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Abstract Gastric cancer is one of the most common cancers globally and has a poor prognosis. MiR‐936 has been reported to regulate cell activity and tumor progression in non‐small cell lung cancer, glioma, and epithelial ovarian cancer. However, the specific role and mechanism of miR‐936 in gastric cancer have not been explored. In present study, gastric cancer cells were transfected with miR‐936 mimic, and cell proliferation, cell cycle distribution, cell apoptosis, migration and invasion were assessed via cell‐counting kit‐8, flow cytometry, wound healing, and transwell assay, respectively. Dual luciferase reporter assay was used to check miR‐936 binding to its downstream target. It was shown that miR‐936 was downregulated in gastric cancer tissues and cells. Erb‐B2 Receptor Tyrosine Kinase 4 (ERBB4) was confirmed as a direct target of miR‐936 and negatively regulated its expression by miR‐936. Overexpression of miR‐936 suppressed cell proliferation, cell cycle progression, cell migration and invasion, and enhanced cell apoptosis in gastric cancer cells, which could be reversed by further ERBB4 overexpression. Western blot results showed that miR‐936/ERBB4 axis regulated Akt‐related pathways to control gastric cancer cell activities. Therefore, our data suggest that miR‐936 overexpression inhibits cell proliferation and invasion and promotes cell apoptosis through Akt‐related pathways by targeting ERBB4, which provides novel insight to target miR‐936 or miR‐936/ERBB4 axis for the treatment of gastric cancer.

AIM: To analyze the risk factors of corneal epithelial dysfunction(CED)after pars plana vitrectomy(PPV).METHODS: Clinical data of 235 patients with 235 eyes of PPV from July 2016 to June 2018 in our hospital were retrospectively analyzed. The age, sex and related medical history of the patients(such as ocular lesions and systemic diseases)were collected, and the intraocular fillers, operation time, postoperative intraocular pressure were recorded. Logistic regression was used to analyze the risk factors of CED after PPV.RESULTS: The incidence of CED after PPV was 16.6%(39/235), and the incidence of persistent corneal epithelial lesion was 1.3%(3/235). Logistic regression showed that age, preoperative xerophthalmia, diabetes mellitus, Silicone oil filling, postoperative high intraocular pressure and operation time were risk factors for CED after PPV. The OR values were 1.270, 5.218, 18.598, 4.659, 10.799 and 1.104, respectively.CONCLUSION: Age, preoperative xerophthalmia, diabetes mellitus, silicone oil filling, postoperative high intraocular pressure and operation time are risk factors for CED after PPV.

Angular ligands are a class of important linkers to design and construct new metal–organic frameworks (MOFs). Herein, solvothermal reaction of 4,4′-(4H-1,2,4-triazole-3,5-diyl)dibenzoic acid (TZDB), a triazole-inserted dicarboxylate, acetate, and Cu(NO3)2·3H2O afforded a copper(II)-organic framework of Cu-TZDB. Structural analysis shows that Cu-TZDB displays an unusual (4,6)-c topological network concomitant with the generation of metalloligand [Cu(TZDB)(H2O)2] in situ. Due to its bi-channel cavities replete with triazolate, coordinated water and methyl groups, Cu-TZDB exhibits CO2 selective adsorption over N2 and CH4, which was not only predicted by ideal adsorption solution theory (IAST), but also verified by dynamic column breakthrough tests. [ABSTRACT FROM AUTHOR]

The use of gaseous CO in Pd-catalyzed carbonylative quinolone synthesis presents challenges related to safety and precise pressure control. In response, a streamlined non-gaseous synthesis of 4-quinolone compounds has been developed. This study introduces a tunable CO-releasing system utilizing Fe(CO)5 activated by a dual-base system of piperazine and triethylamine. This alternative liquid CO resource facilitates the palladium-catalyzed carbonylative C-C coupling and subsequent intramolecular cyclization. By tuning the tandem kinetics of carbonylation and cyclization, this non-gaseous method achieves the successful synthesis of 22 distinct 4-quinolones with excellent yields. This is achieved through the three-component condensation of sub-stoichiometric amounts of Fe(CO)5 with 2-iodoaniline and terminal alkynes. Operando mechanistic studies have revealed a novel CO transfer mechanism that facilitates homogeneous carbonylative cyclization, distinguishing this method from traditional techniques. In addition to addressing safety concerns, this approach also provides precise control over selectivity, with significant implications for pharmaceutical research and the efficient synthesis of pharmaceutical and bioactive compounds. [ABSTRACT FROM AUTHOR]

