Metastable Crystals Research Articles

Editorial

Editorial

Stabilizing Effect of Soluplus on Erlotinib Metastable Crystal Form in Microparticles and Amorphous Solid Dispersions.

Microparticles (MPs) and amorphous solid dispersions (SDs) are effective methods to improve the dissolution of insoluble drugs. However, stability is a concern for these two high-energy systems, resulting from high surface area and amorphous polymorph, respectively. As an amphiphilic polymer, Soluplus (SOL) is usually used as a carrier in SDs. In this study, erlotinib microparticles (ERL MPs) and erlotinib solid dispersions (ERL SDs) were prepared with SOL by bottom-up technology and solvent evaporation. The solid-state properties of ERL MPs and ERL SDs were characterized by Differential Scanning Calorimetry (DSC), Powder X-Ray Diffraction (PXRD) and Scanning Electron Microscopy (SEM). The ERL MPs existed in a metastable crystal form A while the ERL SDs existed in an amorphous state. Fourier transform infrared spectroscopy (FT-IR) showed that there was a hydrogen bond interaction between the N-H group of ERL and the carbonyl group of SOL in ERL MPs and SDs. The dissolution profiles of ERL SDs and ERL MPs were improved significantly. ERL MPs showed better stability than ERL SDs in accelerated stability test. The discrepant stabilizing effects of polymer SOL in two systems may provide effective ideas for solubilization of insoluble drugs and the stability of drugs after recrystallization.

A Microstructural and Compositional Study of ε-Fe2O3 Crystals in the Hare’s Fur Jian Ware

The Jian kilns in the present-day Jianyang County of Fujian Province are well known for their thick and lustrous black-glazed porcelain production. The hare’s fur (HF) glazed Jian wares characterized by radial fur-like strips, as one of the most typical representatives of black-glazed tea bowls, originate from phase separation of glaze melt and crystallization of iron oxides. In this study, various techniques were performed on the yellowish-brown HF samples, including portable energy-dispersive X-ray fluorescence (PXRF), synchrotron X-ray absorption near-edge spectroscopy (XANES), optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy (RS). The objective of this study was to well understand the microstructure characteristics and chemical compositions of glaze patterns. Results showed that the main constituents of the ceramic glaze were alumina (10.61–16.43 wt.%), silica (62.20–77.07 wt.%), calcium (3.85–6.97 wt.%), and iron oxide (4.10–8.35 wt.%). The studies provided evidence that metastable epsilon-iron oxide crystals (ε-Fe2O3) formed on the brownish-yellow glazed surface. Microstructural analysis revealed that there were three types of crystal structures in the glaze surface: One consisted of well-grown leaf-like or dendritic-like structure with highly ordered branches at micrometers scales; another comprised flower-like clusters accompanied by branches radiating from the center, petals growing along the branches, and needles on both sides of the petals; the last type involved a honeycomb structure tightly packed with plentiful spherical or irregular-shaped particles. In addition, ε-Fe2O3 crystals in the cross-section of the glaze showed a gradient distribution.

Formation of corundum in direct contact with quartz and biotite in clockwise <i>P–T</i> trajectory from the Sør Rondane Mountains, East Antarctica

We have found corundum in direct contact with quartz and biotite and as inclusions in garnet in the pelitic gneisses of northern Austkampane in the Northeastern (NE) Terrane of the Sør Rondane Mountains (SRM), East Antarctica. Our samples, which include corundum–bearing gneisses, show petrographic features such as staurolite inclusions in garnet, compositional zoning of orthoamphibole with Al decreasing toward the rims, and late–stage cordierite formation, and these features are characteristic of a clockwise P–T trajectory. The observations are consistent with the proposed regional clockwise P–T evolution of the NE Terrane in the SRM. The corundum and other inclusions observed in the garnet porphyroblasts are interpreted to have formed owing to either staurolite breakdown or metastable crystallization relative to kyanite prior to the peak metamorphism. The close association of biotite and quartz surrounding corundum inclusions suggests fluid– or melt–related processes. These petrographic features imply that the corundum and quartz (rarely observed in high–grade metamorphic rocks) formed as a result of metastable crystallization during the prograde stage of the clockwise P–T evolution of a continental collision zone.

