Search Results (17)

Isosymmetric phase transitions (IPTs) represent a rare class of solid-state transformations in which substantial structural reorganization occurs without a change in crystallographic symmetry. These phenomena, though subtle, can have a profound impact on the physical and functional properties of materials, offering novel opportunities for property tuning without chemical modification. This review provides a comprehensive overview of the experimental and computational methods used to detect and characterize IPTs, including single-crystal and powder X-ray diffraction, Raman and FT-IR spectroscopy, differential scanning calorimetry, and advanced simulation techniques such as density functional theory, molecular dynamics, and crystal structure prediction. Special emphasis is placed on correlating local structural rearrangements—such as hydrogen-bond reconfiguration, polyhedral tilting, and molecular fragment reorientation—with macroscopic thermodynamic signatures. A broad selection of examples from the literature is discussed, covering molecular crystals, coordination compounds, organic functional materials, simple salts, and inorganic oxides, with detailed tables summarizing pressure- and temperature-induced IPTs. The review also analyses the primary factors that trigger IPTs, particularly temperature and pressure, and examines their role in governing structural stability and transformation pathways. By combining structural, spectroscopic, and thermodynamic perspectives, this work aims to consolidate the understanding of IPT mechanisms and to highlight their significance for the design of responsive crystalline materials. Full article

Human angiotensin-I-converting enzyme (ACE) is involved in vasoregulation, inflammation, and neurodegenerative disorders. The enzyme is formed of two domains; the C-domain (cACE) is primarily involved in blood pressure regulation, whereas the N-domain (nACE) is strongly linked to fibrosis; hence, designing domain-specific inhibitors could make a difference between treating one condition without having a negative effect on another. AnCE (a close homologue of ACE) is derived from Drosophila melanogaster and has a high similarity specifically to cACE. Due to high similarity and ease of crystallisation, AnCE has been chosen as a model protein for ACE studies and for the design of ACE inhibitors. In this study, enzyme kinetic assays and X-ray crystallography techniques revealed the significance of using dipeptides as selective inhibitors for AnCE and how this knowledge could be applied to cACE and nACE. All the dipeptides tested in this study were shown to bind AnCE in two distinct locations, i.e., the non-prime and prime subsites. It was found that a hydrophobic residue at the S1 and S1′ subsites, with a tryptophan at the S2 and S2′ subsites, showed highest affinity towards AnCE. It was also observed that a key pocket within the S2′ subsite had a major influence on the binding orientation within the prime subsites and could potentially explain ACE’s dipeptidyl carboxypeptidase activity. Importantly these dipeptides are found in functional foods, making them potentially available from diets. Knowledge of the dipeptide binding presented here could aid in the development of ACE domain-specific inhibitors. Full article

The study of high-pressure sound velocity is an important part of shock wave physics, and the study of ultra-high pressure sound velocity of iron is of great significance to many research fields such as geophysics, solid state physics, and crystallography. At present, the measurement of sound velocity is usually carried out by the catch-up sparse wave method and windowed VISAR technology, which is complex in structure and not highly adaptable. In particular, for the ultra-high pressure sonic velocity measurement of metals, it is limited by the loading platform and window materials and cannot realize the high temperature and high-pressure environment of the earth’s inner core. In this paper, the sound velocity measurement of iron under high temperature and high-pressure environment (78 GPa) is realized based on the two-stage light gas cannon experimental platform. The side-side sparse wave method was used to establish a coupling model of high-spatially resolved optical group and fiber bundle. A multiplexed all-fiber laser interferometry velocity measurement system (DISAR) was built, and the spatial resolution was better than 20 μm. In this paper, we will provide a feasible route for a method for measuring the high spatiotemporal resolution velocity. Full article

2,3-dihydro-5,6,7,8-tetranitro-1,4-benzodioxine (TNBD), molecular formula = C₈H₄N₄O₁₀, is a completely nitrated aromatic ring 1,4-benzodioxane derivative. The convenient method of TNBD synthesis was developed (yield = 81%). The detailed structure of this compound was investigated by X-ray crystallography. The results of the thermal analysis (TG) obtained with twice re-crystallized material revealed the onset at 240 °C (partial sublimation started) and melting at 286 °C. The investigated material degraded completely at 290–329 °C. The experimental density of 1.85 g/cm³ of TNBD was determined by X-ray crystallography. The spectral properties of TNBD (NMR, FT-IR and Raman) were explored. The detonation properties of TNBD calculated by the EXPLO 5 code were slightly superior in comparison to standard high-energy material—tetryl (detonation velocity of TNBD—7727 m/s; detonation pressure—278 kbar; and tetryl—7570 m/s and 226.4 kbar at 1.614 g/cm³, or 260 kbar at higher density at 1.71 g/cm³. The obtained preliminary results might suggest TNBD can be a potential thermostable high-energy and -density material (HEDM). Full article

