Detonation of fulminating gold produces heterogeneous gold nanoparticles.

Fulminating gold, the first high-explosive compound to be discovered, disintegrates into a mysterious cloud of purple smoke, the nature of which has been speculated upon since its discovery in the 15th century. In this work, we show that the colour of the smoke is due to the presence of gold nanoparticles.

Morphological Control of Crystalline Savolitinib via the Volatile Deep Eutectic Solvent Technique.

Savolitinib is a compound that can crystallize in an undesirable, high aspect ratio needle morphology. This morphology type may cause issues in downstream processing. This paper demonstrates a unique method to alter the crystal morphology of savolitinib to make it more processable, resulting in the active pharmaceutical ingredient (API) crystallizing out in considerably more processable stellates. The volatile deep eutectic solvent technique presents a simple and scalable method for changing the crystal morphology while maintaining the polymorph of the API in this case, confirmed via powder X-ray diffraction and differential scanning calorimetry analysis.

Improved air-stability and conductivity in the 75Li2S·25P2S5 solid-state electrolyte system: the role of Li7P3S11.

Doping modification is regarded as a simple and effective method for increasing the ionic conductivity and air stability of solid state electrolytes. In this work, a series of (100-x)(0.75Li2S·0.25P2S5)·xP2O5 (mol%) (x = 0, 1, 2, 3 and 4) glass-ceramic electrolytes were synthesized by a two-step ball milling technique. Various characterization techniques (including powder X-ray diffraction, Raman and solid-state nuclear magnetic resonance) have proved that the addition of P2O5 can stimulate 75Li2S·25P2S5 system to generate the high ionic conductivity phase Li7P3S11. Through the doping optimization strategy, 98(0.75Li2S·0.25P2S5)·2P2O5 glass-ceramic (2PO) not only had a 3.6 times higher ionic conductivity than the undoped sample but also had higher air stability. Its ionic conductivity remained in the same order of magnitude after 10 minutes in the air. We further investigated the reasons why 2PO has a relatively high air stability using powder X-ray diffraction and scanning electron microscopy in terms of crystal structure degradation and morphology changes. In comparison to the undoped sample, the high ionic conductivity phases (ß-Li3PS4 and Li7P3S11) of 2PO were better preserved, and less impurity and unknown peaks were generated over a short period of exposure time. In addition, the morphology of 2PO only changed slightly after 10 minutes of exposure. Despite the fact that the particles aggregated significantly after several days of exposure, 2PO tended to form a protective layer composed of S8, which might allow some particles to be shielded from attack by moisture, slowing down the decay of material properties.

Crystal structures, Hirshfeld analysis, and energy framework analysis of two differently 3'-substituted 4-methylchalcones: 3'-(N=CHC6H4-p-CH3)-4-methylchalcone and 3'-(NHCOCH3)-4-methylchalcone.

Two crystal structures of chalcones, or 1,3-diarylprop-2-en-1-ones, are presented; both contain a p-methyl substitution on the 3-Ring, but differ with respect to the m-substitution on the 1-Ring. Their systematic names are (2E)-3-(4-methylphenyl)-1-(3-{[(4-methylphenyl)methylidene]amino}phenyl)prop-2-en-1-one (C24H21NO) and N-{3-[(2E)-3-(4-methylphenyl)prop-2-enoyl]phenyl}acetamide (C18H17NO2), which are abbreviated as 3'-(N=CHC6H4-p-CH3)-4-methylchalcone and 3'-(NHCOCH3)-4-methylchalcone, respectively. Both chalcones represent the first reported acetamide-substituted and imino-substituted chalcone crystal structures, adding to the robust library of chalcone structures within the Cambridge Structural Database. The crystal structure of 3'-(N=CHC6H4-p-CH3)-4-methylchalcone exhibits close contacts between the enone O atom and the substituent arene ring, in addition to C...C interactions between the substituent arene rings. The structure of 3'-(NHCOCH3)-4-methylchalcone exhibits a unique interaction between the enone O atom and the 1-Ring substituent, contributing to its antiparallel crystal packing. In addition, both structures exhibit π-stacking, which occurs between the 1-Ring and R-Ring for 3'-(N=CHC6H4-p-CH3)-4-methylchalcone, and between the 1-Ring and 3-Ring for 3'-(NHCOCH3)-4-methylchalcone.

