Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Impact of molecular symmetry on crystallization pathways in highly supersaturated KH₂PO₄ solutions.

ABSTRACT: Solute structure and its evolution in supersaturated aqueous solutions are key clues to understand Ostwald's step rule. Here, we measure the structural evolution of solute molecules in highly supersaturated solutions of KH₂PO₄ (KDP) and NH₄H₂PO₄ (ADP) using a combination of electrostatic levitation and synchrotron X-ray scattering. The measurement reveals the existence of a solution-solution transition in KDP solution, caused by changing molecular symmetries and structural evolution of the solution with supersaturation. Moreover, we find that the molecular symmetry of H₂PO₄^- impacts on phase selection. These findings manifest that molecular symmetry and its structural evolution can govern the crystallization pathways in aqueous solutions, explaining the microscopic origin of Ostwald's step rule.

SUBMITTER: Cho YC

PROVIDER: S-EPMC11006877 | biostudies-literature | 2024 Apr

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Impact of molecular symmetry on crystallization pathways in highly supersaturated KH2PO4 solutions.

Cho Yong Chan YC Lee Sooheyong S Wang Lei L Lee Yun-Hee YH Kim Seongheun S Lee Hyun-Hwi HH Lee John Jonghyun JJ Lee Geun Woo GW

Nature communications 20240410 1

Solute structure and its evolution in supersaturated aqueous solutions are key clues to understand Ostwald's step rule. Here, we measure the structural evolution of solute molecules in highly supersaturated solutions of KH2PO4 (KDP) and NH4H2PO4 (ADP) using a combination of electrostatic levitation and synchrotron X-ray scattering. The measurement reveals the existence of a solution-solution transition in KDP solution, caused by changing mol ...[more]

PMID: 38600081

Similar Datasets

Second harmonic generation responses of KH2PO4: importance of K and breaking down of Kleinman symmetry.

Project description:The second harmonic generation (SHG) responses of the paraelectric and ferroelectric phases of KH2PO4 (KDP) were calculated by first-principles density functional theory (DFT) calculations, and the individual atom contributions to the SHG responses were analyzed by the atom response theory (ART). We show that the occurrence of static polarization does not enhance the SHG responses of the ferroelectric KDP, and that the Kleinman symmetry is reasonably well obeyed for the paraelectric phase, but not for the ferroelectric phase despite that the latter has a larger bandgap. This is caused most likely by the fact that the ferroelectric phase has lower-symmetry local structures than does the paraelectric phase. The contribution to the SHG response of an individual K+ ion is comparable to that of an individual O2- ion. The contributions of the O2- and K+ ions arise overwhelmingly from the polarizable parts of the electronic structure, namely, from the valence bands of the O-2p nonbonding states and from the conduction bands of the K-3d states.

| S-EPMC9055420 | biostudies-literature

Single Crystallization of Cs4PbBr6 Perovskite from Supersaturated Organic Solutions Optimized Through Solubility Studies.

Project description:We demonstrate the fabrication of millimeter-sized single crystals of 0D-Cs4PbBr6 grown in a supersaturated solution consisting of organic solvents without HBr (aq). One of the precursors, CsBr, was dissolved in ethylene glycol (EG) mixed with dimethyl sulfoxide, which is a good solvent for the other precursor, PbBr2. At a solvent ratio of 20 vol % EG, the solubility of cesium bromide decreased and the title compound, Cs4PbBr6, was selectively formed, whereas, with an EG ratio of 80 vol %, 3D-CsPbBr3 was formed. A phase diagram (solubility curve) of Cs4PbBr6 in the mixed solvent containing 20 vol % EG was obtained by visually observing dissolution and crystal precipitation while changing the temperature. Because the solubility was proportional to the temperature, the solubility curve demonstrated an upper critical solution phenomenon. The solubility near the boiling point of the solution (150 °C) was approximately 0.14 M. A single crystal of Cs4PbBr6 was formed by growing a seed crystal in a supersaturated solution on the low-temperature side of the solubility curve. X-ray analysis established the crystal structure; a fluorescence emission at 520 nm with a full width at half maximum of 20 nm confirms the composition of the single crystal to be Cs4PbBr6.

| S-EPMC9850476 | biostudies-literature

Laser-Induced Shockwave Crystallization in Supersaturated Solutions and Conceivable Clustering in Undersaturated Aqueous Potassium Nitrate Solutions.