Study of the activation barrier of metastable liquid crystallization by metadynamics

The crystallization of Lennard-Jones fluid under weak supercooling was studied in molecular dynamics simulation with the metadynamics method. The Steinhardt parameter Q6 for a group of particles around a random atom and the system's potential energy were chosen to describe phase transition. The change in collective variables was observed in the process of overcoming the activation barrier of crystallization. The critical nucleus formation data were obtained. Keywords: metadynamics, Lennard-Jones fluid, metastability, activation barrier.

A true color palette: binary metastable photonic pigments

Different from the traditional concept that binary photonic crystals can only reproduce mixed colors due to the simple superposition of the photonic band gaps, precisely addressable "true colors" obtained from volume fraction deviation of binary photonic crystals with metastable structures are reported here. Inspired by the mussels' adhesion and longhorn beetles' photonic scales, a binary metastable amorphous photonic crystal was obtained by enhancing the driving forces and customizing the surface roughness of building blocks to regulate the thermodynamic and dynamic factors simultaneously. By controlling the volume fraction of two building blocks, the tunable photonic bandgap varies linearly in the visible region. Furthermore, the "true violet" that cannot be obtained by conventional color mixing is reproduced with the particular ultraviolet characteristics of red photonic pigment's metastable structures, which complement the palette effect of "true colors". Meanwhile, due to the self-adhesion and post-modification of building blocks, the stability of photonic pigments is further improved. The binary photonic pigments not only solve the dilemma of mixed colors, but also realize the tunability and multiplicity of "true colors", offering a new choice for the color palette of the world.

Focal conic flowers, dislocation rings, and undulation textures in smectic liquid crystal Janus droplets.

Liquid crystalline phases of matter often exhibit visually stunning patterns or textures. Mostly, these liquid crystal (LC) configurations are uniquely determined by bulk LC elasticity, surface anchoring conditions, and confinement geometry. Here, we experimentally explore defect textures of the smectic LC phase in unique confining geometries with variable curvature. We show that a complex range of director configurations can arise from a single system, depending on sample processing procedures. Specifically, we report on LC textures in Janus drops comprised of silicone oil and 8CB in its smectic-A LC phase. The Janus droplets were made in aqueous suspension using solvent-induced phase separation. After drop creation, smectic layers form in the LC compartment, but their self-assembly is frustrated by the need to accommodate both the bowl-shaped cavity geometry and homeotropic (perpendicular) anchoring conditions at boundaries. A variety of stable and metastable smectic textures arise, including focal conic domains, dislocation rings, and undulations. We experimentally characterize their stabilities and follow their spatiotemporal evolution. Overall, a range of fabrication kinetics produce very different intermediate and final states. The observations elucidate assembly mechanisms and suggest new routes for fabrication of complex soft material structures in Janus drops and other confinement geometries.

Self-evolving materials based on metastable-to-stable crystal transition of a polymorphic polyolefin.

Living organisms can self-evolve with time in order to adapt to the natural environment. Analogically, self-evolving materials also show similar properties based on non-equilibrium structural transformation. The common design of these materials tends to rely on solutions and hydrogels, yet only little attention has been paid to dry materials. To break this limitation, a new principle for developing self-evolving materials from a commercialized polymorphic polyolefin via programmable crystal transition is proposed. The self-evolving materials can encode information on patterns and morphing by the metastable crystal phase. Dynamically, this phase transforms to the stable crystal phase so that the encoded information self-evolves with time, displaying the autonomous characteristic. Moreover, this process can be interrupted at an arbitrary time through solvent-induced recrystallization. These advantages have been demonstrated by fabricating an edible period indicator and imitating sophisticated human body language. It is believed that this work may inspire future research studies on self-evolving materials based on the non-equilibrium process of dry materials.

