Prenucleation Clusters Research Articles

Direct observation of liquid pre-crystallization intermediates during the reduction of aqueous tetrachloroaurate by sulfide ions

Phenomena preceding precipitation of gold(i) sulfide in the reaction of aqueous tetrachloroauric acid with sodium sulfide have been studied applying several time-resolved in situ techniques. As can be deduced from UV-vis absorption spectroscopy, soluble species ("pre-nucleation clusters") emerge within several seconds and slightly change with time; the spectra, along with the previous data for the immobilized products, are indicative of disordered matter with Au(I)-S bonding and the gap of about 1.5 eV. In situ tapping-mode atomic force microscopy (AFM) directly imaged "soft" droplet-like species from 20-50 nm to about 200 nm in the lateral size and the continuous film condensed on the highly oriented pyrolytic graphite (HOPG) support. Small-angle X-ray scattering (SAXS) revealed quasi-particles ("liquid clusters") growing to about 12 nm for 30 min, and slowly afterwards. Dynamic light scattering (DLS) was preferentially due to the larger species, although the liquid clusters within 20 nm comprise more than 80% of the total volume of the fluid products. The entities, which exist in solution for many hours before sudden gold sulfide sedimentation, are considered as "dense liquid" intermediates involved in a non-classical nucleation pathway.

Pre-nucleation clusters as solute precursors in crystallisation

Crystallisation is at the heart of various scientific disciplines, but still the understanding of the molecular mechanisms underlying phase separation and the formation of the first solid particles in aqueous solution is rather limited. In this review, classical nucleation theory, as well as established concepts of spinodal decomposition and liquid-liquid demixing, is introduced together with a description of the recently proposed pre-nucleation cluster pathway. The features of pre-nucleation clusters are presented and discussed in relation to recent modifications of the classical and established models for phase separation, together with a review of experimental work and computer simulations on the characteristics of pre-nucleation clusters of calcium phosphate, calcium carbonate, iron(oxy)(hydr)oxide, silica, and also amino acids as an example of small organic molecules. The role of pre-nucleation clusters as solute precursors in the emergence of a new phase is summarized, and the link between the chemical speciation of homogeneous solutions and the process of phase separation via pre-nucleation clusters is highlighted.

Computational study of the Rayleigh light scattering properties of atmospheric pre-nucleation clusters

The Rayleigh and hyper Rayleigh scattering properties of the binary (H2SO4)(H2O)n and ternary (H2SO4)(NH3)(H2O)n clusters are investigated using a quantum mechanical response theory approach. The molecular Rayleigh scattering intensities are expressed using the dipole polarizability α and hyperpolarizability β tensors. Using density functional theory, we elucidate the effect of cluster morphology on the scattering properties using a combinatorial sampling approach. We find that the Rayleigh scattering intensity depends quadratically on the number of water molecules in the cluster and that a single ammonia molecule is able to induce a high anisotropy, which further increases the scattering intensity. The hyper Rayleigh scattering activities are found to be extremely low. This study presents the first attempt to map the scattering of atmospheric molecular clusters using a bottom-up approach.

3P085 X線1分子追跡法を用いたタンパク質過飽和溶液中における核形成前駆体クラスターの動態観察(01E. 蛋白質:計測・解析の方法論,ポスター,第52回日本生物物理学会年会(2014年度))

3P085 X線1分子追跡法を用いたタンパク質過飽和溶液中における核形成前駆体クラスターの動態観察(01E. 蛋白質:計測・解析の方法論,ポスター,第52回日本生物物理学会年会(2014年度))

Observing Assembly of Complex Inorganic Materials from Polyoxometalate Building Blocks