AIM:To observe, analyze and compare the effect of minimally external surgery under microscopy and traditional external surgery on the treatment of non-complicated rhegmatogenous retinal detachment. METHODS:The clinical data of 53 patients with 53 eyes of non-complicated rhegmatogenous retinal detachment in our hospital was analyzed retrospectively, of which the minimally external retinal detachment surgery under microscopy was performed in 25 patients with 25 eyes of non-complicated rhegmatogenous retinal detachment(the research group), and the traditional external retinal detachment surgery was performed in 28 patients with 28 eyes of non-complicated rhegmatogenous retinal detachment(the control group). All surgeries were performed by the same surgeon, and the clinical efficacy and complications of the two groups were compared and analyzed. RESULTS: In postoperative hole closure, there was no significant difference in the primary rate of reattachment of the retina between the two groups(P>0.05). There was a statistically significant difference in postoperative complications between the two groups(PP>0.05). There was a statistically significant difference in operative time between the two groups(PCONCLUSION: The effect of minimally external retinal surgery under microscopy and traditional external retinal surgery is similar in the treatment of non-complicated rhegmatogenous retinal detachment, but the minimally external retinal surgery has the advantages of shorter time, less damage and fewer complications.

Design and construction of highly porous and diverse zeolite-like metal–organic frameworks (ZMOFs) still remain a great challenge due to the limitation of current synthetic strategies. A double six-membered ring (D6R) is regarded as an effective but challenging secondary building unit to target ZMOFs. One most recent example of kex-MOF-1 is elegantly constructed from inorganic and organic D6Rs. Nevertheless, there is no documented structure built from pure inorganic D6Rs. Herein, solvothermal reactions between an angular dicarboxylate ligand and rare-earth (RE) ions in the presence of 2-fluorobenzoic acid afforded both 3-periodic RE-MOFs. Considering the newly formed nonanuclear RE clusters and ditopic linkers respectively behaving as pure inorganic D6Rs and connecting edges, both compounds display the well-known zeolitic topology of gme and result in two isostructural RE(Yb/Y)-ZMOFs. Thanks to the long distance of the ditopic ligand, both RE-ZMOFs possess considerably high surface areas and pore volumes, and subsequently demonstrate relatively high gravimetric methane storage working capacities. [ABSTRACT FROM AUTHOR]

In pursuit of novel adsorbents with efficient adsorptive gas storage and separation capabilities remains highly desired and challenging. Although the documented zirconium‐tricarboxylate‐based metal–organic frameworks (MOFs) have displayed a variety of topologies encompassing underlying and geometry mismatch ones, the employed organic linkers are exclusively rigid and poorly presenting one type of conformation in the resultant structures. Herein, a used and semirigid tricarboxylate ligand of H3TATAB was judiciously selected to isolate a zirconium‐based spe‐MOF after the preliminary discovery of srl‐MOF. Single‐crystal X‐ray diffraction reveals that the fully deprotonated TATAB linker in spe‐MOF exhibits two distinct conformers, concomitant with popular Oh and rare S6 symmetrical Zr6 molecular building blocks, generating an unprecedented (3,3,12,12)‐c nondefault topology. Specifically, the spe‐MOF exhibits structurally higher complexity, hierarchical micropores, open metal sites free and rich electronegative groups on the pore surfaces, leading to relatively high methane storage capacity without considering the missing‐linker defects and efficient MTO product separation performance. [ABSTRACT FROM AUTHOR]