Controllable metastable growth of perovskite single crystals for highly sensitive X-ray detection

MAPbBr3 single crystals (SCs) were obtained by a low-temperature controllable metastable crystallization method, which regulates the growth process to low temperature and ensures excellent optoelectronic properties of the as-prepared SCs.

Variational theory of crystal growth and its application for analysis of forming processes for metastable phases in overcooled metallic melts with eutectic composition

The new crystallization theory for overcooled metastable melt is developed; it is based on variational mechanical principles and takes into account regularities of forming and diffusion growth of equilibrium crystals as well as diffusion-free growth of metastable crystals. Calculations for the melt Fe83B17 were conducted on the model; they displayed that simultaneous nucleation and growth of Fe and Fe2B with metastable phase Fe3B are observed in overcooled melt, and growth speed of near-critical dimensional crystals of Fe3B exceeds crystal growth speed of Fe and Fe2B. The effect of diffusion-free growth is observed for Fe3B crystals, when quickly growing Fe3B crystal surface catches boron atoms. Quasi-equilibrium phase diagram for overcooled Fe-B melt was built on the base of the developed theory; it takes into account both equilibrium crystal growth and metastable phase growth. The obtained diagram allows to predict the values of components concentration near the surface of growing crystals both for Fe and Fe2B crystals meeting the requirements of local equi-librium condition on their surface and for Fe3B metastable crystals which are characterized by diffusion-free growth stipulated by high motion speed of crystal surface.

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

Trevor Evans. 26 April 1927—10 October 2010

Trevor Evans was responsible for revealing the main physical processes which take place in natural diamond both in the upper mantle of the earth, where it is stabilized by high pressure and temperature, and as it is ejected by volcanic action to the surface. By measuring the activation energies required for graphitization, he clarified the reason for its very long life as a metastable crystal, valuable both as a gemstone and as an industrial abrasive. He learned how to make diamond specimens for examination in the transmission electron microscope, which enabled his discovery of dislocation loops and platelet precipitates in nitrogen-containing (type 1) stones. In a series of exacting laboratory experiments under geologically relevant conditions he pioneered the study of the emergence of nitrogen from solution to precipitation during the ejection process. In synthetic diamonds, using high-energy electron irradiation, he was able to reproduce the sequence of all the various types of nitrogen aggregation found in natural diamond. His work played a major role underpinning the characterization of gemstones, explaining many features of their colour. For many years he led diamond research in the UK, supported by De Beers. His work stimulated and has been confirmed by research in many other laboratories around the world.

Preparation, Stabilization, and Dissolution Enhancement of Vortioxetine Hydrobromide Metastable Polymorphs in Silica Nanopores

The development of metastable form crystals of active pharmaceutical ingredients is an effective method to improve the bioavailability of poorly soluble drugs, while the thermodynamic instability p...

The silanization process for the hydrothermal synthesis of hierarchical titanium silicalite-1

The silanization is an important approach for hierarchical zeolite preparation. Although the influences of the silanization conditions have been detailed studied, the differences in the reactivity of the zeolite precursor should further be analyzed. In this paper, hierarchical titanium silicalite-1 (HTS) was prepared with trimethoxy[3-(phenylamino)propyl]silane (TMPAPS) under the nTMPAPS:nSi = 0.04–0.20 and nTi:nSi = 0.005–0.04 conditions, the changes of the corresponding physicochemical properties were analyzed, and the influences of the condensation activities between silicon/titanium to the organosialne were deduced and verified by density functional theory (DFT) calculations. Generally, more supermicropores and mesopores can be created in the metastable sponge-like HTS crystals with higher TMPAPS and titanium contents. In comparison, the free energy barrier in the condensation reaction with titanium (1.31 eV) is lower than silicon (1.55 eV), it's preferential to prepare HTS with more intracrystalline secondary porosity by increasing the nTi:nSi. More importantly, the titanium can be isolated by the organosilane, and HTS with more framework titanium can be synthesized by silanization.