The carboxylation of unsaturated amine and alcohol compounds, including 4-benzylamino-1-phenyl-1-butyne (homopropargylamine), 2-butyne-1-ol (propargylic alcohol), and 2,3-butadiene-1-ol (allenylmethyl alcohol), using the hydroxidogold(I) complex, AuOH(IPr) [IPr = 1,3-bis(2,6-diisopropylphenyl)-imidazol-2-ylidene], produces corresponding alkenylgold(I) complexes with a cyclic urethane or carbonate framework in high yields. The reaction takes place in aprotic THF at room temperature under the atmospheric pressure of CO₂ in the absence of base additives. The products were characterized by NMR spectroscopy, elemental analysis, and X-ray crystallography. The functionalized alkenyl complexes prepared from the alkynes can be protonated by treatment with an equimolar amount of acetic acid to afford five- or six-membered carboxylation products, whereas the related alkenyl complex derived from allenylmethyl alcohol decomposed to recover the starting allene via ring-opening decarboxylation. Full article

Modifying crystallization plates can significantly impact the success rate and quality of protein crystal growth, making it a helpful strategy in protein crystallography. However, appropriate methods for preparing nano-sized particles with a high specific surface area and strategies for applying these nanoparticles to form suitable coatings on crystallization plate surfaces still need to be clarified. Here, we utilized both an ultrasonic crusher and a high-pressure homogenizer to create a nano metal–organic framework (MOF), specifically HKUST-1, and introduced a solvent evaporation method for producing MOF coatings on 96-well crystallization plates to induce protein crystal growth. The morphology of MOF coatings on the resin surface of the plate well was characterized using optical and scanning electron microscopy. Compared to the control group, crystallization screening experiments on nine proteins confirmed the effectiveness of plates with MOF coatings. Applying MOF coatings to crystallization plates is an easy-to-use, time-efficient, and potent tool for initiating crystallization experiments. Full article

Since its introduction in the early 1970s, high pressure crystallography (HPX) has shown great potential for the investigation of different types of matter. Using diamond anvil cells, HPX is an emerging technique that has been rapidly implemented, making it available to biologists, and there is immense potential for utilizing this technique in biological systems in the future. At the molecular level, high-pressure crystallographic investigation provides information on structural characteristics that not only determine the native conformation of a protein but also the conformations with higher free-energy, thus revealing function-related structural changes and properties that can be modified as a result of pressurization. The increase in the number of crystal structures of different macromolecules determined under high pressure over the last five decades can be ascribed mainly to two factors: the emergence of high-pressure cells with very large, open angles, and the advent of third generation synchrotron sources. The use of high pressure crystallography as a research tool has been shown to contribute to the advancements in the basic fields of biochemistry (protein misfolding and aggregation), biophysics (protein stability), and biotechnology (food processing). Presently, with a growing interest in biomedicine and nanotechnology, this nonstandard method appears to be a valid instrument for probing more challenging and complex systems. In this review, we present the method, highlight a selection of recent applications, and describe challenges for high pressure macromolecular crystallography (HPMX). Full article