Amide‐functionalized metal–organic frameworks (AFMOFs) as a subclass of MOF materials have received great interest recently because of their intriguing structures and diverse potential applications. In this work, solvothermal reactions between indium nitrate and two mixed‐linkers afforded two new isoreticular 8‐connected trinuclear indium‐based AFMOFs of [(In3O)(OH)(L2)2(IN)2]⋅(solv)x (2‐In) and [(In3O)(OH)(L2)2(AIN)2]⋅(solv)x (NH2‐2‐In) (H2L2=4,4′‐(carbonylimino)dibenzoic acid and HIN=isonicotinic acid or HAIN=3‐aminoisonicotinic acid), respectively. Moreover, by means of reticular chemistry, an extended network of [(In3O)(OH)(L3)2(PB)2]⋅(solv)x(3‐In) (H2L3=4,4′‐(terephthaloylbis(azanediyl))dibenzoic acid, HPB=4‐(4‐pyridyl)benzoic acid) was also successfully realized after prolongation of the former dicarboxylate linker and HIN, resulting in a truly 8‐connected isoreticular AFMOF platform. These frameworks were structurally determined by single‐crystal X‐ray diffraction (SCXRD). Sorption studies further demonstrate that 2‐In and NH2‐2‐In exhibit not only high surface areas and pore volumes but also relatively high carbon capture capabilities (the CO2 uptakes reach 60.0 and 75.5 cm3 g−1 at 298 K and 760 torr, respectively) due to the presences of amide and/or amine functional groups. The selectivity of CO2/N2 and CO2/CH4 calculated by IAST are 10.18 and 12.43, 4.20 and 4.23 for 2‐In and NH2‐2‐In, respectively, which were additionally evaluated by mixed‐gases dynamic breakthrough experiments. In addition, high‐pressure gas sorption measurements show that both materials could take up moderate amounts of natural gas. [ABSTRACT FROM AUTHOR]

Luminescent metal–organic frameworks (MOFs) have displayed extensively potential applications for photocatalysis, photoluminescence, electroluminescence, chemical sensors et al. Herein, five new Cd/Zn−organic frameworks of [Cd(HL)C 2 H 5 OH] ( 1 ), [Cd(HL)(2,2′-Bpy)H 2 O] ( 2 ), [Cd 2 (HL) 2 (Phen) 2 ] ( 3 ), [Zn(HL)BIMB] ( 4 ), [Cd 3 (HL) 3 (4,4′-Bpy)DMF]·(H 2 O) ( 5 ) have been deliberately constructed via solvothermal reactions of d 10 transition metal salts, i.e. Cd(NO 3 ) 2 ∙4H 2 O or Zn(NO 3 ) 2 ·6H 2 O, and a V-shaped semi-rigid organic linker of 4,4'-(hydroxymethanediyl) dibenzoic acid (H 3 L) along with the auxiliary poly-nitrogen ligands of 2,2′-Bpy(2,2′-bipyridine), Phen(phenanthroline), BIMB(1,1′-benzene-1,4-diyldimethanediyl-bis-1H-imidazole) and 4,4′-Bpy(4,4′-bipyridine). The crystal structures of compounds 1 – 5 were precisely determined by single-crystal X-ray diffraction (SC-XRD), Powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy (FT-IR) and Thermogravimetic analysis (TGA). As revealed by SC-XRD, the isolated 1 presents a 2-periodic framework encompassing side-by-side channel-typed helical tubes. Compounds 2 – 4 display Z-shaped 1-periodic single chains, concomitant with twin chains and tubular structure, respectively. Interestingly, compound 5 demonstrates a two-fold interpenetrated 3-periodic skeleton in the presence of a rigid pillar of 4,4′-Bpy. Additionally, photoluminescence properties of 1 – 5 were lastly investigated. [ABSTRACT FROM AUTHOR]

