Crystal Growth & Design最新文献

Iron oxides are multifunctional materials that have been extensively explored for many applications, including in novel biomedical applications. However, boosting their ability for biomedical purposes remains a significant challenge. Many strategies have been proposed to increase the feasibility of iron oxides for biomedical applications, such as doping and defect engineering, compositing and decorating, surface and interface engineering, and structure and morphology development. This review focuses on the essential advancements of iron oxides for their implementation in biomedical applications. The discussion starts with the design of iron oxides in biomedical applications, such as drug delivery, heat delivery, contrast agents, biomedical nanorobots, and disease-sensing systems. We also discuss the obstacle of iron oxides in biomedical applications and continue by proposing a plausible strategy to enhance the feasibility of iron oxides in biomedical applications. The provided discussion and perspectives can enrich the information and pave the way to finding strategies to enhance the feasibility of iron oxides in biomedical-related applications. We believe that our review also could shed light on how to bring iron oxides close to real implementation for biomedical purposes.

A new flexible Zn-based metal–organic framework (IAM-9) containing a tetraarylpyrrolo[3,2-b]pyrrole (TAPP) dicarboxylate linker has been synthesized when using DEF as the solvent. Single-crystal-to-single-crystal structural transformation upon methanol exchange clearly demonstrates the dynamic nature of IAM-9, which is further confirmed by the powder X-ray diffraction studies and the gated adsorption isotherm for C₂H₂. Structural analysis suggests that the flexible Zn-carboxylate connection is primarily responsible for the observed structural changes. IAM-9 exhibits a solvent-dependent and size-selective flexibility and could readily convert between open and contracted phases upon adsorption or removal of small-sized solvent molecules. Our studies also show that the flexible structure of IAM-9 can selectively recognize DEF through the concurrent multiple interactions between adaptive host and DEF molecules. Owing to the π-expanded TAPP linker used, the photophysical properties of IAM-9 have also been studied. Compared with the organic linker, IAM-9 exhibits a considerably higher fluorescence quantum yield and larger two-photon absorption cross section.

Crystallization-induced diastereomeric transformation of a solid solution salt composed of a chiral primary amine, 4-cyano-1-aminoindane, and di-p-toluoyl-l-tartaric acid was achieved using (pentamethylcyclopentadienyl)iridium(III) diiodide dimer as a racemization catalyst. The enrichment continued until the composition of the solid phase was in equilibrium with that of the liquid phase at 0% diastereomeric excess.

Design and synthesis of multinary metal–organic frameworks (MOFs) are of paramount importance but challenging. Nevertheless, pore space partitioning has provided a valuable avenue to isolate ternary MOFs bearing advanced gas storage and separation properties. Herein, a rare (3,3,8)-c Fe-BQDC-BTC-TPBTC MOF was constructed by means of solvothermal reaction between iron ions, a zigzag dicarboxylate H₂BQDC ligand and another two C₃-symmetry TPBTC and H₃BTC linkers. In contrast to the frequently observed single hexagonal channel type, the acs net within Fe-BQDC-BTC-TPBTC possesses two types of hexagonal channels. One of them is capable of fitting two differently sized C₃-symmetry ligands, engendering an unusual quaternary MOF with a new partially partitioned acs 2/3-plus net eventually. Fe-BQDC-BTC-TPBTC demonstrates a complex bimodal porous system concomitant with a potential separation property toward the MTO product of ethylene and propene mixtures as verified by single gas adsorption and transient column breakthrough experiments, respectively.

This study applies an innovative two-stage continuous manufacturing process for atorvastatin calcium (ASC), focusing on the integration of process intensification through spherical agglomeration. The integrated continuous crystallization–spherical agglomeration (CCSA) process significantly improves the crystallization of active pharmaceutical ingredients (APIs), traditionally focused on downstream processing efficiency. The method integrates continuous crystallization with spherical agglomeration in a two-stage continuous mixed suspension mixed product removal (MSMPR) system. This integration enables the decoupling of nucleation and growth mechanisms from agglomeration, facilitating the continuous production of ASC with optimized physical and processing properties. The intensified system not only enhances particle size and morphology but also significantly improves the downstream processing efficiency, such as filtration, drying, and tableting, while maintaining or enhancing the drug molecule’s efficacy. It also allows for bypassing certain downstream unit operations, such as granulation, that are generally bottleneck processes in ASC manufacturing. The versatility of this approach is evident in its ability to tailor the properties of ASC for maximum bioavailability and processing efficiency, marking a significant advancement in the implementation of process intensification in ASC manufacturing via a novel spherical agglomeration route combined with continuous manufacturing.