Understanding the aqueous state of discrete metal-oxo clusters, prenucleation clusters, and even simple ions is valuable for controlling the growth of metal-oxide materials from water. Niobium polyoxometalates (Nb-POMs) are unique in the aqueous metal-oxo cluster landscape in their unusual solubility behavior: specifically, their solubility in water increases with increasing ion-pairing contact with their counterions, and thus provides a rare opportunity to observe these and related solution phenomena. Here, we isolate in the solid state the monomeric and dimeric building blocks, capped Keggin ions, of the extended Keggin chain materials that are now well-known: not only in Nb-POM chemistry, but Mo and V POM chemistry as well. Rb13[GeNb13O41]·23H2O (Rb1), Cs10.6[H2.4GeNb13O41]·27H2O (Cs1) and Cs18H6[(NbOH)SiNb12O40]2·38H2O (Cs2) were characterized by single-crystal X-ray diffraction. Small angle X-ray scattering (SAXS) of solutions of Rb1 and Cs1 in varying conditions revealed oligomerization of the monomers into chain structures: the extent of oligomerization is controlled by pH, concentration, and the counterion. We distinctly observe chains of up to six Keggin ions in solution, with the large alkali cations for charge-balance. This combined solid state and solution study reveals in great detail the growth of a complex material from discrete monomeric building blocks. The fundamentals of the processes we are able to directly observe in this study, ion-association and hydrolysis leading to condensation, universally control the self-assembly and precipitation of materials from water.

Structural motifs of pre-nucleation clusters

Structural motifs of pre-nucleation clusters prepared in single, optically levitated supersaturated aqueous aerosol microparticles containing CaBr2 as a model system are reported. Cluster formation is identified by means of X-ray absorption in the Br K-edge regime. The salt concentration beyond the saturation point is varied by controlling the humidity in the ambient atmosphere surrounding the 15-30 μm microdroplets. This leads to the formation of metastable supersaturated liquid particles. Distinct spectral shifts in near-edge spectra as a function of salt concentration are observed, in which the energy position of the Br K-edge is red-shifted by up to 7.1 ± 0.4 eV if the dilute solution is compared to the solid. The K-edge positions of supersaturated solutions are found between these limits. The changes in electronic structure are rationalized in terms of the formation of pre-nucleation clusters. This assumption is verified by spectral simulations using first-principle density functional theory and molecular dynamics calculations, in which structural motifs are considered, explaining the experimental results. These consist of solvated CaBr2 moieties, rather than building blocks forming calcium bromide hexahydrates, the crystal system that is formed by drying aqueous CaBr2 solutions.

Water in the formation of biogenic minerals: Peeling away the hydration layers

Minerals of biogenic origin form and crystallize from aqueous environments at ambient temperatures and pressures. The in vivo environment either intracellular or intercellular, contains many components that modulate both the activity of the ions which associate to form the mineral, as well as the activity and structure of the crowded water. Most of the studies about the mechanism of mineralization, that is, the detailed pathways by which the mineral ions proceed from solution to crystal state, have been carried out in relatively dilute solutions and clean solutions. These studies have considered both thermodynamic and kinetic controls. Most have not considered the water itself. Is the water a passive bystander, or is it intimately a participant in the mineral ion densification reaction? A wide range of experiments show that the mineralization pathways proceed through a series of densification stages with intermediates, such as a "dense liquid" phase and the prenucleation clusters that form within it. This is in contrast to the idea of a single step phase transition, but consistent with the Gibbs concept of discontinuous phase transitions from supersaturated mother liquor to crystal. Further changes in the water structure at every surface and interface during densification guides the free energy trajectory leading to the crystalline state. In vertebrates, mineralization takes place in a hydrated collagen matrix, thus water must be considered as a direct participant. Although different in detail, the crystallization of calcium phosphates, as apatite, and calcium carbonates, as calcite, are mechanistically identical from the viewpoint of water.

Heterogeneous Crystallization of Proteins: Is it a Prenucleation Clusters Mediated Process?

Several studies have shown that heterogeneous agents are able to reduce required starting protein concentration and induction time for crystallization. However, in many cases, the molecular mechani...

Ion-association complexes unite classical and non-classical theories for the biomimetic nucleation of calcium phosphate

Despite its importance in many industrial, geological and biological processes, the mechanism of crystallization from supersaturated solutions remains a matter of debate. Recent discoveries show that in many solution systems nanometre-sized structural units are already present before nucleation. Still little is known about the structure and role of these so-called pre-nucleation clusters. Here we present a combination of in situ investigations, which show that for the crystallization of calcium phosphate these nanometre-sized units are in fact calcium triphosphate complexes. Under conditions in which apatite forms from an amorphous calcium phosphate precursor, these complexes aggregate and take up an extra calcium ion to form amorphous calcium phosphate, which is a fractal of Ca(2)(HPO(4))(3)(2-) clusters. The calcium triphosphate complex also forms the basis of the crystal structure of octacalcium phosphate and apatite. Finally, we demonstrate how the existence of these complexes lowers the energy barrier to nucleation and unites classical and non-classical nucleation theories.