Herein we demonstrate how the combined use of the molecular building block (MBB) approach and reticular chemistry allows the fabrication of a highly stable, ultra-microporous metal–organic framework (MOF) that is an efficient sorbent for the challenging separation of propane/propylene. [ABSTRACT FROM AUTHOR]

Reactive blue 21 (RB21), a phthalocyanine dye, is frequently used in the textile industry and has been rarely researched for decontamination in wastewater. Moreover, no existing approach exhibits effective removal capability. It is therefore highly imperative to quest for alternative solution to address this problem. MOFs have recently appeared as new functional materials for environmental remediation due to their intrinsic features of high porosities and light response. Although a few MOFs are inherently responsive to visible light, most MOF materials can mainly harvest UV light; this dramatically limits the utilization of solar energy. Inspired by our previous results that the dye@MOF composite could effectively photodegrade organic dyes under visible-light irradiation, in the current study, three yellow/red/blue cationic dyes were successfully assembled into an identical MOF host singly, dually, and triply; this led to the formation of seven new multi-dye@MOF composites. Systematic investigations reveal that the seven composites can comparatively photodegrade RB21 under visible-light irradiation. Among them, the composite triple-dye@MOF displays the most efficient performance of 95.36%, which is far superior to that of the commercial P25. This finding may open up a new avenue to construct novel composites towards addressing some unresolved environmental issues, i.e. the decontamination of ultra-stubborn dyes in an aqueous solution. [ABSTRACT FROM AUTHOR]

Through solvothermal reaction of In(NO3)3·5H2O and a highly conjugated carboxylate-based tritopic linker, a doubly interpenetrated indium–organic framework, 1, has been successfully prepared. As revealed by single-crystal X-ray diffraction, the isolated 1 displays an anionic framework and channel-type interior spaces replete with imidazole rings and free carboxylate oxygens. Due to its unique structural features, 1 demonstrates not only selective adsorption of cationic MB concomitant with anionic MO molecules with high selectivity, uptake, and adsorption rate, and good reversibility and recyclability, but also photocatalytic activity to efficiently decompose dyes MB and MO under the illumination of either UV or visible light due to the formation of MB@1 and MO/1 composites. The new finding of visible light responsive MB@1 and MO/1 composites may open up more applications. [ABSTRACT FROM AUTHOR]

A hydrothermal reaction between mixed linkers and mixed metals, alkaline earth 4MgCO3·Mg(OH)2·5H2O and 3d Ni(CH3COO3)2·4H2O, resulted in a unique metal–organic framework of SNNU-99 that was impressively isolated and structurally characterized. SNNU-99 was constructed from an unprecedented decanuclear Mg/Ni-based secondary building unit and represents the first (3,10)-connected 3-period net. Alternatively, SNNU-99 can be described through an unusual kgd layer pillared through 2-connected linkers. Due to its specifically structural feature, SNNU-99 has demonstrated selective CO2 adsorption over N2. [ABSTRACT FROM AUTHOR]

Using isoreticular chemistry allows the design and construction of a new rare-earth metal (RE) fcu-MOF with a suitable aperture size for practical steric adsorptive separations. The judicious choice of a relatively short organic building block, namely fumarate, to bridge the 12-connected RE hexanuclear clusters has afforded the contraction of the well-defined RE-fcu-MOF triangular window aperture, the sole access to the two interconnected octahedral and tetrahedral cages. The newly constructed RE (Y3+ and Tb3+) fcu-MOF analogues display unprecedented total exclusion of branched paraffins from normal paraffins. The resultant window aperture size of about 4.7 Å, regarded as a sorbate-size cut-off, enabled a complete sieving of branched paraffins from normal paraffins. The results are supported by collective single gas and mixed gas/vapor adsorption and calorimetric studies. [ABSTRACT FROM AUTHOR]