Rapid sol-gel synthesis of honeycomb-layered Na3Ni2BiO6 and orthorhombic Na3Ca2BiO6.

The A3M2M'O6 type materials Na3Ca2BiO6 and Na3Ni2BiO6 were successfully synthesised through two sol-gel techniques - a method based on a natural deep eutectic solvent, and a biopolymer-mediated synthesis. The materials were analysed using Scanning Electron Microscopy to determine if there was a difference in final morphology between the two methods, and it was found that the natural deep eutectic solvent method resulted in a more porous morphology. For both materials, the optimum dwell temperature was found to be 800 °C, which in the case of Na3Ca2BiO6 was a much less energy-intensive synthesis process than its seminal solid-state synthesis. Magnetic susceptibility measurements were undertaken on both materials. It was found that Na3Ca2BiO6 exhibits only weak, temperature independent paramagnetism. Na3Ni2BiO6 was found to be antiferromagnetic, with a Néel temperature of 12 K, in line with previously reported results.

True molecular conformation and structure determination by three-dimensional electron diffraction of PAH by-products potentially useful for electronic applications.

The true molecular conformation and the crystal structure of benzo[e]dinaphtho[2,3-a;1',2',3',4'-ghi]fluoranthene, 7,14-diphenylnaphtho[1,2,3,4-cde]bisanthene and 7,16-diphenylnaphtho[1,2,3,4-cde]helianthrene were determined ab initio by 3D electron diffraction. All three molecules are remarkable polycyclic aromatic hydrocarbons. The molecular conformation of two of these compounds could not be determined via classical spectroscopic methods due to the large size of the molecule and the occurrence of multiple and reciprocally connected aromatic rings. The molecular structure of the third molecule was previously considered provisional. These compounds were isolated as by-products in the synthesis of similar products and were at the same time nanocrystalline and available only in very limited amounts. 3D electron diffraction data, taken from submicrometric single crystals, allowed for direct ab initio structure solution and the unbiased determination of the internal molecular conformation. Detailed synthetic routes and spectroscopic analyses are also discussed. Based on many-body perturbation theory simulations, benzo[e]dinaphtho[2,3-a;1',2',3',4'-ghi]fluoranthene may be a promising candidate for triplet-triplet annihilation and 7,14-diphenylnaphtho[1,2,3,4-cde]bisanthene may be a promising candidate for intermolecular singlet fission in the solid state.

New and Unforeseen Crystal Growth Processes for a Metal Oxide.

The synthesis of corundum (α-Al2O3) via a layered Al2O3-MoO3 system was directly observed for the first time. This revealed a new crystal growth process with three key features: (1) the formation of an Al2(MoO4)3 intermediate layer through a solid-solid interaction in the temperature range of ∼705-860 °C; (2) the melting of the Al2(MoO4)3 layer between approximately 870 and 890 °C; and (3) the decomposition of Al2(MoO4)3 to corundum between 950 and 1100 °C. This molten intermediate decomposition (MIND) mechanism produced corundum, which was light bluish-gray in color and was defined in CIE (L* a* b*) color space as L* = 76.65, a* = -1.09, and b* = -6.20. The reagents used in this study were the same as those used in MoO3 flux growth studies on the synthesis of corundum, therefore demonstrating that the previous work only gave a superficial treatment of the mechanism of formation.

Synthesis of porous high-temperature superconductors via a melamine formaldehyde sacrificial template.

Nanostructured high-temperature superconductors YBa2Cu3O6+δ and Bi2Sr2CaCu2O8+δ were synthesised using a melamine formaldehyde sponge as a sacrificial template, via three solution-based approaches. In the case of YBa2Cu3O6+δ , a modified Pechini method produced a material with a superconducting transition at 92 K and a specific surface area of 4.22 m2 g-1. Further analysis with Hg porosimetry determined that the sponge exhibited a porosity of 82%. In the case of Bi2Sr2CaCu2O8+δ , this method produced a material that exhibited superconductivity at 86 K with a specific surface area of 9.62 m2 g-1. Hg-porosimetry determined that the BSCCO sponge exhibited a porosity of 78%.