Plant growth inhibitors (PGIs) in rice (Oryza sativa), or rice allelochemicals, are secondary metabolites that are either exudated by rice plants to cope with natural competitors or produced during the decomposition of rice by-products in the paddy fields. Of these, the major groups of rice PGIs include phenolics, flavonoids, terpenoids, alkaloids, steroids, and fatty acids, which also exhibit potential medicinal and pharmaceutical properties. Recently, the exploitation of rice PGIs has attracted considerable attention from scientists worldwide. The biosynthesis, exudation, and release of PGIs are dependent on environmental conditions, relevant gene expression, and biodiversity among rice varieties. Along with the mechanism clarification, numerous analytical methods have been improved to effectively support the identification and isolation of rice PGIs during the last few decades. This paper provides an overview of rice PGIs and techniques used for determining and extracting those compounds from rice. In particular, the features, advantages, and limitations of conventional and upgraded extraction methods are comprehensively reported and discussed. The conventional extraction methods have been gradually replaced by advanced techniques consisting of pressurized liquid extraction (PLE), microwave-assisted extraction (MAE), and solid-phase extraction (SPE). Meanwhile, thin-layer chromatography (TLC), liquid chromatography (LC), gas chromatography (GC), mass spectrometry (MS), nuclear magnetic resonance (NMR), high-resolution mass spectrometry (HR-MS), infrared spectroscopy (IR), near-infrared spectroscopy (NIRS), and X-ray crystallography are major tools for rice PGI identification and confirmation. With smart agriculture becoming more prevalent, the statistics of rice PGIs and extraction methods will help to provide useful datasets for building an autonomous model for safer weed control. Conceivably, the efficient exploitation of rice PGIs will not only help to increase the yield and economic value of rice but may also pave the way for research directions on the development of smart and sustainable rice farming methods. Full article

The investigation of molecular crystals at high pressure is a sought-after trend in crystallography, pharmaceutics, solid state chemistry, and materials sciences. The di-p-tolyl disulfide (CH₃−C₆H₄−S−)₂ system is a bright example of high-pressure polymorphism. It contains “conventional” solid–solid transition and a “hidden” form which may be obtained only from solution at elevated pressure. In this work, we apply force field and periodic DFT computational techniques to evaluate the thermodynamic stability of three di-p-tolyl disulfide polymorphs as a function of pressure. Theoretical pressures and driving forces for polymorphic transitions are defined, showing that the compressibility of the γ phase is the key point for higher stability at elevated pressures. Transition state energies are also estimated for α → β and α → γ transitions from thermodynamic characteristics of crystal structures, not exceeding 5 kJ/mol. The β → γ transition does not occur experimentally in the 0.0–2.8 GPa pressure range because transition state energy is greater than 18 kJ/mol. Relations between free Gibbs energy (in assumption of enthalpy) of phases α, β, and γ, as a function of pressure, are suggested to supplement and refine experimental data. A brief discussion of the computational techniques used for high-pressure phase transitions is provided. Full article

Protein crystallization plays a fundamental role in structural biology and chemistry, drug discovery, and crystallography itself. Determining how to improve the crystal growth is necessary and vital during the whole process. According to the recently published data, crystallizing proteins on nanoporous surfaces (i.e., metal–organic framework, abbreviated as MOF) is faster and demands less protein. However, dispersing micro-sized MOF materials uniformly is still a challenge and limiting process in protein crystallization. Here, we investigate the uniformity of micro-sized MOF under the treatment of the high-pressure homogenizer. At various pressures, the MOF is split into particles of different sizes, including the uniform and stable nano-sized MOF. Crystallization experiments demonstrated its enhancement in protein crystallization, and the number of crystals is significantly increased in the presence of nano-sized MOF. This work explores the use of nano-sized MOF solids to crystallize proteins of limited availability (i.e., insufficient for conventional methods) or of a hard-to-crystallize nature. Full article

New insight into the superconducting properties of HgBa₂CuO₄ (Hg-1201) cuprates is provided by combined measurements of electrical resistivity and single crystal X-ray diffraction under pressure. The changes induced by increasing pressure up to 20 GPa in optimally doped single crystals were investigated. The resistivity measurements as a function of temperature show a metallic behavior up to ~10 GPa that gradually passes into an insulating state, typical of charge ordering, which totally suppresses superconductivity above 13 GPa. The changes in resistivity are accompanied by the apparition of sharp Bragg peaks in the X-ray diffraction patterns, indicating that the charge ordering is accompanied by a 3D oxygen ordering. Considering that pressure induces a charge transfer of about 0.02 at 10 GPa, our results are the first observation of charge order competing with superconductivity developed in the overdoped region of the phase diagram of a Hg-based cuprate. Full article