Using isoreticular chemistry allows the design and construction of a new rare-earth metal (RE) fcu-MOF with a suitable aperture size for practical steric adsorptive separations. The judicious choice of a relatively short organic building block, namely fumarate, to bridge the 12-connected RE hexanuclear clusters has afforded the contraction of the well-defined RE-fcu-MOF triangular window aperture, the sole access to the two interconnected octahedral and tetrahedral cages. The newly constructed RE (Y3+ and Tb3+) fcu-MOF analogues display unprecedented total exclusion of branched paraffins from normal paraffins. The resultant window aperture size of about 4.7 Å, regarded as a sorbate-size cut-off, enabled a complete sieving of branched paraffins from normal paraffins. The results are supported by collective single gas and mixed gas/vapor adsorption and calorimetric studies. [ABSTRACT FROM AUTHOR]

We synthesized a new organo-diphosphonic acid ligand H2O3PCH(Ph)NH(CH2)2NH(Ph)CHPO3H2 [ethane-1,2-diamino-N,N′-bis(benzyl phosphonic)acid, H4edbbp] and its two complexes [NH3CH(CH3)CH2NH3]2M2(edbbp)2·H2O [M=Zn(II) (1), Cd(II) (2)] in this paper. The complexes 1–2 were structurally characterized by means of X-ray single crystal diffraction. The central ion (M=Zn or Cd) has a distorted square-pyramidal coordination environment by three oxygen atoms from phosphonate units and two nitrogen atoms of H4edbbp. The fundamental structural units [M2(edbbp)2]4- are linked by extensive intermolecular hydrogen bonds between 1,2-propyldiamine cations and phosphonate oxygen atoms, forming a one-dimensional chain structure. The third-order nonlinear optical (NLO) properties of 2 were determined by Z-scan techniques. NLO refractive index n2, χ(3) of 2''s, and hyperpolarizability γ values were calculated to be 1.31×10-17m2W-1, 3.19×10-11 and 8.57×10-30esu, respectively. The results indicate that complex 2 exhibits very strong NLO absorption and self-focusing effects. [Copyright &y& Elsevier]

Correction for ‘A dual-functional indium–organic framework towards organic pollutant decontamination via physically selective adsorption and chemical photodegradation’ by Qing Li et al., J. Mater. Chem. A, 2017, DOI: 10.1039/c7ta02216f. [ABSTRACT FROM AUTHOR]

Correction for ‘Topology meets MOF chemistry for pore-aperture fine tuning: ftw-MOF platform for energy-efficient separations via adsorption kinetics or molecular sieving’ by Dong-Xu Xue et al., Chem. Commun., 2018, DOI: URL10.1039/c8cc03841d/URL. [ABSTRACT FROM AUTHOR]

Tailored access for adsorbents is possible by using metal–organic frameworks (MOFs) with the appropriate pore‐aperture size. In their Communication on page 14353 ff., M. Eddaoudi and co‐workers construct a new rare earth metal (RE) fcu‐MOF with a triangular window aperture which provides unrivalled total exclusion of branched paraffins from normal paraffins. The optimal aperture size results from selecting the shortest linker from the available ditopic ligands. [ABSTRACT FROM AUTHOR]

The existence of donor effector cell subsets responsible for either gut or skin graft-versus-host disease (GvHD) is still undetermined. We examined the trafficking and role of donor CD8+ intra-epithelial lymphocytes (IELs) in the gut and skin epithelia concerning αEβ7 integrin (CD103) expression, using a rat acute lethal GvHD model. Most CD103+ donor cells were CD8+ and showed a proliferative activity in the target epithelia. On the other hand, activated donor T cells in the host lymphoid tissues did not express CD103, indicating the presence of CD8+ IEL precursors in the lymphoid tissues that may up-regulate CD103 only after migrating to the target organs. At the late stage of GvHD, while >80% of the donor CD8+ IELs were CD103+ in the gut epithelium, both CD4+ and CD103+CD8+ T cells evenly accumulated in the skin epidermis. The CD103 expression by donor CD8+ IELs especially in the gut was also correlated with the clinical GvHD manifestations. Furthermore, the selective removal of gut lymph nodes (LNs) but not skin LNs suppressed the infiltration of CD103+ donor IELs in the gut and alleviated intestinal GvHD. In conclusion, CD103+CD8+ donor T cells predominantly infiltrate into the gut epithelium and are responsible for the manifestations of intestinal GvHD. This pathology is at least partly dependent on the gut LNs. [ABSTRACT FROM AUTHOR]

