26 research outputs found

    A porous metal-organic framework with ultrahigh acetylene uptake capacity under ambient conditions

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    Acetylene, an important petrochemical raw material, is very difficult to store safely under compression because of its highly explosive nature. Here we present a porous metal-organic framework named FJI-H8, with both suitable pore space and rich open metal sites, for efficient storage of acetylene under ambient conditions. Compared with existing reports, FJI-H8 shows a record-high gravimetric acetylene uptake of 224 cm(3) (STP) g(−1) and the second-highest volumetric uptake of 196 cm(3) (STP) cm(−3) at 295 K and 1 atm. Increasing the storage temperature to 308 K has only a small effect on its acetylene storage capacity (∼200 cm(3) (STP) g(−1)). Furthermore, FJI-H8 exhibits an excellent repeatability with only 3.8% loss of its acetylene storage capacity after five cycles of adsorption–desorption tests. Grand canonical Monte Carlo simulation reveals that not only open metal sites but also the suitable pore space and geometry play key roles in its remarkable acetylene uptake

    Proteins from Avastin® (bevacizumab) Show Tyrosine Nitrations for which the Consequences Are Completely Unclear

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    Avastin® (bevacizumab) is a protein drug widely used for cancer treatment although its further use is questionable due to serious side effects reported. As no systematic proteomic study on posttranslational modifications (PTMs) was reported so far, it was the aim of the current study to use a gel-based proteomics method for determination of Avastin®-protein(s)

    Adsorptive Separation of Methylfuran and Dimethylfuran by a Robust Porous Organic Cage

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    As vital raw materials in the chemical industry, 2-methylfuran (MeF) and 2,5-dimethylfuran (DMeF) are commonly produced as mixtures. The selective separation of MeF and DMeF is crucial yet challenging, with significant industrial and economic implications. This study presents an energy-efficient separation technique using a robust calix[4]resorcinarene-based supramolecular porous organic cage (POC), CPOC-301, to effectively capture DMeF from an equimolar MeF/DMeF mixture within 2 h, yielding 95.3% purity. The exceptional separation efficiency stems from the superior structural stability of CPOC-301, maintaining its initial porous crystalline structure during separation. Calculations show that CPOC-301 forms more C–H···π hydrogen bonds with DMeF versus MeF, accounting for its DMeF selectivity. CPOC-301 can be easily regenerated via heat under a vacuum and reused for over five adsorption–desorption cycles without significant performance loss. This work introduces an approach to separate similar organic molecules effectively using POC materials

    Comparative Stability and Sorption Study of Two <i><b>the</b></i>-type Metal–Organic Frameworks with Different Multiplicate Metal–Ligand Interactions in Secondary Building Units

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    By regulating secondary building units and inducing multiplicate metal–ligand interactions, an unstable anionic framework <b>MOF-Mn<sub>4</sub>Cl</b> is structurally modified into a robust neutral framework <b>MOF-Mn<sub>4</sub></b>. Although possessing same network topology, <b>MOF-Mn<sub>4</sub></b> shows a high BET surface area of 1718 m<sup>2</sup>/g, which is about an 8 times enhancement over <b>MOF-Mn<sub>4</sub>Cl</b>

    Stabilization of Allylic Amine N‑Oxide through Cocrystallization with Pyrogallol[4]arene

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    An active allylic amine N-oxide (ANO) molecule was cocrystallized with pyrogallol[4]­arene through intermolecular hydrogen bonds and π···π interactions. Interestingly, [2,3]-Meisenheimer rearrangement of the ANO was suppressed, which was analyzed in detail in the solid state by single crystal X-ray crystallography in varying temperatures. Additionally, this work provides not only a new strategy to stabilize reactive chemicals, but also a unique method to elucidate their structures

    Self-Assembly of Polyhedral Indium–Organic Nanocages

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    A synthetic strategy to construct discrete indium–organic polyhedra has been illustrated based on small three-membered windows from a 2,5-pyridinedicarboxylate (PDC) ligand with an angle of 120°. [Et<sub>2</sub>NH<sub>2</sub>]<sub>6</sub>[In<sub>6</sub>(PDC)<sub>12</sub>] (<b>InOF-10</b>) is a high-symmetry octahedron with eight three-membered windows, and [Et<sub>2</sub>NH<sub>2</sub>]<sub>18</sub>[In<sub>18</sub>(BPDC)<sub>6</sub>(PDC)<sub>30</sub>] (<b>InOF-11</b>) is a complex polyhedron derived from 3-edge-removed octahedra with an auxiliary biphenyl-3,3′-dicarboxylate (BPDC) ligand. Moreover, the sorption behavior of the latter is also well investigated