Cyclometalated Pt(II)‐Terpyridine Metallomesogen: What Is Visible or Invisible That Is a Matter of Molecular Packing and Orientation

AbstractAn anisotropic light emitting metallomesogen (PtM) consisting of a cyclometalated platinum(II)–terpyridine (Pt(II)–tpy) chromophore and a flexible dendron is newly synthesized as a thermal‐induced and polarization‐induced solid‐state luminescence switching material. The self‐assembled PtM is uniaxially aligned by mechanical shearing within the mesophase resulting in high optical anisotropy with chromophores. The shear‐induced metastable PtM crystal exhibits emission change depending on the polarization direction and thermally triggered reversible emission quenching‐recovery characteristic. In order to precisely control the optical feature of the PtM, the self‐assembled supramolecular structure and thermal‐sensitive photophysical properties are characterized. Based on the multiresponsive luminescence switching system of PtM, a multiplexed optical code is encrypted with a simple coating and its feasibility for optical anticounterfeiting applications is demonstrated.

Spray‐dried sol‐gel glass‐ceramic powders based on the tunable thermal expansion of quartz and keatite solid solutions

AbstractLithium aluminosilicate glass‐ceramic powders were synthesized by the heat treatment of spray‐dried sol‐gel glassy nanobeads, obtaining quartz solid solution (Qss) and keatite solid solution (Kss) crystals. Their composition ranged between 75 mol% SiO2 and pure silica along the spodumene join. The metastable crystals displayed tunable coefficients of thermal expansion ranging from +30 × 10−6 to −2.7 × 10−6 K−1 at room temperature, as obtained from their crystallographic characterization. The solid solution boundaries of Kss could be extended to 85 mol% SiO2. Concurrently, X‐ray diffraction measurements performed in situ at high temperature and at cryogenic conditions confirmed the known linear shift of the high‐low quartz inversion temperature upon increasing Al+Li doping. The obtained results qualify aerosol synthesis as a very versatile method for the production of glass‐ceramic powders in the LAS system.

The fate of compound with AgF2:AgO stoichiometry-A theoretical study.

Metal oxyfluorides constitute a broad group of chemical compounds with a rich spectrum of crystal structures and properties. Surprisingly though, none of the ternary oxyfluorides contains a cation from group 11 of the periodic table. Intending to find one, we focused on the silver derivative, the Ag2OF2 system, which may be considered as the 1:1 "adduct" of AgF2 (i.e., an antiferromagnetic positive U charge transfer insulator) and AgO (i.e., a diamagnetic disproportionated negative charge transfer insulator). Here, possible crystal structures of the silver oxyfluoride were studied using evolutionary algorithms based on the density functional theory approach. We analyzed the oxidation states of silver in the low-energy structures, possible magnetic interactions, and energetic stability with respect to the available substrates. Our findings suggest that silver oxyfluoride, if obtained, may form a metastable crystal with cations in three different oxidation states of the same element. Due to the small energy difference, existence of a fully disproportionated metallic compound cannot be ruled out. Finally, we outlined a prospect for the synthesis of polytypes of interest using diverse synthetic approaches, starting from the direct fluorination of Ag2O.

Morphological and structural study of crystals in black-to-brown glazes of Yaozhou ware (Song dynasty) using imaging and spectroscopic techniques