Determining nanorod dimensions in dispersion with size anisotropy nanoparticle tracking analysis.

Control over nanorod dimensions is critical to their application, requiring fast, robust characterisation of their volume and aspect ratio whilst in their working medium. Here, we present an extension of Nanoparticle Tracking Analysis which determines the aspect ratio of nanoparticles from the polarisation state of scattered light in addition to a hydrodynamic diameter from Brownian motion. These data, in principle, permit the determination of nanorod dimensions of any composition using Nanoparticle Tracking Analysis. The results are compared with transmission electron microscopy and show that this technique can additionally determine the aggregation state of the nanorod dispersion if single nanorod dimensions are determined with a complementary technique. We also show it is possible to differentiate nanoparticles of similar hydrodynamic diameter by their depolarised scattering. Finally, we assess the ability of the technique to output nanorod dimensions and suggest ways to further improve the approach. This technique will enable rapid characterisation of nanorods in suspension, which are important tools for nanotechnology.

Laser-induced convection shifts size distributions in nanoparticle tracking analysis.

This work discusses the effects of increasing laser power on the size data derived from NTA for particles of known size and scatterers in solutions of flufenamic acid in ethanol. We find that whilst a higher laser power reveals more particles as expected, their residence time changes due to laser-induced convection. This reduced residence time decreases the number of tracks available for individual particle size determination, shifting the size distribution to smaller values. This problem is overcome by using a shutter to inhibit the development of convection currents, increasing particle residence time and reducing the error on the size distribution. The detailed understanding of laser-induced convection permits more robust size characterisation of mesoscopic organic clusters, which play a key role in two-step nucleation theory.

Structure determination, thermal stability and dissolution rate of δ-indomethacin.

The structure solution of the δ-polymorph of indomethacin was obtained using three-dimensional electron diffraction. This form shows a significantly enhanced dissolution rate compared with the more common and better studied α- and γ-polymorphs, indicating better biopharmaceutical properties for medicinal applications. The structure was solved in non-centrosymmetric space group P21 and comprises two molecules in the asymmetric unit. Packing and molecule conformation closely resemble indomethacin methyl ester and indomethacin methanol solvate. Knowledge of the structure allowed the rational interpretation of spectroscopic IR and Raman data for δ-polymorph and a tentative interpretation for still unsolved indomethacin polymorphs. Finally, we observed a solid-solid transition from δ-polymorph to α-polymorph that can be driven by similarities in molecular conformation.

Improved photodegradation of anionic dyes using a complex graphitic carbon nitride and iron-based metal-organic framework material.

Introducing heterostructures to graphitic carbon nitrides (g-C3N4) can improve the activity of visible-light-driven catalysts for the efficient treatment of multiple toxic pollutants in water. Here, we report for the first time that a complex material can be constructed from oxygen-doped g-C3N4 and a MIL-53(Fe) metal-organic framework using facile hydrothermal synthesis and recycled polyethylene terephthalate from plastic waste. The novel multi-walled nanotube structure of the O-g-C3N4/MIL-53(Fe) composite, which enables the unique interfacial charge transfer at the heterojunction, showed an obvious enhancement in the separation efficiency of the photochemical electron-hole pairs. This resulted in a narrow bandgap energy (2.30 eV, compared to 2.55 eV in O-g-C3N4), high photocurrent intensity (0.17 mA cm-2, compared to 0.12 mA cm-2 and 0.09 mA cm-2 in MIL-53(Fe) and O-g-C3N4, respectively) and excellent catalytic performance in the photodegradation of anionic azo dyes (95% for RR 195 and 99% for RY 145 degraded after 4 h, and only a minor change in the efficiency observed after four consecutive tests). These results demonstrate the development of new catalysts made from waste feedstocks that show high stability, ease of fabrication and can operate in natural light for environmental remediation.

