Crystal Polymorphism Research Articles

D–π–A-type fluorinated tolanes with a diphenylamino group: crystal polymorphism formation and photophysical behavior

Ph2N-Substituted fluorinated tolanes produced two polymorphisms, which display a distinct photoluminescence behavior; one polymorphism showed green PL and the other exhibited yellow PL.

New patterns of twist-bend liquid crystal phase behaviour: the synthesis and characterisation of the 1-(4-cyanobiphenyl-4'-yl)-10-(4-alkylaniline-benzylidene-4'-oxy)decanes (CB10O·m).

The synthesis and characterisation of the 1-(4-cyanobiphenyl-4'-yl)-10-(4-alkylanilinebenzylidene-4'-oxy)decanes (CB10O·m) are reported. This series shows a rich liquid crystal polymorphism including twist-bend nematic and smectic phases. All the homologues reported exhibit an enantiotropic conventional nematic phase. For the homologues with m ≤ 10, the local packing in the nematic phases and the layer spacing in the smectic phases indicates an intercalated arrangement of the molecules. An intercalated smectic CA phase is observed if m/11 ≈ 0.5. Either side of this condition, the twist-bend nematic phase is observed, a novel pattern of behaviour for a series on increasing a terminal chain length. For longer chain lengths, m = 12, 14, 16 and 18, two twist-bend smectic C (SmCTB) phases are observed, and the packing of the molecules is now of a bilayer-type. The higher temperature variant is termed SmCTB-SH in which SH (single helix) refers to the presence of a short, distorted clock-type helix. In the lower temperature SmCTB-DH phase, an additional longer helix is superimposed on the short one, and DH denotes double helix.

Impact of free energy of polymers on polymorphism of polymer-grafted nanoparticles.

Colloidal crystals have gathered wide attention as a model material for optical applications because of their feasibility in controlling the propagation of light by their crystal structure and lattice spacing as well as the simplicity of their fabrication. However, due to the simple interaction between colloids, the colloidal crystal structures that can be formed are limited. It is also difficult to adjust the lattice spacing. Furthermore, colloidal crystals are fragile compared to other crystals. In this study, we focused on polymer-grafted nanoparticles (PGNP) as a possible solution to these unresolved issues. We expected that PGNPs, composed of two distinct layers (the hard core of a nanoparticle and the soft corona of grafted polymers on the surface), will demonstrate similar behaviors as star polymers and hard spheres. We also predicted that PGNPs may exhibit polymorphism because the interaction between PGNPs strongly depends upon their grafting density and the length of the grafted polymer chains. Moreover, we expected that crystals made from PGNPs will be structurally tough due to the entanglement of grafted polymers. From exploration of crystal polymorphs of PGNPs by molecular dynamics simulations, we found face-centered cubic (FCC)/hexagonal close-packed (HCP) and body-centered cubic (BCC) crystals, depending on the length of the grafted polymer chains. When the chains were short, PGNPs behaved like hard spheres and crystals were arranged in FCC/HCP structure, much like the phase transition observed in an Alder transition. When the chains were long enough, the increase in the free energy of grafted polymers was no longer negligible and crystals were arranged in BCC structure, which has a lower density than FCC/HCP. When the chains were not too short or long, FCC/HCP structures were first observed when the volume fraction of system was small, but a phase transition occurred when the system was further compressed and the crystals arranged themselves in a BCC structure. These results most likely have laid strong foundations for future simulations and experimental studies of PGNP crystals.

Tricolor fluorescence switching in the three crystal polymorphs of tetraphenylethylene modified fluorenone AIEgen

We employ the molecular design strategy of introducing multiple weak interactions and twisted molecular structure into the same molecular system to synthesize a new AIEgen, which exhibited stimuli-responsive crystalline tricolor fluorescent switching.

Zwitterionic iodonium species afford halogen bond-based porous organic frameworks.

Porous architectures characterized by parallel channels arranged in honeycomb or rectangular patterns are identified in two polymorphic crystals of a zwitterionic 4-(aryliodonio)-benzenesulfonate. The channels are filled with disordered water molecules which can be reversibly removed on heating. Consistent with the remarkable strength and directionality of the halogen bonds (XBs) driving the crystal packing formation, the porous structure is stable and fully preserved on almost quantitative removal and readsorption of water. The porous systems described here are the first reported cases of one-component 3D organic frameworks whose assembly is driven by XB only (XOFs). These systems are a proof of concept for the ability of zwitterionic aryliodonium tectons in affording robust one-component 3D XOFs. The high directionality and strength of the XBs formed by these zwitterions and the geometrical constraints resulting from the tendency of their hypervalent iodine atoms to act as bidentate XB donors might be key factors in determining this ability.