Abstract: A dearomatized complex [RuH(PN3P)(CO)] (PN3P N, N′-bis(di-tert-butylphosphino)-2,6-diaminopyridine) (3) was prepared by reaction of the aromatic complex [RuH(Cl)(PN3P)(CO)] (2) with t-BuOK in THF. Further treatment of 3 with formic acid led to the formation of a rearomatized complex (4). These new complexes were fully characterized and the molecular structure of complex 4 was further confirmed by X-ray crystallography. In complex 4, a distorted square-pyramidal geometry around the ruthenium center was observed, with the CO ligand trans to the pyridinic nitrogen atom and the hydride located in the apical position. The dearomatized complex 3 displays efficient catalytic activity for hydrogen transfer of ketones in isopropanol. [Copyright &y& Elsevier]

In this work, we present the implementation of reticular chemistry and the molecular building block approach to unveil the appropriateness of Rare Earth (RE) based Metal-Organic Frameworks (MOFs) with fcu topology for H 2 S removal applications. Markedly, RE- fcu -MOFs, having different pore aperture sizes in the range of 4.7–6.0 Å and different functionalities, showed excellent properties for the removal of H 2 S from CO 2 and CH 4 containing gases such as natural gas, biogas and landfill gas. A series of cyclic mixed gas breakthrough experiments were carried out on three isoreticular fcu -MOFs, containing linkers of different lengths (between 8.4 and 5 Å), by using simulated natural gas mixture containing CO 2 /H 2 S/CH 4 (5%/5%/90%) under different adsorption and regeneration conditions. The fcu -MOF platform has good H 2 S removal capacity with a high H 2 S/CO 2 selectivity, outperforming benchmark materials like activated carbon and Zeolites in many aspects. The comparison of H 2 S removal performance with the related structures of the RE- fcu -MOFs provides insightful information to shed light on the relationship between the structural features of the MOF and its associated H 2 S separation properties. The excellent H 2 S/CO 2 and H 2 S/CH 4 selectivity of these materials offer great prospective for the production of pure H 2 S, with acceptable levels of CO 2 for Claus process to produce elemental sulfur. [ABSTRACT FROM AUTHOR]

A water-soluble polypyridine copper complex Cu(dpp)(ClO 4 ) 2 ( 1 , dpp = 2,9-di(pyridin-2-yl)-1,10-Phenanthroline) enables to electrocatalyze H 2 generation from neutral phosphate buffer solution at a relatively low overpotential of 520 mV vs. SHE. Sustained proton reduction catalysis occurs at glassy carbon electrode at −1.4 V vs. SHE for 2 h to give H 2 with TONs of 734 mol H 2 (mol catalyst) −1 cm −2 and 95% Faradaic yield. CVs, UV–Vis spectra, SEM, EDX and Tyndall analysis reveals that 1 has the desired stability and functions as a molecular electrocatalyst under the conditions. Due to the relatively low overpotential and high stability, light-driven hydrogen production based on 1 were also carried out with a TONs of 6 mol H 2 (mol catalyst) −1 in an aqueous solution. [ABSTRACT FROM AUTHOR]