Project description:In this study, a newly developed setup based on laser-induced shockwave crystallization coupled with electric conductivity monitoring was employed to study the growth of crystals in supersaturated solutions and to investigate possible clustering in undersaturated solutions of potassium nitrate (KNO3). A comparison was drawn between crystals induced by laser irradiation, by shockwaves, and spontaneously in terms of crystals' mean size, shape, and size distribution. The size distribution of produced crystals by shockwaves was also characterized in terms of laser irradiation time. The results show that produced crystals by shockwaves propagation have the sharpest size distribution and the smallest mean dimensions compared to crystals grown spontaneously or by direct laser induction. Real-time monitoring of nucleation was also performed in supersaturated solutions, while decrease in conductivity was observed in undersaturated solutions as a function of laser irradiation time.

| S-EPMC9631718 | biostudies-literature

Diffusionless (chemically partitionless) crystallization and subsequent decomposition of supersaturated solid solutions in Sn-Bi eutectic alloy.

Project description:Results of a study on microstructural evolution of eutectic Sn-57 wt.% Bi processed with cooling rates of 10-2, 1 K s-1 and approximately 105 K s-1 are presented. In order to distinguish different mechanisms of microstructure formation, a comparison with microstructures of different hypoeutectic alloys with compositions down to below the maximum solubility of Bi in Sn-Bi is undertaken. It is found that at the cooling rates of 10-2 and 1 K s-1, coupled eutectic growth occurs, leading to lamellar structures with different length scales. At the rapid quenching rates of approximately 105 K s-1, structure formation in the eutectic alloy is qualitatively different. Partitionless solidification resulting in a supersaturated solid solution with the initial composition is observed in both eutectic and hypoeutectic alloys. It is shown that the observed microstructure of the rapidly solidified alloys forms by the decomposition of the supersaturated solid solution. This article is part of the theme issue 'Heterogeneous materials: metastable and non-ergodic internal structures'.

| S-EPMC6460057 | biostudies-literature

Supersaturated calcium carbonate solutions are classical.

Project description:Mechanisms of CaCO3 nucleation from solutions that depend on multistage pathways and the existence of species far more complex than simple ions or ion pairs have recently been proposed. Herein, we provide a tightly coupled theoretical and experimental study on the pathways that precede the initial stages of CaCO3 nucleation. Starting from molecular simulations, we succeed in correctly predicting bulk thermodynamic quantities and experimental data, including equilibrium constants, titration curves, and detailed x-ray absorption spectra taken from the supersaturated CaCO3 solutions. The picture that emerges is in complete agreement with classical views of cluster populations in which ions and ion pairs dominate, with the concomitant free energy landscapes following classical nucleation theory.

| S-EPMC5786440 | biostudies-literature

Impact of heterocirculene molecular symmetry upon two-dimensional crystallization.

Project description:Despite the development of crystal engineering, it remains a great challenge to predict the crystal structure even for the simplest molecules, and a clear link between molecular and crystal symmetry is missing in general. Here we demonstrate that the two-dimensional (2D) crystallization of heterocirculenes on a Au(111) surface is greatly affected by the molecular symmetry. By means of ultrahigh vacuum scanning tunneling microscopy, we observe a variety of 2D crystalline structures in the coverage range from submonolayer to monolayer for D(8h)-symmetric sulflower (C16S8), whereas D(4h)-symmetric selenosulflower (C16S4Se4) forms square and rectangular lattices at submonolayer and monolayer coverages, respectively. No long-range ordered structure is observed for C(1h)-symmetric selenosulflower (C16S5Se3) self-assembling at submonolayer coverage. Such different self-assembly behaviors for the heterocirculenes with reduced molecular symmetries derive from the tendency toward close packing and the molecular symmetry retention in 2D crystallization due to van der Waals interactions.

| S-EPMC4067611 | biostudies-literature

Real-Time Observation of CaCO3 Mineralization in Highly Supersaturated Graphene Liquid Cells.