Tuning polymorphs of precipitated calcium carbonate from discarded eggshells: effects of polyelectrolyte and salt concentration.

Biowaste eggshells are a valuable source of calcium carbonate suitable for various applications. In this study, spherical vaterite and calcite calcium carbonate polymorphs have been synthesised from discarded eggshells by the precipitation technique at ambient temperature. The influence of initial salt concentration with different polyelectrolytes such as ethylene glycol (EG), polyethylene glycol (PEG, 600 and 6000), and poly(sodium 4-styrenesulfonate) (PSS) at various w/v% concentrations on the polymorph crystal formation of precipitated calcium carbonate (PCC) particles was studied. The results indicated that PCC crystals with spherical, star-shaped and yarn shaped morphologies can be obtained based on the concentration of calcium ions and the presence of different polyelectrolyte solution. At low salt molar concentration, PEG-6000 and PSS polyelectrolytes were found to promote the formation of spherical vaterite calcium carbonate particles with particle mean diameters of 5.05 μm and 2.17 μm, respectively. Furthermore, silver nanoparticles were also loaded into the PCC particles in situ, and the surface area significantly increased from 2.2813 m2 g−1 in untreated ground eggshells to 30.4632 m2 g−1 in PCC particles in the presence of PSS and silver colloid solution. The EDS mapping revealed the average wt% of silver atoms loaded in PCC particles in the presence of PSS polyelectrolyte was lower (1.44 wt%) than in the presence of PEG-6000 (4.27 wt%) due to the silver encapsulation possibility during the core–shell formation, as confirmed by SEM images. The silver nanoparticle-loaded PCC particles in this study can be incorporated into the polymer matrix and employed for antimicrobial food packaging or wound dressing application.

Otolith Analyses Highlight Morpho-Functional Differences of Three Species of Mullet (Mugilidae) from Transitional Water

Otoliths are used in taxonomy and ichthyology as they can provide a wide range of information about specimens. They are an essential tool to monitor the most sensitive species for a sustainable exploitation level. Despite the increasing use of sagittae in research, their inter- and intra-specific variability and eco-functionality are still poorly explored. This paper aims to investigate the inter- and intra-specific variability of Mugilidae sagittae using morphological and morphometrical analysis, as well as scanning electron microscopy and shape analysis. The sagittae of 74 specimens belonging to three different Mugilidae species, collected from a coastal lagoon, were analyzed to give an accurate description of their morphology, morphometry, shape and crystalline habits. The results highlighted the intra- and inter-specific variability of sagittae, showing morphometrical differences among species and slight differences between left and right sagittae in C. labrosus individuals. Moreover, SEM images showed a peculiar crystal organization, with several different crystal habits and polymorphs. This study provides an accurate description of sagittae in the studied species, deepening the knowledge on inter- and intra-specific variations and crystal habits and providing data which will be useful for future studies on otoliths. With this data, it will be possible to improve conservation and exploitation sustainability in sensitive habitats.

GABA-Controlled Synthesis of the Metastable Polymorphic Form and Crystallization Behavior with a Chiral Malic Acid

GABA-Controlled Synthesis of the Metastable Polymorphic Form and Crystallization Behavior with a Chiral Malic Acid

Heterogeneous Nucleation Effects of Talc Particles on Polymorphic Crystallization of Cocoa Butter

Polymorphic crystallization of cocoa butter (CB) in a bulk system was examined for the influence of adding talc particles at different concentrations (0.1–5%). While the system was cooled from the melt and subsequently heated, changes in the heat flow and crystal structure of CB were analyzed using differential scanning calorimetry (DSC) and synchrotron radiation X-ray diffraction (SR-XRD). Synchrotron radiation microbeam X-ray diffraction (SR-μ-XRD) was employed to determine lamellar-plane directions of CB crystals occurring with talc addition. At any cooling rates (0.1–15 °C/min) applied, talc promoted CB crystallization to elevate the onset crystallization temperature logarithmically with the increasing concentration of talc; this effect became more prominent at higher cooling rates. Talc also acted as a polymorphic stabilizer so that CB crystallized in more stable forms even when cooled at highest rate of 15 °C/min. Moreover, a highly ordered lamellar-plane direction was extensively observed for CB crystals occurring with 0.1% talc addition, which was disturbed by 0.5% talc addition probably due to the spatial dispersion of densely populated talc particles in their randomized orientation. These heterogeneous nucleation effects indicate the potential of talc particles to be used for the quality and productivity control of CB-based products.