The introduction of multigrain crystallography (MGC) applied in a laser-heated diamond anvil cell (LH-DAC) using synchrotron X-rays has provided a new path to investigate the microstructural evolution of materials at extreme conditions, allowing for simultaneous investigations of phase identification, strain state determination, and orientation relations across phase transitions in a single experiment. Here, we applied this method to a sample of San Carlos olivine beginning at ambient conditions and through the α-olivine → γ-ringwoodite phase transition. At ambient temperatures, by measuring the evolution of individual Bragg reflections, olivine shows profuse angular streaking consistent with the onset of yielding at a measured stress of ~1.5 GPa, considerably lower than previously reported, which may have implications for mantle evolution. Furthermore, γ-ringwoodite phase was found to nucleate as micron to sub-micron grains imbedded with small amounts of a secondary phase at 15 GPa and 1000 °C. Using MGC, we were able to extract and refine individual crystallites of the secondary unknown phase where it was found to have a structure consistent with the ε-phase previously described in chondritic meteorites. Full article

The results of the monitoring of the [4 + 4] photocycloaddition reaction path in single crystals of bi(anthracene-9,10-dimethylene) at high pressure are presented. The crystal structures for several steps of the phototransformation at 0.3 GPa and 1.0 GPa were determined and analysed. The applied high pressure did not halt the photochemical reaction and almost 100% of the product molecules were obtained, although the reaction was very slowly reversible similarly to that of ambient conditions. During the crystal phototransformation the intramolecular geometry, molecular orientation and intermolecular interactions of the reactant changed more and more towards the values observed for the product. The initial increase in the unit cell volume brought about by the photochemical reaction was diminished by high pressure. High pressure itself did not significantly influence the intramolecular geometry of the reactant and product molecules, but it influenced the intermolecular interactions. Full article

The cornerstone of molecular magnetism is a detailed understanding of the relationship between structure and magnetic behaviour, i.e., the development of magneto-structural correlations. Traditionally, the synthetic chemist approaches this challenge by making multiple compounds that share a similar magnetic core but differ in peripheral ligation. Changes in the ligand framework induce changes in the bond angles and distances around the metal ions, which are manifested in changes to magnetic susceptibility and magnetisation data. This approach requires the synthesis of a series of different ligands and assumes that the chemical/electronic nature of the ligands and their coordination to the metal, the nature and number of counter ions and how they are positioned in the crystal lattice, and the molecular and crystallographic symmetry have no effect on the measured magnetic properties. In short, the assumption is that everything outwith the magnetic core is inconsequential, which is a huge oversimplification. The ideal scenario would be to have the same complex available in multiple structural conformations, and this is something that can be achieved through the application of external hydrostatic pressure, correlating structural changes observed through high-pressure single crystal X-ray crystallography with changes observed in high-pressure magnetometry, in tandem with high-pressure inelastic neutron scattering (INS), high-pressure electron paramagnetic resonance (EPR) spectroscopy, and high-pressure absorption/emission/Raman spectroscopy. In this review, which summarises our work in this area over the last 15 years, we show that the application of pressure to molecule-based magnets can (reversibly) (1) lead to changes in bond angles, distances, and Jahn–Teller orientations; (2) break and form bonds; (3) induce polymerisation/depolymerisation; (4) enforce multiple phase transitions; (5) instigate piezochromism; (6) change the magnitude and sign of pairwise exchange interactions and magnetic anisotropy, and (7) lead to significant increases in magnetic ordering temperatures. Full article

We studied the photochemical reactivity of salts of 4-(2,4,6-triisopropylbenzoyl)benzoic acid with propane-1,2-diamine (1), methanamine (2), cyclohexanamine (3), and morpholine (4), for compounds (1), (3), and (4) at 0.1 MPa and for compounds (1) and (2) at 1.3 GPa and 1.0 GPa, respectively. The changes in the values of the unit cell parameters after UV irradiation and the values of the intramolecular geometrical parameters indicated the possibility of the occurrence of the Norrish–Yang reaction in the case of all the compounds. The analysis of the intramolecular geometry and free spaces revealed which o-isopropyl group takes part in the reaction. For (1), the same o-isopropyl group should be reactive at ambient and high pressures. In the case of (2), high pressure caused the phase transition from the space group I2/a with one molecule in the asymmetric unit cell to the space group P$\overline{1}$ with two asymmetric molecules. The analysis of voids indicated that the Norrish–Yang reaction is less probable for one of the two molecules. For the other molecule, the intramolecular geometrical parameters showed that except for the Norrish–Yang reaction, the concurrent reaction leading to the formation of a five-membered ring can also proceed. In (3), both o-isopropyl groups are able to react; however, the bigger volume of a void near 2-isopropyl may be the factor determining the reactivity. For (4), only one o-isopropyl should be reactive. Full article