Structural effects of halogen bonding in iodochalcones.

The structures of three iodochalcones, functionalized with fluorine or a nitro group, have been investigated to explore the impact of different molecular electrostatic distributions on the halogen bonding within each crystal structure. The strongly withdrawing nitro group presented a switch of the halogen bond from a lateral to a linear motif. Surprisingly, this appears to be influenced by a net positive shift in charge distribution around the lateral edges of the σ-hole, making the lateral I...I bonding motif less preferable. A channel of amphoteric I...I type II halogen bonds is observed for a chalcone molecule, which was not previously reported in chalcones, alongside an example of the common synthon involving extended linear chains of I...O2N donor-acceptor halogen bonds. This work shows that halogenated chalcones may be an interesting target for developing halogen bonding as a significant tool within crystal engineering, a thus far underexplored area for this common structural motif.

3D Electron Diffraction Structure Determination of Terrylene, a Promising Candidate for Intermolecular Singlet Fission.

Herein we demonstrate the prowess of the 3D electron diffraction approach by unveiling the structure of terrylene, the third member in the series of peri-condensed naphthalene analogues, which has eluded structure determination for 65 years. The structure was determined by direct methods using electron diffraction data and corroborated by dispersion-inclusive density functional theory optimizations. Terrylene crystalizes in the monoclinic space group P21 /a, arranging in a sandwich-herringbone packing motif, similar to analogous compounds. Having solved the crystal structure, we use many-body perturbation theory to evaluate the excited-state properties of terrylene in the solid-state. We find that terrylene is a promising candidate for intermolecular singlet fission, comparable to tetracene and rubrene.

A new olanzapine cocrystal obtained from volatile deep eutectic solvents and determined by 3D electron diffraction.

A previously unknown cocrystal of olanzapine and phenol was identified from a volatile deep eutectic solvent as the intermediate species in the crystallization of olanzapine. This new nanocrystalline phase was investigated by electron diffraction, powder X-ray diffraction and differential scanning calorimetry. The structure was determined by simulated annealing using 3D electron diffraction data and confirmed using DFT-D optimizations. Olanzapine and phenol cocrystallize in the triclinic space group P1, supporting the hypothesis of a dimeric growth unit, where a centrosymmetric dimer is stabilized by multiple weak C-H...π interactions and forms double N-H...N hydrogen bonding with adjacent dimers.

Crystal structures of three functionalized chalcones: 4'-di-methyl-amino-3-nitro-chalcone, 3-di-methyl-amino-3'-nitrochalcone and 3'-nitro-chalcone.

The structure of three functionalized chalcones (1,3-di-aryl-prop-2-en-1-ones), containing combinations of nitro and di-methyl-amino functional groups, are presented, namely, 1-[4-(di-methyl-amino)-phen-yl]-3-(3-nitro-phen-yl)prop-2-en-1-one, C17H16N2O3, Gp8m, 3-[3-(di-methyl-amino)-phen-yl]-1-(3-nitro-phen-yl)prop-2-en-1-one, C17H16N2O3, Hm7m and 1-(3-nitro-phen-yl)-3-phenyl-prop-2-en-1-one, C15H11NO3, Hm1-. Each of the mol-ecules contains bonding motifs seen in previously solved crystal structures of functionalized chalcones, adding to the large dataset available for these small organic mol-ecules. The structures of all three of the title compounds contain similar bonding motifs, resulting in two-dimensional planes of mol-ecules formed via C-H⋯O hydrogen-bonding inter-actions involving the nitro- and ketone groups. The structure of Hm1- is very similar to the crystal structure of a previously solved isomer [Jing (2009 ▸). Acta Cryst. E65, o2510].

Crystal structure and Hirshfeld analysis of 3'-bromo-4-methyl-chalcone and 3'-cyano-4-methyl-chalcone.

