The spontaneous formation of cyclodextrin (CD)-oil inclusion complexes (ICs) and their further growth into patterned crystals present a bottom-up route to the fabrication of periodic macroscopic structure. Although the inclusion processes are well established for the molecules, understanding intermediate structures during the crystal growth and emerging of persistent crystalline order has been lacking. Here we build a hierarchy of oriented micro/nanostructures of CD-oil ICs in solution by choosing different oil guests including several straight-chain alkanes of C12, C14 and C16, oleic acid (OA), glycerol trioleate (TG) and soybean oil (SO), in an attempt to reveal the roles of oil guests in the formation of their crystallites. Remarkably, the ICs tend to grow into clusters and terminate at a certain finite size as long columns or lamella plates with well-defined facets, dependent on the type of oil used. For the first time, we report a non-equilibrium growth of crystallites with surface faceting directed by the guests by means of Arching and Bundling.

Structure-based drug design is highly dependent on the availability of structures of the protein of interest in complex with lead compounds. Ideally, this information can be used to guide the chemical optimization of a compound into a pharmaceutical drug candidate. A limitation of the main structural method used today - conventional X-ray crystallography - is that it only provides structural information about the protein complex in its frozen state. Serial crystallography is a relatively new approach that offers the possibility to study protein structures at room temperature (RT). Here, we explore the use of serial crystallography to determine the structures of the pharmaceutical target, soluble epoxide hydrolase. We introduce a new method to screen for optimal microcrystallization conditions suitable for use in serial crystallography and present a number of RT ligand-bound structures of our target protein. From a comparison between the RT structural data and previously published cryo-temperature structures, we describe an example of a temperature-dependent difference in the ligand-binding mode and observe that flexible loops are better resolved at RT. Finally, we discuss the current limitations and potential future advances of serial crystallography for use within pharmaceutical drug discovery.

Organometallic lead halide perovskite powders have gained widespread attention for their intriguing properties, showcasing remarkable performance in the optoelectronic applications. In this study, formamidinium lead iodide (α-FAPbI3) microcrystals (MCs) is synthesized using retrograde solubility-driven crystallization. Additionally, methylammonium lead bromide (MAPbBr3) and cesium lead iodide (δ-CsPbI3) MCs are prepared through a sonochemical process, employing low-grade PbX2 (X = I & Br) precursors and an eco-friendly green solvent (γ-Valerolactone). The study encompasses an analysis of the structural, optical, thermal, elemental, and morphological characteristics of FAPbI3, MAPbBr3, and CsPbI3 MCs. Upon analysing phase stability, a phase transition in FAPbI3 MCs is observed after 2 weeks. To address this issue, a powder-based mechanochemical method is employed to synthesize stable mixed cation perovskite powders (MCPs) by subjecting FAPbI3 and MAPbBr3 MCs with varying concentrations of CsPbI3. Furthermore, the performance of mixed cation perovskites are examined using the Solar Cell Capacitance Simulator (SCAPS-1D) software. The impact of cesium incorporation in the photovoltaic characteristics is elucidated. All mixed cation absorbers exhibited optimal device performance with a thickness ranging between 0.6-1.5 µm. It\'s worth noting that the MCPs exhibit impressive ambient stability, remaining structurally intact and retaining their properties without significant degradation for 70 days of ambient exposure.