Both isostructural amide-functionalized rare-earth metal–organic frameworks have been judiciously and successfully designed and constructed by virtue of topology-guided approach and solvothermal reaction method. Both materials exhibit not only relatively high surface areas and pore volumes, but also selective adsorption propylene over ethylene, exemplifying potential application toward MTO product separation. [Display omitted] • Both rare-earth amide-functionalized MOFs were synthesized via topology-guided approach. • Both materials exhibit relatively high surface areas and pore volumes. • The rich amide-functionality contributes to selective adsorption C 3 H 6 over C 2 H 4. Topology is playing an important role for the reticular chemistry of metal–organic frameworks (MOFs). We herein report two isostructural rare-earth amide-functionalized MOFs by virtue of topology-guided strategy and solvothermal reactions. Both MOFs display the desired (3,8,12)-c pek topological network and encompass dual cage-like and channel pore geometry replete with amide functionality. Low-pressure gas adsorption measurements show that both materials exhibit relatively high surface areas and pore volumes. Moreover, both materials selectively adsorb propylene over ethylene in a wide range of composition as revealed by high C 3 H 6 /C 2 H 4 uptake rations and IAST selectivity. [ABSTRACT FROM AUTHOR]

The efficient single-step purification of ethylene from ternary C 2 mixtures containing ethane and acetylene is challenging and demanding. Herein, we introduce a novel cerium-based metal-organic framework (MOF) of Ce-NTB- rtk synthesized via a ligand-conformer strategy. The Ce-NTB- rtk features a rare tetranuclear cerium cluster and 2D kgd layers pillared by a 3D rtl framework concomitant with an extraordinary (3,3,12)-c network. The compound encompasses microporous cavities replete with a nonpolar microenvironment. Gas sorption and breakthrough experiments demonstrate its superior affinity for C 2 H 6 and C 2 H 2 over C 2 H 4 , enabling effective single-step ethylene purification. Computational simulations reveal that preferential adsorptions are facilitated by different interaction strengths of C-H···O hydrogen bonds. The performance of Ce-NTB- rtk in separation selectivity and regeneration capacity makes it a promising candidate for sustainable and cost-effective ethylene purification, showcasing the potential of MOFs in advanced gas separation applications.

Due to their intrinsic structural features, the design and synthesis of a new type of zeolite-like metal-organic frameworks (ZMOFs) is highly desirable but challenging. Herein, solvothermal reactions between an angular dicarboxylate linker and rare-earth (RE) ions afforded two RE-MOFs, namely, Tb-ZMOF-2 and Tb-ZMOF-3, respectively. Structural analyses reveal that Tb-ZMOF-2 encompasses a novel [4 4 6 4 8 2 ] cage, while Tb-ZMOF-3 contains nonanuclear (i.e., D6R) and hexanuclear (i.e., D4R) RE clusters simultaneously, subsequently resulting in two new zeolitic topologies. Thanks to its high surface area and pore volume, Tb-ZMOF-2 demonstrates considerably high gravimetric and volumetric methane storage working capacities.

Due to the industrial requirements for high production and high quality of ethylene, efficient purification of ethylene from acetylene and ethane is of prime importance but challenging. Dynamic metal-organic frameworks (MOFs) have demonstrated intriguing structural dynamics and diverse applications recently. Among them, although a few flexible ones have exhibited interesting ethylene purification capability, rigid ones were yet barely investigated for such purpose. In this regard, a cerium(III)-based MOF was solvothermally synthesized, which is rigid and assembled from rod molecular building blocks associated with coordinative N , N -dimethylformamide (DMF) molecules. After liberating different degrees of DMF ligands via heating under vacuum or acetone exchange, both partially desolvated compounds of Ce-MOF-1 and Ce-MOF-2 were concertedly isolated in a fashion of single-crystal to single-crystal transformation. Although both newly generated materials crystallize in the same space group, they exhibit dissimilar unit cell parameters and slightly distinct ultramicropore sizes and pore microenvironments, thanks to the discrepancy in the desolvation degree. Consequently, Ce-MOF-1 and Ce-MOF-2 individually demonstrate C 2 H 2 - and C 2 H 6 -selective adsorption behavior, resulting in the potential tandem separation of C 2 H 4 from C 2 H 2 and C 2 H 6 mixtures. The above results were successfully supported by not only single gas adsorption isotherms but also grand canonical Monte Carlo (GCMC) calculation studies and dynamic breakthrough experiments. The present work may pave the way for rigid MOFs aiming at advancing applications via solid-state structural dynamics.