Nucleation and growth of magnetite from solution

The formation of crystalline materials from solution is usually described by the nucleation and growth theory, where atoms or molecules are assumed to assemble directly from solution. For numerous systems, the formation of the thermodynamically stable crystalline phase is additionally preceded by metastable intermediates . More complex pathways have recently been proposed, such as aggregational processes of nanoparticle precursors or pre-nucleation clusters, which seem to contradict the classical theory. Here we show by cryogenic transmission electron microscopy that the nucleation and growth of magnetite-a magnetic iron oxide with numerous bio- and nanotechnological applications-proceed through rapid agglomeration of nanometric primary particles and that in contrast to the nucleation of other minerals, no intermediate amorphous bulk precursor phase is involved. We also demonstrate that these observations can be described within the framework of classical nucleation theory.

“Liquid-like” biomineralization protein assemblies: a key to the regulation of non-classical nucleation

Over the past several decades, numerous studies have attempted to define the general role that proteins play in the nucleation of biominerals in organisms. Recently, with the emergence of the non-classical nucleation scheme involving pre-nucleation cluster formation, amorphous mineral cluster assembly, and maturation/stabilization scenarios, there is a growing realization that proteins could efficiently regulate many steps in this process, resulting in precise control over the development of biogenic crystals or the indefinite stabilization of amorphous mineral phases in a wide variety of organisms. In this Highlight, we present a generic scheme where nucleation-specific biomineralization proteins containing intrinsically disordered and aggregation-prone sequences assemble to form a liquid- or fluid-like phase similar to that formed in the polymer-induced liquid phase (PILP) and in vitro liquid protein systems. This assembled protein phase is compatible with the physical-chemical properties of prenucleation clusters and amorphous mineral clusters, and can provide an environment for subsequent stabilization and/or transformation of the mineral phase under appropriate conditions and locations. We foresee some important applications arising from Nature's use of protein assemblies to create, stabilize, and transform amorphous mineral precursor phases.

Large Hydrogen-Bonded Pre-nucleation (HSO4–)(H2SO4)m(H2O)kand (HSO4–)(NH3)(H2SO4)m(H2O)k Clusters in the Earth’s Atmosphere

The importance of pre-nucleation cluster stability as the key parameter controlling nucleation of atmospheric airborne ions is well-established. In this Article, large ternary ionic (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(H(2)O)(n) clusters have been studied using Density Functional Theory (DFT) and composite ab initio methods. Twenty classes of clusters have been investigated, and thermochemical properties of common atmospheric (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(0)(H(2)O)(k) and (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(1)(H(2)O)(n) clusters (with m, k, and n up to 3) have been obtained. A large amount of new themochemical and structural data ready-to-use for constraining kinetic nucleation models has been reported. We have performed a comprehensive thermochemical analysis of the obtained data and have investigated the impacts of ammonia and negatively charged bisulfate ion on stability of binary clusters in some detail. The comparison of theoretical predictions and experiments shows that the PW91PW91/6-311++G(3df,3pd) results are in very good agreement with both experimental data and high level ab initio CCSD(T)/CBS values and suggest that the PW91PW91/6-311++G(3df,3pd) method is a viable alternative to higher level ab initio methods in studying large pre-nucleation clusters, for which the higher level computations are prohibitively expensive. The uncertainties in both theory and experiments have been investigated, and possible ways of their reduction have been proposed.

Magnetic water treatment – how might it work?

