Stepwise Synthesis of Diverse Isomer MOFs via Metal-Ion Metathesis in a Controlled Single-Crystal-to-Single-Crystal Transformation

Two new metal–organic frameworks (MOFs) based on TMBDI linker (TMBDI = 2,3,5,6-tetramethyl-1,4-diisophthalate) and [M₂(COO)₄] paddlewheel, {[Zn₂(TMBDI)­(H₂O)₂]•2.5DMF•2­(1,4-dioxane)•6H₂O}<i>_n</i> (<b>UPC</b>-<b>6</b>) and {[Co₂(TMBDI) (DMA)₂]•2DMA•5EtOH}_<i>n</i> (<b>UPC</b>-<b>8</b>), have been obtained under solvothermal conditions. Due to the low stability of Zn/Co paddlewheels upon the removal of axial solvates, <b>UPC</b>-<b>6</b> and <b>UPC</b>-<b>8</b> possesses a very low surface area and adsorption capacity. Through metal-ion metathesis in a single-crystal-to-single-crystal fashion, two new Cu­(II) MOFs (termed <b>Cu</b>-<b>UPC</b>-<b>6</b> and <b>Cu</b>-<b>UPC</b>-<b>8</b>) with identical robust frameworks were produced, which could not be prepared by routine solvothermal methods. Meanwhile, the influence of the reaction solvents on the metathesis process were also investigated, and the results show that the form of solvented ions can induce obviously kinetic issues. Through gas adsorption measurements, the stability and porosity of frameworks have been shown improved significantly

A Stable Amino-Functionalized Interpenetrated Metal–Organic Framework Exhibiting Gas Selectivity and Pore-Size-Dependent Catalytic Performance

An amino-functionalized doubly interpenetrated microporous zinc metal–organic framework (UPC-30) has been solvothermally synthesized. UPC-30 can be stable at 190 °C and confirmed by powder X-ray diffraction. Gas adsorption measurements indicate that UPC-30 exhibits high H₂ adsorption heat and CO₂/CH₄ separation efficiency. After the exchange of Me₂NH₂⁺ by Li⁺ in the channels, the H₂ adsorption heat increased by 19.7%. Because of the existence of −NH₂ groups in the channels, UPC-30 can effectively catalyze Knoevenagel condensation reactions with high yield and pore-size-dependent selectivity

Expanded Porous Metal–Organic Frameworks by SCSC: Organic Building Units Modifying and Enhanced Gas-Adsorption Properties

Two amino-functional copper metal–organic frameworks of formula [Cu₃(ATTCA)₂­(H₂O)₃]·2DMF·11H₂O·12EtOH (<b>1</b>) (H₃ATTCA = 2-amino-[1,1:3,1-terphenyl]-4,4,5-tricarboxylic acid, pyz = pyrazine, DMF = dimethylformamide) and [Cu₃(ATTCA)₂­(pyz)­(H₂O)]·2DMF·12H₂O·8EtOH (<b>2</b>) were synthesized under solvothermal conditions and characterized by single-crystal X-ray diffraction, infrared spectroscopy, elemental analyses, thermogravimetric analyses, and powder X-ray diffraction. Single-crystal X-ray diffraction analysis revealed that both complexes <b>1</b> and <b>2</b> are built of the Cu₂(COO)₄ paddlewheel secondary building units with an <i><b>fmj</b></i> topology. Importantly, complex <b>1</b> can be transformed into complex <b>2</b> by the single-crystal to single-crystal transformation of which the coordinated water molecules are replaced with pyz molecules. However, the adsorption abilities of <b>2</b> are obviously lower than those of <b>1</b>, as its pores are partially blocked by pyz molecules. Moreover, gas-adsorption analysis showed that the amino-functional <b>1</b> possesses higher gas-adsorption capacity than UMCM-151 for N₂, H₂, CH₄, and C₂H₂, especially for CO₂

Unprecedented Solvent-Dependent Sensitivities in Highly Efficient Detection of Metal Ions and Nitroaromatic Compounds by a Fluorescent Barium Metal–Organic Framework

The assembly of a fluorescent dicarboxylate ligand with a barium ion resulted in the formation of a 3D metal–organic framework, Ba₅(ADDA)₅(EtOH)₂(H₂O)₃·5DMF (<b>UPC-17</b>), based on a 1D rod-shaped secondary building unit. The unprecedented solvent-dependent sensitivities of <b>UPC-17</b> for the detection of Fe³⁺/Al³⁺ ions and 4-nitrophenol with high efficiency were observed for the first time. Significantly, <b>UPC-17</b> exhibits superior “turn-off” detection for the Fe³⁺ ion in methanol and acetone emulsions but shows “turn-on” detection in tetrahydrofuran emulsion. Furthermore, the visible color changes in the detection process make them easy to distinguish by the naked eye, which further increases its application potential

Green Fabrication of Ultrathin Co₃O₄ Nanosheets from Metal–Organic Framework for Robust High-Rate Supercapacitors

Two-dimensional cobalt oxide (Co₃O₄) is a promising candidate for robust electrochemical capacitors with high performance. Herein, we use 2,3,5,6-tetramethyl-1,4-diisophthalate as a recyclable ligand to construct a Co-based metal–organic framework of <b>UPC-9</b>, and subsequently, we obtain ultrathin hierarchical Co₃O₄ hexagonal nanosheets with a thickness of 3.5 nm through a hydrolysis and calcination process. A remarkable and excellent specific capacitance of 1121 F·g^–1 at a current density of 1 A·g^–1 and 873 F·g^–1 at a current density of 25 A·g^–1 were achieved for the as-prepared asymmetric supercapacitor, which can be attributed to the ultrathin 2D morphology and the rich macroporous and mesoporous structures of the ultrathin Co₃O₄ nanosheets. This synthesis strategy is environmentally benign and economically viable due to the fact that the costly organic ligand molecules are recycled, reducing the materials cost as well as the environmental cost for the synthesis process

DataSheet1_The diversity of trophoblast cells and niches of placenta accreta spectrum disorders revealed by single-cell RNA sequencing.PDF

Placenta accreta spectrum disorders (PAS) are severe pregnancy complications that occur when extravillous trophoblast cells (EVTs) invade beyond the uterine inner myometrium and are characterized by hypervascularity on prenatal ultrasound and catastrophic postpartum hemorrhage. The potential mechanisms remain incompletely understood. With single-cell RNA-sequencing analysis on the representative invasive parts and the normal part obtained from the same PAS placenta, we profiled the pathological landscape of invasive PAS placenta and deciphered an intensified differentiation pathway from progenitor cytotrophoblasts (CTBs) to EVTs via LAMB4+ and KRT6A+ CTBs. In the absence of the decidua, the invasive trophoblasts of various differentiation states interacted with ADIRF+ and DES+ maternal stromal cells. The PAS-associated hypervascularity might be due to the enhanced crosstalk of trophoblasts, stromal cells and vascular endothelial cells. Finally, we presented an immune microenvironmental landscape of invasive PAS. The pathogenesis of PAS could be further explored with current resources for future targeted translational studies.</p