Two crystal structures of chalcones, or 1,3-di-aryl-prop-2-en-1-ones, are presented; both contain a methyl substitution on the 3-Ring, but differ on the 1-Ring, bromo versus cyano. The compounds are 3'-bromo-4-methyl-chalcone [systematic name: 1-(2-bromo-phen-yl)-3-(4-methyl-phen-yl)prop-2-en-1-one], C16H13BrO, and 3'-cyano-4-methyl-chalcone {systematic name: 2-[3-(4-methyl-phen-yl)prop-2-eno-yl]benzo-nitrile}, C17H13NO. Both chalcones meaningfully add to the large dataset of chalcone structures. The crystal structure of 3'-cyano-4-methyl-chalcone exhibits close contacts with the cyano nitro-gen that do not appear in previously reported disubstituted cyano-chalcones, namely inter-actions between the cyano nitro-gen atom and a ring hydrogen atom as well as a methyl hydrogen atom. The structure of 3'-bromo-4-methyl-chalcone exhibits a type I halogen bond, similar to that found in a previously reported structure for 4-bromo-3'-methyl-chalcone.

Metastable crystalline phase formation in deep eutectic systems revealed by simultaneous synchrotron XRD and DSC.

The phase behaviour of various deep eutectic systems was analysed using concurrent synchrotron powder X-ray diffraction and differential scanning calorimetry. Deep eutectic systems containing the pharmaceuticals metacetamol, 2-ethoxybenzamide or benzamide as binary mixtures with phenol revealed new crystalline phases melting either before or with crystals of phenol, highlighting their lower stabilities. Furthermore, in the phenol : 2-ethoxybenzamide system it was shown that multiple metastable phases can form, highlighting the potential for the separation of a hierarchy of crystal structures with differing stabilities from eutectic systems. Through these experiments, we strengthen the idea that eutectic systems can be described by understanding the formation and stabilities of metastable co-crystalline structures. These novel results lead to a deeper understanding of the structure and thermodynamics of deep eutectic solvents, with relevance for analagous systems across materials science.

The solubility and stability of heterocyclic chalcones compared with trans-chalcone.

Heterocyclic chalcones are a recently explored subgroup of chalcones that have sparked interest due to their significant antibacterial and antifungal capabilities. Herein, the structure and solubility of two such compounds, (E)-1-(1H-pyrrol-2-yl)-3-(thiophen-2-yl)prop-2-en-1-one and (E)-3-phenyl-1-(1H-pyrrol-2-yl)prop-2-en-1-one, are assessed. Single crystals of (E)-1-(1H-pyrrol-2-yl)-3-(thiophen-2-yl)prop-2-en-1-one were grown, allowing structural comparisons between the heterocyclic chalcones and (2E)-1,3-diphenylprop-2-en-1-one, trivially known as trans-chalcone. The two heterocyclic chalcones were found to be less soluble in all solvents tested and to have higher melting points than trans-chalcone, probably due to their stronger intermolecular interactions arising from the functionalized rings. Interestingly, however, it was found that the addition of the thiophene ring in (E)-1-(1H-pyrrol-2-yl)-3-(thiophen-2-yl)prop-2-en-1-one increased both the melting point and solubility of the sample compared with (E)-3-phenyl-1-(1H-pyrrol-2-yl)prop-2-en-1-one. This observation may be key for the future crystal engineering of heterocyclic chalcones for pharmaceutical applications.

Visualising early-stage liquid phase organic crystal growth via liquid cell electron microscopy.

Here, we show that the development of nuclei and subsequent growth of a molecular organic crystal system can be induced by electron beam irradiation by exploiting the radiation chemistry of the carrier solvent. The technique of Liquid Cell Electron Microscopy was used to probe the crystal growth of flufenamic acid; a current commercialised active pharmaceutical ingredient. This work demonstrates liquid phase electron microscopy analysis as an essential tool for assessing pharmaceutical crystal growth in their native environment while giving insight into polymorph identification of nano-crystals at their very inception. Possible mechanisms of crystal nucleation due to the electron beam with a focus on radiolysis are discussed along with the innovations this technique offers to the study of pharmaceutical crystals and other low contrast materials.