Claims that passing hard water through a magnetic field somehow influences the structure and morphology of the calcium carbonate that forms when the water is subsequently heated have been met with robust scepticism. This was largely due to the absence of any plausible mechanism whereby water could acquire a long-lasting magnetically-imprinted memory. Recent work challenging classical nucleation theory, insofar as calcium carbonate is concerned, has advanced the idea of liquid-like prenucleation clusters of indeterminate shape that are thermodynamically-stable in calcium carbonate solutions. These nanometer-scale clusters may be the key to the problem; the possible influence on them of a magnetic field via Maxwell-like stress or singlet–triplet mixing of proton dimers leading to a long-lived change in the number of ionic bonds is discussed.

Mixed calcium-magnesium pre-nucleation clusters enrich calcium

Abstract It is demonstrated that magnesium and carbonate ions can form pre-nucleation clusters in analogy to calcium carbonate. If a mixed calcium and magnesium solution is brought in contact with carbonate ions, mixed pre-nucleation clusters form. The equilibrium constants for their formation are reported revealing that over the entire range of possible cation mixing ratios, calcium gets enriched over magnesium in the pre-nucleation clusters. This can explain high magnesium contents in amorphous calcium carbonate. However, this enrichment alone is not sufficient to explain the magnesium content of less than 41 mol% which is found in magnesium calcite biominerals nucleated from seawater.

Colloidal Stabilization of Calcium Carbonate Prenucleation Clusters with Silica

AbstractCalcium carbonate precipitation proceeds via a complex multistage scenario involving neutral ion clusters as precursors and amorphous phases as intermediates, which finally transform to crystals. Although the existence of stable clusters in solution prior to nucleation has been demonstrated, the molecular mechanisms by which they precipitate are still obscure. Here, direct insight into the processes that drive the transformation of individual clusters into amorphous nanoparticles is provided by progressive colloidal stabilization of different transient states in silica‐containing environments. Nucleation of calcium carbonate in the presence of silica can only take place via cluster aggregation at low pH values. At higher pH, prenucleation clusters become colloidally stabilized and cannot aggregate. Nucleation through structural reorganization within the clusters is not observed under these conditions, indicating that this pathway is blocked by kinetic and/or thermodynamic means. The degree of stabilization against nucleation is found to be sufficient to allow for a dramatic enrichment of solutions with prenucleation clusters and enable their isolation into the dry state. This approach renders direct analyses of the clusters by conventional techniques possible and is thus likely to facilitate deeper insight into the chemistry and structure of these elusive species in the future.

Structure and Transformation of Amorphous Calcium Carbonate: A Solid-State 43Ca NMR and Computational Molecular Dynamics Investigation

Amorphous calcium carbonate (ACC) is a metastable precursor to crystalline CaCO3 phases that precipitates by aggregation of ion pairs and prenucleation clusters.(1, 2) We use 43Ca solid-state NMR spectroscopy to probe the local structure and transformation of ACC synthesized from seawater-like solutions with and without Mg2+ and computational molecular dynamics (MD) simulations to provide more detailed molecular-scale understanding of the ACC structure. The 43Ca NMR spectra of ACC collected immediately after synthesis consist of broad, featureless resonances with Gaussian line shapes (FWHH = 27.6 ± 1 ppm) that do not depend on Mg2+ or H2O content. A correlation between 43Ca isotropic chemical shifts and mean Ca–O bond distances for crystalline hydrous and anhydrous calcium carbonate phases indicates indistinguishable maximum mean Ca–O bond lengths of ∼2.45 A for all our samples. This value is near the upper end of the published Ca–O bond distance range for biogenic and synthetic ACCs obtained by Ca-X-ray ...

Assessment of Density Functional Theory in Predicting Structures and Free Energies of Reaction of Atmospheric Prenucleation Clusters.

This work assesses different computational strategies for predicting structures and Gibb's free energies of reaction of atmospheric prenucleation clusters. The performance of 22 Density Functional Theory functionals in predicting equilibrium structures of molecules and water prenucleation clusters of atmospheric relevance is evaluated against experimental data using a test set of eight molecules and prenucleation clusters: SO2, H2SO4, CO2·H2O, CS2·H2O, OCS·H2O, SO2·H2O, SO3·H2O, and H2SO4·H2O. Furthermore, the functionals are tested and compared for their ability to predict the free energy of reaction for the formation of five benchmark atmospheric prenucleation clusters: H2SO4·H2O, H2SO4·(H2O)2, H2SO4·NH3, HSO4(-)·H2O, and HSO4(-)·(H2O)2. The performance is evaluated against experimental data, coupled cluster, and complete basis set extrapolation procedure methods. Our investigation shows that the utilization of the M06-2X functional with the 6-311++G(3df,3pd) basis set represents an improved approach compared to the conventionally used PW91 functional, yielding mean absolute errors of 0.48 kcal/mol and maximum errors of 0.67 kcal/mol compared to experimental results.