Project description:The mineralization dynamics of calcium carbonate is investigated under highly supersaturated conditions using graphene liquid cell transmission electron microscopy. We demonstrate that the mineralization process has three steps: nucleation, diffusion-limited growth, and Ostwald ripening/coalescence. In addition, we show that the polymorphs precipitate in a specific order, from metastable aragonite to stable calcite, thus proving Ostwald's rule of stages. In highly supersaturated solutions, the aragonite phase crystallizes in a stable manner, in addition to the calcite phase.

| S-EPMC7315570 | biostudies-literature

Nanoscale Dynamics of Protein Assembly Networks in Supersaturated Solutions.

Project description:Proteins in solution are conventionally considered macromolecules. Dynamic microscopic structures in supersaturated protein solutions have received increasing attention in the study of protein crystallisation and the formation of misfolded aggregates. Here, we present a method for observing rotational dynamic structures that can detect the interaction of nanoscale lysozyme protein networks via diffracted X-ray tracking (DXT). Our DXT analysis demonstrated that the rearrangement behaviours of lysozyme networks or clusters, which are driven by local density and concentration fluctuations, generate force fields on the femtonewton to attonewton (fN - aN) scale. This quantitative parameter was previously observed in our experiments on supersaturated inorganic solutions. This commonality provides a way to clarify the solution structures of a variety of supersaturated solutions as well as to control nucleation and crystallisation in supersaturated solutions.

| S-EPMC5665898 | biostudies-literature

Effects of Impurities on CaSO4 Crystallization in the Ca(H2PO4)2-H2SO4-H3PO4-H2O System.

Project description:Wet-process phosphoric acid is a fundamental process in the fertilizer industry. The influence of impurities on crystallization kinetics of CaSO4 was investigated in the Ca(H2PO4)2-H2SO4-H3PO4-H2O system using a mixed suspension mixed product removal crystallizer. Effects of Si, Al, Fe, Mg, K, and Na on crystal morphology and structure were examined in the highly acidic system through scanning electron microscopy and high-resolution transmission electron microscopy. Results show that the increase of Mg, K, and Na content facilitates crystal growth. Si, Al, and Fe are beneficial to CaSO4 crystal growth at a certain concentration range. Impurities also affect the crystal morphology, and the addition of Si, Fe, and Na promotes the formation of needle-like crystals compared with other impurities. X-ray diffraction results show that the preferred crystal growth direction is (020), and the interplanar spacing of the crystals is affected by the element radius of the impurities.

| S-EPMC6682056 | biostudies-literature

Upper Midwest lakes are supersaturated with N2.

Project description:Little is known about the exchange of gaseous nitrogen (N2) with the atmosphere in freshwater systems. Although the exchange of N2, driven by excess or deficiencies relative to saturation values, has little relevance to the atmospheric N2 pool due to its large size, it does play an important role in freshwater and marine nitrogen (N) cycling. N-fixation converts N2 to ammonia, which can be used by microbes and phytoplankton, while denitrification/anammox effectively removes it by converting oxidized, inorganic N to N2 We examined N2 saturation to infer net biological nitrogen processes in 34 lakes across 5° latitude varying in trophic status, mixing regime, and bathymetry. Here, we report that nearly all lakes examined in the upper Midwest (USA) were supersaturated with N2 (>85% of samples, n = 248), suggesting lakes are continuously releasing nitrogen to the atmosphere. The traditional paradigm is that freshwaters compensate for N-limitation through N-fixation, but these results indicate that lakes were constantly losing N to the atmosphere via denitrification and/or anammox, suggesting that terrestrial N inputs are needed to balance the internal N cycle.

| S-EPMC7382251 | biostudies-literature