarboxylation of an organic precursor by using a conventional 365 nm UV LED. Local irradiation was conducted focusing the LED light on a 300 µm radius spot on a closed glass crystallization cell. The precursor solution was optimized to avoid the precipitation of the photoreaction organic byproducts and prevent photo-induced pH changes to achieve the formation of calcium carbonate only in the corresponding irradiated area. The crystallization was monitored in real-time by time-lapse imaging. The method is also shown to work in gels. Similarly, it was also shown to photo-activate locally the formation of barium carbonate biomorphs. In the last case, the morphology of these biomimetic structures was tuned by changing the irradiation intensity.

Modular Toolkit of Multifunctional Block Copoly(2-oxazoline)s for the Synthesis of Nanoparticles.

Post-polymerization modification provides an elegant way to introduce chemical functionalities onto macromolecules to produce tailor-made materials with superior properties. This concept was adapted to well-defined block copolymers of the poly(2-oxazoline) family and demonstrated the large potential of these macromolecules as universal toolkit for numerous applications. Triblock copolymers with separated water-soluble, alkyne- and alkene-containing segments were synthesized and orthogonally modified with various low-molecular weight functional molecules by copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) and thiol-ene (TE) click reactions, respectively. Representative toolkit polymers were used for the synthesis of gold, iron oxide and silica nanoparticles.

Phase separation of binary mixtures induced by soft centrifugal fields.

We use the model system ethanol-dodecane to demonstrate that giant critical fluctuations induced by easily accessible weak centrifugal fields as low as 2000g can be observed above the miscibility gap of a binary liquid mixture. Moreover, several degrees above the phase transition, i.e. in the one-phase region, strong gradients of ethanol concentration occur upon centrifugation. In this case, the standard interpretation of sedimentation equilibrium in the analytical ultracentrifuge (AUC) yields an apparent molar mass of ethanol three orders of magnitude higher than the real value. Notably, these composition gradients have no influence on the distribution gradient of solutes such as dyes like Nile red. The thick opaque interphase formed upon centrifugation does not appear as the commonly observed sharp meniscus, but as a turbidity zone, similar to critical opalescence. This layer is a few millimeters thick and separates two fluids with low compositional gradients. All these effects can be qualitatively understood and explained using the Flory-Huggins solution model coupled to classical density functional theory (DFT). In this domain hetero-phase fluctuations can be triggered by gravity even far from the critical point. Taking into account Jean Perrin's approach to external fields in colloids, a self-consistent definition of the Flory effective volume and an explicit calculation of the total free energy per unit volume is possible.

Controlling Protein Nanocage Assembly with Hydrostatic Pressure.

Controlling the assembly and disassembly of nanoscale protein cages for the capture and internalization of protein or non-proteinaceous components is fundamentally important to a diverse range of bionanotechnological applications. Here, we study the reversible, pressure-induced dissociation of a natural protein nanocage, E. coli bacterioferritin (Bfr), using synchrotron radiation small-angle X-ray scattering (SAXS) and circular dichroism (CD). We demonstrate that hydrostatic pressures of 450 MPa are sufficient to completely dissociate the Bfr 24-mer into protein dimers, and the reversibility and kinetics of the reassembly process can be controlled by selecting appropriate buffer conditions. We also demonstrate that the heme B prosthetic group present at the subunit dimer interface influences the stability and pressure lability of the cage, despite its location being discrete from the interdimer interface that is key to cage assembly. This indicates a major cage-stabilizing role for heme within this family of ferritins.