Computer Simulations of Nucleation of Nanoparticle Superclusters from Solution

This paper presents simulation studies of nanoparticle supercluster (NPSC) nucleation from a temperature quenched system. The nanoparticles are represented as 5 nm, spherical gold nanoparticles ligated with alkane thiols. The pair potential accounts for the van der Waals interaction between the metallic cores and ligand-ligand and ligand-solvent interactions. Phenomena well-known for molecular systems are observed including a prenucleation induction period, fluctuating prenucleation clusters that predominately add monomers one at a time, a critical nucleus size, and growth of NPSCs from solution in the presence of an equilibrium supernatant, all consistent with classical nucleation theory. However, only the largest prenucleating clusters are dense, and the cluster size can occasionally range greater than the critical size in the prenucleation regime until a cluster with low enough energy occurs, then nucleation ensues. Late in the nucleation process, the clusters display a crystalline structure that is a random mix of face-centered cubic (fcc) and hexagonal close-packed (hcp) lattices and indistinguishable from a randomized icosahedra structure.

Rethinking the application of the first nucleation theorem to particle formation

The critical cluster is the threshold size above which a cluster will be more likely to grow than to evaporate. In field and laboratory measurements of new particle formation, the number of molecules of a given species in the critical cluster is commonly taken to be the slope of the log-log plot of the formation rate versus the concentration of the species. This analysis is based on an approximate form of the first nucleation theorem, which is derived with the assumption that there are no minima in the free energy surface prior to the maximum at the critical size. However, many atmospherically relevant systems are likely to exhibit such minima, for example, ions surrounded by condensable vapour molecules or certain combinations of acids and bases. We have solved numerically the birth-death equations for both an electrically neutral one-component model system with a local minimum at pre-critical sizes and an ion-induced case. For the ion-induced case, it is verified that the log-log slope of the nucleation rate versus particle concentration plot gives accurately the difference between the cluster sizes at the free energy maximum and minimum, as is expected from the classical form of the ion-induced nucleation rate. However, the results show that applying the nucleation theorem to neutral systems with stable pre-nucleation clusters may lead to erroneous interpretations about the nature of the critical cluster.

Probing the structure and stability of calcium carbonate pre-nucleation clusters

Recent advances in our understanding of the emergence of biomineral phases from solution has provoked new and challenging questions. A consensus is beginning to form, attesting to the existence of pre-nucleation clusters of calcium carbonate in solution, which subsequently aggregate to initiate solid growth. The structure and stability of these clusters has not yet been fully determined; this needs to be addressed if biomineralisation mechanisms are to be exploited. Here, we present the results of an exhaustive computational study in the search for possible candidate pre-nucleation clusters that might arise in clusters up to 80 ions in size. Both anhydrous and hydrated clusters have been studied. A significant sample of the clusters were simulated, using molecular dynamics, to elucidate the metastability of these nanoclusters in water. An analogous study was conducted for hydrated clusters containing aspartate, to observe the effects of this amino acid on the structure and stability of candidate pre-nucleation clusters. Our results suggest that pre-nucleation cluster stability is a balance between ionic coordination and ion hydration. We find that clusters are generally dynamic in the lower limit of stability, forming chains to which ions frequently aggregate or dissolve. Larger calcium carbonate clusters retain a higher level of coordination in solution but swell to maximise hydration. The effect of additives on the structure and stability of clusters as a function of cluster size is intriguing, with trends in our data suggesting that aspartate can limit ion dissolution, but still allow for dynamic ordering and increasing ion hydration. Finally we find a bias in the ionic charge distributions for relatively dense clusters, indicating that these clusters sustain a negatively charged surface.