Chiral symmetry breaking in NaClO3 crystallization from an aqueous solution with perturbations has been of great interest. To understand the mechanism, several models focusing on the early stage of the crystallization have been proposed. However, they are ambiguous because the early stage has been barely explored directly. Here, we investigate the early stages of the crystallization process driven by droplet evaporation using a combination of direct in situ microscopic observations and cryogenic single-crystal XRD experiments. We demonstrate that an achiral crystal having P21/a symmetry, which is newly discovered for a solution growth, first appears in the droplet and then transforms into the chiral crystals. Additionally, determination of the lattice constants by XRD experiments (a = 8.42 Å, b = 5.26 Å, c = 6.70 Å, β = 109.71°) revealed that the achiral phase should be identical to Phase III (a = 8.78 Å, b = 5.17 Å, c = 6.83 Å, β = 110°), which is a high-temperature phase from a melt growth of NaClO3. We advocate further assessment of the achiral crystal and a new pathway for the formation of chiral crystals via crystalline phase transition from achiral Phase III.
We demonstrate that a statistically-significant chiral bias in NaClO 3 chiral crystallization can be provoked by inducing nucleation via the optical trapping of Ag nano-aggregates using a continuous wave visible circularly polarized laser (λ = 532 nm). The laser was focused at the interface between air and an unsaturated NaClO 3 aqueous solution containing Ag nanoparticles. The "dominant" enantiomorph was switchable by changing the handedness of the incident circularly polarized laser, indicating that the chiral bias is enantioselective. Moreover, it has been found that the resulting crystal enantiomeric excess (CEE) reached approximately 25%. The CEE is much higher than the typical enantiomeric excess (EE) in the asymmetric photosynthesis of organic compounds ranging from 0.5 to 2%. The efficient induction of the nucleation and the large chiral bias imply the contribution of localized surface plasmon resonance of the Ag nanoaggregates to chiral nucleation. Our method has potential to offer the benefit for studies on the spatiotemporal nucleation control, optical resolution of chiral compounds and biohomochirality.
Chiral symmetry breaking during the chiral crystallization from a sodium chlorate (NaClO3) aqueous solution is an intriguing phenomenon because it provides insights into the prebiotic process of biohomochirality. However, a mechanism of the emergence and amplification of chirality remains controversial, especially for crystallization from highly supersaturated solution, and one of the hypotheses proposed before is a transition toward the homochiral state during the early stages of crystallization. In this contribution, we directly examined the early stage of crystallization by in situ polarized-light microscopy. The observation revealed that achiral crystals, which appear prior to the formation of chiral crystals, transform to the chiral crystal through two kinds of polymorphic transformations: (1) martensitic transformation (MT) and (2) solution-mediated phase transition (SMPT). The SMPT is remarkably facilitated by contact with a chiral crystal. Notably, the resulting enantiomorph through contact-facilitated SMPT is strongly directed by the contacting enantiomorph. In contrast, the MT yields two enantiomorphs in equal probability. The emergence and amplification of chirality has generally been considered to be a result of direct nucleation of a chiral crystal and its fragmentation. In contrast, our observations provide a possibility that the MT and contact-facilitated SMPT play a role for the emergence and amplification of chirality, respectively.
We reversibly controlled phase conversion between a microdroplet of a NaClO 3 unsaturated aqueous solution and a metastable single crystal, which is usually a short-lived phase in spontaneous crystallization, simply by irradiating a tightly focused visible continuous-wave (CW) laser to the microdroplet. The laser irradiation allowed the metastable crystal to generate and stably grow without a polymorphic transformation. This successful metastable phase control is attributed to the combination of the advantage of optical trapping-induced nucleation that nucleation takes place from unsaturated mother solution and the advantage of microdroplet method, which suppresses additional nucleation leading to the transformation. In situ observation shows the crystal dissolves when the laser irradiation is stopped, whereas the laser irradiation stabilizes the crystal even if the size of the crystal becomes larger than that of focal spot. These observations indicate that a change in the relative magnitudes of chemical potentials between solution/crystalline phases. This change is possibly promoted via crystal growth by trapping of crystalline clusters in optical potential well formed on a crystal surfaces originating from "light propagation" through the crystal. Our results shed a light not only on polymorph control but also on a method to prepare a longer-lived achiral precursor for analysis on achiral−chiral transition by "freezing" a kinetic pathway of chiral crystallization
The control of step bunching by solution flow in 4H-SiC solution growth is proposed. We achieved the solution flow control with the specially designed top-seeded solution growth method as follows: by deviating a seed crystal from the center of a crucible and rotating the crucible in one direction, the solution flow direction was controlled to be parallel or antiparallel to the step-flow direction. After the growth, the widely spaced, accumulated macrosteps were observed and the surface of the grown crystal became rough under the parallel flow. On the other hand, the development of the macrosteps was suppressed under the antiparallel flow. As the growth proceeds, the surface roughness of the growth surface increases under the parallel flow, while the surface roughness decreases under the antiparallel flow. This fact suggests the solution flow control can be an effective method to suppress the step bunching during the solution growth of SiC single crystals.
The formation of crystals from solution requires the initial self-assembly of units of matter into stable periodic structures reaching a critical size. The early stages of this process , called nucleation, are very difficult to visualize. Here we describe a novel method that allows real time observation of the dynamics of nucleation and dissolution of sodium chlorate clusters in an ionic liquid solution using in situ transmission electron microscopy. Using ionic liquids as solvent circumvents the problem of evaporation and charging, while the nucleation frequency was reduced by using saturated solutions. We observe simultaneous formation and dissolution of prenucleation clusters, suggesting that high-density fluctuations leading to solid cluster formation exist even under equilibrium conditions. In situ electron diffraction patterns reveal the simultaneous formation of crystalline nuclei of two polymorphic structures, the stable cubic phase and the metastable monoclinic phase, during the earliest stages of nucleation. These results demonstrate that molecules in solution can form clusters of different polymorphic phases independently of their respective solubility.
Plasmonic manipulation using well-designed triangular trimeric gold nanostructures achieves a giant (greater than 50%) crystal enantiomeric excess (CEE) of sodium chlorate (NaClO 3 ). Stronger asymmetric interactions between molecule and light are pursued to reach high enantiomeric excess. The well-designed gold nanostructures immersed in a saturated NaClO 3 D 2 O solution were irradiated with linear, left-hand, and right-hand circular polarizations of a 1064 nm continuous-wave laser. Within seconds of the start of the irradiation, an achiral metastable crystal was formed at the laser focus, and further irradiation induced a subsequent polymorphic transition to the chiral crystal. The crystal chirality is sensitive to the handedness of circular polarization, allowing for efficient enantioselectivity. The mechanisms to achieve this giant CEE are proposed based on the results of electromagnetic field analysis generated near the nanostructure by the finite element method.
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