The human NQO1 (hNQO1) is a flavin adenine nucleotide (FAD)-dependent oxidoreductase that catalyzes the two-electron reduction of quinones to hydroquinones, being essential for the antioxidant defense system, stabilization of tumor suppressors, and activation of quinone-based chemotherapeutics. Moreover, it is overexpressed in several tumors, which makes it an attractive cancer drug target. To decipher new structural insights into the flavin reductive half-reaction of the catalytic mechanism of hNQO1, we have carried serial crystallography experiments at new ID29 beamline of the ESRF to determine, to the best of our knowledge, the first structure of the hNQO1 in complex with NADH. We have also performed molecular dynamics simulations of free hNQO1 and in complex with NADH. This is the first structural evidence that the hNQO1 functional cooperativity is driven by structural communication between the active sites through long-range propagation of cooperative effects across the hNQO1 structure. Both structural results and MD simulations have supported that the binding of NADH significantly decreases protein dynamics and stabilizes hNQO1 especially at the dimer core and interface. Altogether, these results pave the way for future time-resolved studies, both at x-ray free-electron lasers and synchrotrons, of the dynamics of hNQO1 upon binding to NADH as well as during the FAD cofactor reductive half-reaction. This knowledge will allow us to reveal unprecedented structural information of the relevance of the dynamics during the catalytic function of hNQO1.

A considerable bottleneck in serial crystallography at XFEL and synchrotron sources is the efficient production of large quantities of homogenous, well diffracting microcrystals. Efficient high-throughput screening of batch-grown microcrystals and the determination of ground-state structures from different conditions is thus of considerable value in the early stages of a project. Here, a highly sample-efficient methodology to measure serial crystallography data from microcrystals by raster scanning within standard in situ 96-well crystallization plates is described. Structures were determined from very small quantities of microcrystal suspension and the results were compared with those from other sample-delivery methods. The analysis of a two-dimensional batch crystallization screen using this method is also described as a useful guide for further optimization and the selection of appropriate conditions for scaling up microcrystallization.

In this work, three series of micro-sized heterometallic europium-containing terephthalate MOFs, (Eu1-xLnx)2bdc3·nH2O (Ln = La, Gd, Lu), are synthesized via an ultrasound-assisted method in an aqueous medium. La3+ and Gd3+-doped terephthalates are isostructural to Eu2bdc3·4H2O. Lu3+-doped compounds are isostructural to Eu2bdc3·4H2O with Lu contents lower than 95 at.%. The compounds that are isostructural to Lu2bdc3·2.5H2O are formed at higher Lu3+ concentrations for the (Eu1-xLux)2bdc3·nH2O series. All materials consist of micrometer-sized particles. The particle shape is determined by the crystalline phase. All the synthesized samples demonstrate an \"antenna\" effect: a bright-red emission corresponding to the 5D0-7FJ transitions of Eu3+ ions is observed upon 310 nm excitation into the singlet electronic excited state of terephthalate ions. The fine structure of the emission spectra is determined by the crystalline phase due to the different local symmetries of the Eu3+ ions in the different kinds of crystalline structures. The photoluminescence quantum yield and 5D0 excited state lifetime of Eu3+ are equal to 11 ± 2% and 0.44 ± 0.01 ms, respectively, for the Ln2bdc3·4H2O structures. For the (Eu1-xLux)2bdc3·2.5H2O compounds, significant increases in the photoluminescence quantum yield and 5D0 excited state lifetime of Eu3+ are observed, reaching 23% and 1.62 ms, respectively.

Biodegradable plastics are attracting attention as a solution to the problems caused by plastic waste. Among biodegradable plastics, polylactide (PLA) and poly (butylene succinate) (PBS) are particularly noteworthy because of their excellent biodegradability. However, the drawbacks of their mechanical properties prompts the need to compound them to achieve the desired strength. The characteristics of the interface of the composite material determine the realization of its final performance. The study of the interface and microstructure of composites is essential for the development of products from degradable polymers. The morphology evolution and microcrystal structure of spin-casted fully biodegradable (PLA/PBS) blend films were investigated using atomic force microscopy (AFM)-based nanomechanical mapping. Results show that intact blend films present an obvious phase separation, where the PBS phase is uniformly dispersed in the PLA phase in the form of pores. Furthermore, the size and number of the PBS phase have a power exponential relationship and linear relationship with PBS loading, respectively. Intriguingly, after annealing at 80 °C for 30 min, the PLA phase formed an orderly petal-like microcrystalline structure centered on the PBS phase. Moreover, the microcrystalline morphology changed from a \"daisy type\" to a \"sunflower type\" with the increased size of the PBS phase. Since the size of the PBS phase is controllable, a new method for preparing microscopic patterns using fully biodegradable polymers is proposed.