The Yaozhou kiln complex (Shaanxi, China) is a famous black-to-brown ceramic production center due to its significant volume of production, long manufacturing history (from Tang Dynasty to Yuan Dynasty) and variety of decorations. In this work, four representative types of black-to-brown ware from the Yaozhou kilns were selected to study the morphology, structure and distribution of the precipitated crystals in the glazes using a series of imaging and analytical techniques (optical microscopy, XRF, SEM-EDS, TEM-EDS, μRS and UV–vis-IR). The results show that the rare metastable ε-Fe2O3 phase, already observed in typical sauce glaze, was also detected in other types of brown glaze decorations, such as light brown stripes on a darker background or irregular brown spots on a black background. Cross-section analyses also showed a three well-separated layered crystalline distribution in the glazes of lighter brown colors as it has been noted in glazes from Qilizhen kilns. Raman analyses revealed that the crystals contained in third layer are of varying nature: ε-Fe2O3 in the sauce glaze and magnetite in the light brown stripes. The peak shifts and line broadenings observed in the Raman spectra of ε-Fe2O3 crystals were also investigated. They are the result of Al, Ti and Mg substitutions, which were identified using TEM-EDS. Such ionic substitutions would stabilize the metastable ε-Fe2O3 crystals by increasing the cationic disorder. In addition, Mg-, Ca- and Fe-rich spinel crystals were observed for the first time in a black glaze of Yaozhou wares.

Influence of Substitutional Groups on the Ordering and Crystallization of Amphiphilic Silsesquioxanes at the Air-Water Interface.

We report on the surface ordering and crystallization sequences in differently organic-substituted amphiphilic polyhedral silsesquioxane (POSS) variants induced by regulated compression at the air-water interface. Such molecular systems floating at the interface serve as a model system to study dynamic crystallization mediated by weak interactions. In situ grazing incidence X-ray scattering (GIXS) measurements, performed at a synchrotron X-ray source using a liquid surface diffractometer and corroborated with Brewster angle microscopy, revealed transformations for the different POSS variants (viz. trisilanol isobutyl POSS (TBPOSS), trisilanol cyclohexyl POSS (TCHPOSS), disilanol octaisobutly POSS (DOBPOSS), and trisilanol isooctyl POSS (TOPOSS)) from a weakly correlated monolayer structure to appreciably different structural and crystalline phases in various packing schemes. GIXS measurements revealed a stable nature of the crystallization of DOBPOSS, varying degrees of metastable crystallization for TCHPOSS and TBPOSS, and complete absence of crystalline phase in TOPOSS molecules. Incidentally, for all POSS variants showing crystalline phases, the motifs always assembled in a triclinic lattice with P1̅ symmetry. For the metastable crystals, preferential surface ordering of the crystallites promotes selective crystalline planes to exhibit preferred tilt angles with respect to the interface. The structural transformations of the differently substituted POSS molecules and their variations therein are attributed to the changing balance of the hydrophobic vs hydrophilic interaction in the layers, which is determined by the anisotropic shape and distribution of substitutional groups over the nanosized core cage of the monomer, steric interaction between nearest dimeric neighbors, as well as the in-plane and out-of-plane assembly of the overlayers.

Iron oxide and jadeite nucleation in high alumina glass-ceramics prepared from secondary aluminum dross

Secondary aluminum dross (SAD) is a solid waste of aluminum dross after it is extracted aluminum. Soda-lime-aluminosilicate (SLAS) glass-ceramics with high alumina contents (over 30 wt%) were successfully manufactured from SAD using pyrometallurgy without additional nucleation agents. The nucleation process of SLAS glass was studied, and 670 °C was selected as the nucleation temperature according to differential scanning calorimetry and X-ray diffraction results. Field-emission transmission electron microscopy was applied to study the microstructure of the specimens thermally treated at 670 °C for 3 and 12 h. Nucleation consisted of two parts: iron oxide nucleation and jadeite nucleation. During iron oxide nucleation, when the thermal treatment time increased from 3 to 12 h, the iron oxides first congregated in an amorphous phase and a small amount of metastable crystal; then, the congregated iron oxides crystallized into hematite and magnetite, which acted as crystal nuclei. During jadeite nucleation, the jadeite spontaneously crystallized from the glass matrix after thermal treatment at 670 °C. When the thermal treatment time increased from 3 to 12 h, the size of the jadeite crystals increased from approximately 6 to 12 nm. Jadeite crystals with a diameter of 12 nm acted as crystal nuclei. For glass-ceramics with a high content of aluminum and sodium, jadeite crystals can act as crystal nuclei without additional nucleation agents.