Nuclear Magnetic Resonance (NMR) study of Palm Kernel Stearin: Effects of cooling rate on crystallization behaviour

In this study, effects of different cooling rates (0.5,3.3,4.7 and 6.9 °C/min) on the crystallization behavior of palm-kernel-stearin (PKS) were studied by low-field NMR relaxometry. According to results, solid fat content (SFC), longitudinal relaxation time (T1), second moment (M2) and degree of crystallinity (%) of the samples increased with increase in cooling rate from 0.5 to 6.9 °C/min. In contrast, transverse relaxation time (T2) demonstrated an opposite behavior with respect to T1 and decreased when the cooling rate increased. Additionally, effects of cooling rate on the changes of polymorph structures were detected by X-ray measurements. Degree of crystallinity showed high Pearson correlation values (α ≤ 0.05) with SFC (r= 0.771) and T1(r= 0.932). Changes in the crystal polymorphs could also be explained by NMR parameters to some extent as can be observed by the strong correlation between the β crystal content and T2 (r= 0.927). At the highest cooling rate, β′ crystals were the dominant polymorphic form and constituted 75(%) of the total crystals present. Results of this study suggested that NMR relaxometry could be used as a complementary tool to interpret the crystallization behavior of PKS.

Mean-Field Effects on the Phosphorescence of Dinuclear Re(I) Complex Polymorphs.

A computational study rationalizes the different phosphorescence colors of two highly emitting crystal polymorphs of a dinuclear Re(I) complex, [Re2(μ-Cl)2(CO)6(μ-4,5-(Me3Si)2pyridazine)]. The electrostatic interactions between the charge distributions on neighboring molecules inside the crystal are responsible for the different stabilization of the emitting triplet state because of the different molecular packing. These self-consistent effects play a major role in the phosphorescence of crystals made of polar and polarizable molecular units, offering a powerful handle to tune the luminescence wavelength in the solid state through supramolecular engineering.

Low Temperature and High-Pressure Study of Bending L-Leucinium Hydrogen Maleate Crystals

The polymorphism of molecular crystals is a well-known phenomenon, resulting in modifications of physicochemical properties of solid phases. Low temperatures and high pressures are widely used to find phase transitions and quench new solid forms. In this study, L-Leucinium hydrogen maleate (LLHM), the first molecular crystal that preserves its anomalous plasticity at cryogenic temperatures, is studied at extreme conditions using Raman spectroscopy and optical microscopy. LLHM was cooled down to 11 K without any phase transition, while high pressure impact leads to perceptible changes in crystal structure in the interval of 0.0–1.35 GPa using pentane-isopentane media. Surprisingly, pressure transmitting media (PTM) play a significant role in the behavior of the LLHM system at extreme conditions—we did not find any phase change up to 3.05 GPa using paraffin as PTM. A phase transition of LLHM to amorphous form or solid–solid phase transition(s) that results in crystal fracture is reported at high pressures. LLHM stability at low temperatures suggests an alluring idea to prove LLHM preserves plasticity below 77 K.

Combining Structural Rugosity and Crystal Packing Comparison: A Route to More Polymorphs?

In this study, we have combined structural comparisons and the rugosity model to investigate experimental and predicted crystal structures from previous results of a crystal structure prediction study on a group of three rigid, planar small molecules, 2-methyl-, 3-methyl-, and 2,3-dimethyl-benzo[b]thiophene 1,1-dioxide. The results of the crystal structure comparisons provided some insights into the possibility that pairs of predictions, close in energy, might be related by potential phase transitions. In particular, we observed that for some pairs of predictions, a transformation from one type of crystal packing to the other would require only small shifts between adjacent molecules. This raised the question of whether only a few of these predictions can effectively be experimentally isolated. The calculations of the structural rugosity, a parameter that correlates surface rugosity with ease of crystallization, indicated smooth surfaces only for a few predictions. With the aim to isolate new polymorphs, we performed a small experimental study, limited to a few common solvents and crystallizations from the melt. Crystallizations from the melt selectively produced single crystals of new polymorphs for the 3-methyl- and the 2,3-methyl-benzothiophene derivatives. These showed good correlations with the above calculations, suggesting that the combination of crystal structure analysis and experimental screening might represent a useful approach in polymorphism screenings.