    Constructing Crystalline Heterometallic Indium–Organic Frameworks by the Bifunctional Method

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    In this work, we systematically report four indium–organic framework (InOF) crystals, which comprise the In­(CO<sub>2</sub>)<sub>4</sub> monomer for [InCu­(inc)<sub>4</sub>]­(NO<sub>3</sub>) (<b>InOF-5</b>) and [Me<sub>2</sub>NH<sub>2</sub>]<sub>2</sub>[In<sub>2</sub>(Cu<sub>4</sub>I<sub>4</sub>)­(pdc)<sub>4</sub>] (<b>InOF</b>-<b>6</b>), the In­(OH)­(CO<sub>2</sub>)<sub>2</sub> chain for [In<sub>2</sub>(Cu<sub>4</sub>I<sub>4</sub>)­(OH)<sub>2</sub>(nia)<sub>4</sub>] (<b>InOF-7</b>), and In<sub>3</sub>O­(CO<sub>2</sub>)<sub>6</sub> clusters for [(In<sub>3</sub>O)<sub>2</sub>(Cu<sub>4</sub>I<sub>4</sub>)<sub>3</sub>(nia)<sub>12</sub>(H<sub>2</sub>O)<sub>6</sub>]­(NO<sub>3</sub>)<sub>2</sub> (<b>InOF-8</b>). With the help of the ligand-oriented bifunctional method, a series of novel heterometallic indium–organic frameworks can be easily achieved through the way the pyridyl N-affinitive sites connect to Cu-based units and the COO<sup>–</sup>-affinitive sites to In­(III) centers. This new strategy will open the door to the construction of multifunctional and heterometallic InOF materials

    Thiacalix[4]arene-Supported Kite-Like Heterometallic Tetranuclear Zn<sup>II</sup>Ln<sup>III</sup><sub>3</sub> (Ln = Gd, Tb, Dy, Ho) Complexes

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    Four kite-like tetranuclear Zn<sup>II</sup>Ln<sup>III</sup><sub>3</sub> (Ln= Gd <b>1</b>, Tb <b>2</b>, Dy <b>3</b>, Ho <b>4</b>) clusters supported by <i>p</i>-<i>tert</i>-butylthiacalix­[4]­arene (H<sub>4</sub>BTC4A) have been prepared under solvothermal conditions and structurally characterized by single crystal X-ray diffraction and powder X-ray diffraction (PXRD). In the structures of these four complexes, each of them is capped by two tail-to-tail <i>p</i>-<i>tert</i>-butylthiacalix­[4]­arene molecules to form a bent sandwich-like unit. The photoluminescent analyses reveal that the H<sub>4</sub>BTC4A is an efficient sensitizer for Tb<sup>3+</sup> ions in <b>2</b>. The magnetic properties of complexes <b>1</b>–<b>4</b> are also investigated, in which complex <b>3</b> exhibits slow magnetization relaxation typical for single molecule magnets

    Thiacalix[4]arene-Supported Kite-Like Heterometallic Tetranuclear Zn<sup>II</sup>Ln<sup>III</sup><sub>3</sub> (Ln = Gd, Tb, Dy, Ho) Complexes

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    Four kite-like tetranuclear Zn<sup>II</sup>Ln<sup>III</sup><sub>3</sub> (Ln= Gd <b>1</b>, Tb <b>2</b>, Dy <b>3</b>, Ho <b>4</b>) clusters supported by <i>p</i>-<i>tert</i>-butylthiacalix­[4]­arene (H<sub>4</sub>BTC4A) have been prepared under solvothermal conditions and structurally characterized by single crystal X-ray diffraction and powder X-ray diffraction (PXRD). In the structures of these four complexes, each of them is capped by two tail-to-tail <i>p</i>-<i>tert</i>-butylthiacalix­[4]­arene molecules to form a bent sandwich-like unit. The photoluminescent analyses reveal that the H<sub>4</sub>BTC4A is an efficient sensitizer for Tb<sup>3+</sup> ions in <b>2</b>. The magnetic properties of complexes <b>1</b>–<b>4</b> are also investigated, in which complex <b>3</b> exhibits slow magnetization relaxation typical for single molecule magnets
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