Olaparib (OLA) is an insoluble targeting antitumor drug for the treatment of ovarian cancer. Herein, polyamorphism of OLA was systematically studied aiming to improve its solubility and dissolution properties. Three amorphous forms of OLA were prepared by ball milling (form I), rotary evaporation (form II), and melting (form III) methods, and the effects of polyamorphism on the morphology, thermodynamic properties, dissolution and gelation phenomenon, and the stability of OLA were studied for the first time. The results indicate that morphology has an impact on the gelation process of amorphous forms and thereby affects the dissolution of the drug. Among them, form II shows the best solubility and dissolution rate due to its slightest gelation, as well as relatively good stability and tabletability, which exhibits good application prospects in the amorphous solid formulation development of OLA.

This study aims to prepare a stable crystal-co-agglomeration (CCA) process for combining the antibiotics trimethoprim (TMP) and the anti-inflammatory niflumic acid (NFA) as well as the enhancement of powder properties. A novel TMP–NFA salt monohydrate was synthesized and characterized through multitechniques for the first time. Subsequently, the antibacterial effectiveness of TMP–NFA salt monohydrate against Staphylococcus aureus and Shigella flexneri was found to be improved (P < 0.05) compared with that of TMP at certain concentrations, achieving a synergistic effect of TMP and NFA. Based on these findings, spherical agglomerates of TMP–NFA salt monohydrate with superior powder properties including improved flowability (Carr’s index decreased by 37.5% and Hausner’s ratio decreased by 16.3%) and tabletability were produced using an efficient CCA process. Hence, the optimized spherical agglomerates of the drug–drug salt technique provide a promising approach to simultaneously enhance the powder properties and synergistic effect of active pharmaceutical ingredients. The development of such drug–drug salts holds great potential for advancing pharmaceutical formulations and therapeutic outcomes.

A desirable MOF-on-MOF-based ratiometric fluorescent probe (denoted as HPU-26@ZIF-8@Cit@Eu) was designed through the seed-mediated method for classifying phenylglyoxylic acid (PGA, a real internal exposure level of styrene) and 2,6-dipicolinic acid (DPA, a unique bacterial endospore biomarker) with high selectivity and sensitivity. Characterization techniques were carried out with the PXRD pattern, XPS spectra, UV–vis absorption spectra, and DFT-calculated HOMO and LUMO energies for proven mechanisms. The results indicated that PGA could affect the LMCT-ET process in HPU-26 and be binded to Eu³⁺ in ZIF-8, thus resulting in a significant increase both in the blue fluorescence emission peak at 476 nm and the red fluorescence emission peak at 620 nm. According to the fluorescence intensity ratio (I₆₂₀/I₄₇₆), the limit of detection (LOD) reached as low as 0.63 μM within a wide concentration range from 0 to 100 μM, and a noticeable color change from blue to red could be observed. However, upon exposure to DPA, the energy transfer between Zn²⁺ and the ligand was influenced sharply, without prejudice to the fluorescent intensity of Eu³⁺ in ZIF-8. These phenomena made this probe with a stable reference signal have an ultralow LOD of 0.26 μM for DPA in the range of 0–175 μM, converting the fluorescence color from dark blue to bright blue. Meanwhile, the developed probe was applied to the construction of logic gates and hydrogel-based film for the determination of PGA and DPA in real samples with the help of a smartphone.

Pharmaceutical cocrystals are of interest to the pharmaceutical industry due to their novel potential for improving the physicochemical characteristics of old APIs. However, cocrystal screening and following synthetic optimization consume time and effort. A two-component crystalline phase of (S)-ibuprofen and l-phenylalanine with 2:3 stoichiometry (Ibu-Phe) is reported. High-quality Ibu-Phe cocrystal was synthesized easily by the liquid-assisted grinding (LAG) method, but some impurities remained. The crystal structure of Ibu-Phe can be solved ab initio from 3D ED/MicroED. Furthermore, a nearly pure Ibu-Phe cocrystal sample can be obtained under the guidance of stoichiometry from 3D ED/MicroED following synthesis optimization in a few attempts.

Robust and reliable synthons can facilitate the synthesis of predictable and complex supramolecular assemblies. In this study, we employ triply activated halogen-bond donors as a driver for cocrystal formation and examine the influence of the sigma-hole potential for controlling the stoichiometry of binary cocrystals of phenazine. Six new crystal structures are presented for ketone:phenazine binary cocrystals as well as six crystal structures for ester:phenazine cocrystals. The combination of structural chemistry and theory provides an increased understanding of how controlled variation of the molecular electrostatic potential on the halogen-bond atom can control the stoichiometry in the resulting binary cocrystals.