Dopamine- and citrate-mediated, rapid synthesis of hollow calcium carbonate nanoparticles: Their formation, metastability and transformation

Exquisite design of calcium carbonate (CaCO3) is essential to meet the demands on the properties of functional materials for various applications, where additives play a crucial role in controlling over size, orientation, polymorph, and hierarchical structure. However, we are far from achieving the elaborate control over their structures and morphologies by use of the individual additive. Herein, we develop a simple and template-free approach for the rapid fabrication of hollow CaCO3-based nanocarriers via dual-additive mediated crystallization. The roles of additives and the impact of corresponding concentrations are systematically investigated to achieve a tunable and reliable design of CaCO3 particles, simultaneously yielding clues of how the additives mediated the formation of different morphology of amorphous calcium carbonate (ACC). Compared to single citrate-mediated ACC, dual-additive mediated hollow ACC renders them the prolonged stability and also facilitates their oriented crystallization into the homogeneous hierarchical architectures. Therefore, our findings indicate that the combined additives of dopamine and citrate exert synergistic effects on hollow structure formation and metastability as well as the subsequent crystallization, which contributes to deeper insight into additive-mediated crystallization pathway. These findings may offer new opportunities to design CaCO3-based materials with controllable morphology and crystal polymorphs.

Memory Effect and Crystallization of (R, S)-2-Chloromandelic Acid Glass.

(R, S)-2-Chloromandelic acid, which can crystallize in racemic crystals (forms α and β) or a conglomerate (form γ), has been studied for its glass-forming behavior. Below the glass transition temperature, samples of the title compound crack into pieces. Correlation plots of DSC results have been used to investigate what determines the cracking and its occurrence temperature. We found that the latter is influenced by the polymorph from which the melt state has been obtained, showing that a certain memory of the previous crystalline phase persists in the undercooled melt. Moreover, this residual structure could be eliminated by elongating the annealing period or increasing the annealing temperature. Investigation using broadband dielectric spectroscopy confirmed such a memory effect. Finally, we studied the role of cracking in the control of the crystallization. In contrast with previous literature on other glass-forming molecular systems, we verified that the crystallization upon reheating is not impacted by the occurrence of cracks in the glassy state. This observation challenges the current views on polymorphic crystallization from organic glasses.

Direct observation of the moment of nucleation from a solution by TEM

Abstract Recent discoveries of various nucleation processes make understanding the initial processes of crystallization, where atoms and molecules come together to form a crystal nucleus, difficult. Herein, transmission electron microscopy is used to directly visualize the moment of nucleation from a solution and to show that the singular phenomena of nanoparticles are critical to understanding nucleation. Our work revealed that nanoparticles undergo precipitation and dissolution even in undersaturated and equilibrium conditions, that crystal polymorphs formed at different frequencies compete, that molecules follow various nucleation pathways in the same solution, and that the hydration layer plays a critical role in crystallization. The observations visually support the common belief that dehydration is the greatest barrier to crystallization in an aqueous solution. These results are expected to contribute to the development of a unified nucleation model.

Enabling Large-Scale Condensed-Phase Hybrid Density Functional Theory-Based Ab Initio Molecular Dynamics II: Extensions to the Isobaric-Isoenthalpic and Isobaric-Isothermal Ensembles.