Currently, X-ray crystallography, which typically uses synchrotron sources, remains the dominant method for structural determination of proteins and other biomolecules. However, small protein crystals do not provide sufficiently high-resolution diffraction patterns and suffer radiation damage; therefore, conventional X-ray crystallography needs larger protein crystals. The burgeoning method of serial crystallography using X-ray free-electron lasers (XFELs) avoids these challenges: it affords excellent structural data from weakly diffracting objects, including tiny crystals. An XFEL is implemented by irradiating microjets of suspensions of microcrystals with very intense X-ray beams. However, while the method for creating microcrystalline microjets is well established, little attention is given to the growth of high-quality nano/microcrystals suitable for XFEL experiments. In this study, in order to assist the growth of such crystals, we calculate the mean crystal size and the time needed to grow crystals to the desired size in batch crystallization (the predominant method for preparing the required microcrystalline slurries); this time is reckoned theoretically both for microcrystals and for crystals larger than the upper limit of the Gibbs-Thomson effect. The impact of the omnipresent impurities on the growth of microcrystals is also considered quantitatively. Experiments, performed with the model protein lysozyme, support the theoretical predictions.

β-Cyclodextrin (β-CD) can combine with oil and other guest molecules to form amphiphilic inclusion complexes (ICs), which can be adsorbed on the oil-water interface to reduce the interfacial tension and stabilize Pickering emulsions. However, the subtle change of β-CD in the process of emulsion preparation is easily ignored. In this study, β-CD and ginger oil (GO) were used to prepare the Pickering emulsion by high-speed shearing homogenization without an exogenous emulsifier. The stability of the emulsion was characterized by microscopic observation, staining analysis, and creaming index (CI). Results showed that the flocculation of the obtained Pickering emulsion was serious, and the surface of the droplets was rough with lamellar particles. In order to elucidate the formation process of the layered particles, the GO/β-CD ICs were further prepared by ball milling method, and the X-ray diffraction (XRD), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), and interfacial tension analyses found that β-CD and GO first formed amphiphilic nanoscale small particles (ICs) through the host-guest interaction, and the formed small particles were further self-assembled into lamellar micron-scale amphiphilic ICs microcrystals. These amphiphilic ICs and microcrystals aggregated at the oil-water interface and finally formed the Pickering emulsion. In this study, by exploring the formation process and evolution of GO/β-CD self-assembly, the formation process and stabilization mechanism of the β-CD-stabilized GO Pickering emulsion were clarified preliminarily, with the aim of providing a theoretical basis for the development of high-performance CD-stabilized Pickering emulsions.

The series of luminescent NaYF4:Sm3+ nano- and microcrystalline materials co-doped by La3+, Gd3+, and Lu3+ ions were synthesized by hydrothermal method using rare earth chlorides as the precursors and citric acid as a stabilizing agent. The phase composition of synthesized compounds was studied by PXRD. All synthesized materials except ones with high La3+ content (where LaF3 is formed) have a β-NaYF4 crystalline phase. SEM images demonstrate that all particles have shape of hexagonal prisms. The type and content of doping REE significantly effect on the particle size. Upon 400 nm excitation, phosphors exhibit distinct emission peaks in visible part of the spectrum attributed to 4G5/2→6HJ transitions (J = 5/2-11/2) of Sm3+ ion. Increasing the samarium (III) content results in concentration quenching by dipole-dipole interactions, the optimum Sm3+concentration is found to be of 2%. Co-doping by non-luminescent La3+, Gd3+ and Lu3+ ions leads to an increase in emission intensity. This effect was explained from the Sm3+ local symmetry point of view.