In the previous paper of this series [Ko, H.-Y. et al. J. Chem. Theory Comput. 2020, 16, 3757-3785], we presented a theoretical and algorithmic framework based on a localized representation of the occupied space that exploits the inherent sparsity in the real-space evaluation of the exact exchange (EXX) interaction in finite-gap systems. This was accompanied by a detailed description of exx, a massively parallel hybrid message-passing interface MPI/OpenMP implementation of this approach in Quantum ESPRESSO (QE) that enables linear scaling hybrid density functional theory (DFT)-based ab initio molecular dynamics (AIMD) in the microcanonical/canonical (NVE/NVT) ensembles of condensed-phase systems containing 500-1000 atoms (in fixed orthorhombic cells) with a wall time cost comparable to semi-local DFT. In this work, we extend the current capabilities of exx to enable hybrid DFT-based AIMD simulations of large-scale condensed-phase systems with general and fluctuating cells in the isobaric-isoenthalpic/isobaric-isothermal (NpH/NpT) ensembles. The theoretical extensions to this approach include an analytical derivation of the EXX contribution to the stress tensor for systems in general simulation cells with a computational complexity that scales linearly with system size. The corresponding algorithmic extensions to exx include optimized routines that (i) handle both static and fluctuating simulation cells with non-orthogonal lattice symmetries, (ii) solve Poisson's equation in general/non-orthogonal cells via an automated selection of the auxiliary grid directions in the Natan-Kronik representation of the discrete Laplacian operator, and (iii) evaluate the EXX contribution to the stress tensor. Using this approach, we perform a case study on a variety of condensed-phase systems (including liquid water, a benzene molecular crystal polymorph, and semi-conducting crystalline silicon) and demonstrate that the EXX contributions to the energy and stress tensor simultaneously converge with an appropriate choice of exx parameters. This is followed by a critical assessment of the computational performance of the extended exx module across several different high-performance computing architectures via case studies on (i) the computational complexity due to lattice symmetry during NpT simulations of three different ice polymorphs (i.e., ice Ih, II, and III) and (ii) the strong/weak parallel scaling during large-scale NpT simulations of liquid water. We demonstrate that the robust and highly scalable implementation of this approach in the extended exx module is capable of evaluating the EXX contribution to the stress tensor with negligible cost (<1%) as well as all other EXX-related quantities needed during NpT simulations of liquid water (with a very tight 150 Ry planewave cutoff) in ≈5.2 s ((H2O)128) and ≈6.8 s ((H2O)256) per AIMD step. As such, the extended exx module presented in this work brings us another step closer to routinely performing hybrid DFT-based AIMD simulations of sufficient duration for large-scale condensed-phase systems across a wide range of thermodynamic conditions.

Chasing the Co-crystal Disappearing Polymorph with Ab Initio Methods

Crystal polymorphism has a major impact on material properties such as thermal stability, bioavailability, and solubility. The application of co-crystals in the pharmaceutical industry requires polymorph screening to avoid unwanted phase transitions, which can cause property reduction. In this work, three polymorphs of urea–barbituric acid (1:1) co-crystals were investigated to describe the dynamic character of their H-bond networks and to explain the disappearance of the polar polymorph. For the studied polymorphs, Born–Oppenheimer molecular dynamics simulations were performed. Detailed analysis of hydrogen bonds and power spectra calculations were conducted using the obtained trajectories. The relative stability of each polymorph has been considered in terms of NVT and NVE ensembles. The results of computations were discussed in light of the analysis of H-bond propensities, coordination scores, and the obtained experimental data. To our knowledge, the polar form of urea–barbituric acid co-crystal can be called one of the first known examples of co-crystal disappearing polymorph.

Nanocrystalline single-phase high-entropy alloy synthesized by using intermetallic compound type (TiZrHf)-(NiCuCo) high-entropy metallic glass precursor

‘AB’ intermetallic compound (IC) type (TiZrHf)-(NiCuCo) high-entropy metallic glass precursor (HE-MGP) has been designed under considering physical and thermodynamic relations between constitutive elements, such as atomic size difference, electronegativity difference, mixing enthalpy and entropy, and phase stability, for development of nanocrystalline single-phase high-entropy alloy. The IC type HE-MGP exhibits high thermal stability and polymorphic crystallization behavior. From the systematic investigations on crystallization kinetics and microstructural evolution, it was found that the HE-MGP crystallized into nanocrystalline single-phase high-entropy alloy with B2 structure by polymorphic crystallization, and nucleation and growth rates for crystallization processing strongly depend on the annealing temperature. Our approach and discovery provide an effective way to develop the nanocrystalline single-phase high-entropy alloys by designing IC type HE-MGP.

Effects of crystallization temperature on the characteristics of sugar crystals in date fruit syrup as measured by differential scanning calorimetry (DSC), polarized microscopy (PLM), and X-ray diffraction (XRD).

Characteristics of sugar crystals are important for developing set-syrup due to their contribution to the desired mouth feel when consumed. Two types of set-syrup (i.e. seeds with and without) were developed by storing the syrup at -20, 4 and 15°C. The melting temperatures (onset and peak), and enthalpy of set-syrup without seeds (SN) were 30.2°C, 74.6°C and 42.2kJ/kg respectively. In the case of SN, enthalpy decreased with the decrease of crystallization temperature (P < 0.05), while there was insignificant change in the case of set-syrup with seeds (SW) (P > 0.05). Polarized Light Microscopy (PLM) images showed that finer crystals were formed in the cases of set-syrups (i.e. SN and SW) as the storage temperature was decreased. X-ray diffraction (XRD) analysis showed the formation of different polymorphic sugar crystals. Crystallization temperatures at 4 and -20°C can be used to produce finer crystals with varied polymorphic characteristics.