How to accurately detect and efficiently sweep Cr(VI) from contaminated water has come into focus. Zirconium-based metal-organic frameworks (MOFs) play vital roles in water environmental chemistry due to excellent hydrolysis-resistant stability. However, as photochemical probes and photocatalysts, poor performances in detection sensitivity, selectivity, and photosensitiveness limit sole Zr-MOFs' applications. So, it is urgent to quest valid strategies to break through the dilemmas. Embedding luminous dyes into MOFs has been considered one of the most feasible avenues. Herein, a dual-emissive RhB@Zr-MOF with orange-yellow fluorescence has been assembled by in situ-encapsulating rhodamine B (RhB) into a zirconium-biquinoline-based MOF. Actually, within RhB@Zr-MOF, the aggregation fluorescence quenching (ACQ) effect of RhB molecules was effectively avoided. Notably, RhB@Zr-MOF exhibits a rapid fluorescence quenching response toward Cr(VI) ions with high selectivity, sensitivity, and anti-interference abilities. More interestingly, unlike the most widely reported fluorescence resonance energy transfer (FRET) between MOFs and encapsulated guest modules, photoinduced electron transfer from RhB to Zr-MOF has been confirmed by modeling the ground state and excited states of RhB@Zr-MOF using density functional theory (DFT) and time-dependent DFT (TD-DFT). The effective electron transfer makes RhB@Zr-MOF more sensitive in probing Cr 2 O 7 2- and CrO 4 2- ions with ultralow detection limit (DL) values of 6.27 and 5.26 ppb, respectively. Prominently, the detection sensitivity based on DL values has been increased about 6 and 9 times, respectively, compared with pristine Zr-MOF. Moreover, rather negative CB and positive VB potentials make RhB@Zr-MOF have excellent photochemical scavenging ability toward Cr(VI) and MO.

Reticular chemistry and methane storage materials have been predominately focused on finite metal-cluster-based metal-organic frameworks (MOFs). In contrast, MOFs constructed from infinite rod secondary building units (SBUs), i.e., rod MOFs, are less developed, and the existing ones are typically built from simple one-way helical, zigzag, or (mixed)polyhedron SBUs. Herein, inspired by a recent unveiled structure of Zn 6 (H 2 O) 3 (BTP) 4 and by means of an amide-functionalized preliminary single tricarboxylate, a subsequent mixed tricarboxylate, and dicarboxylate linkers, an intricate three-way rod MOF and the next three isoreticular three-way rod MOFs have been successfully realized, namely, 3W-ROD-1 and 3W-ROD-2-X (X = -OH, -F, and -CH 3 ), respectively. The structural analyses disclosed that the four compounds were constructed from unprecedented three-way invariant nonintersecting trigonal rod-packing SBUs cross-linked via the noncovalent-interaction-driven self-assembly of pseudo hexacarboxylates with the original tricarboxylate or different functional ditopic linkers, resulting in cage-like pore geometries accessible via ultramicroporous apertures concomitant with the complex topology transitivity, namely, 18 42 and 18 44. Sorption studies show that the apparent surface areas of these materials are among the most highly porous materials for rod MOFs. Due to the presence of favorable pocket sites created by X, ketone, and proximal amide groups as revealed by Monte Carlo molecular dynamics (MCMD) computational calculations, the MOFs exhibit impressive methane storage working capacities, outperforming the well-known rod Ni-MOF-74 and representing the highest values among rigid rod MOFs.

In pursuit of novel adsorbents with efficient adsorptive gas storage and separation capabilities remains highly desired and challenging. Although the documented zirconium-tricarboxylate-based metal-organic frameworks (MOFs) have displayed a variety of topologies encompassing underlying and geometry mismatch ones, the employed organic linkers are exclusively rigid and poorly presenting one type of conformation in the resultant structures. Herein, a used and semirigid tricarboxylate ligand of H 3 TATAB was judiciously selected to isolate a zirconium-based spe-MOF after the preliminary discovery of srl-MOF. Single-crystal X-ray diffraction reveals that the fully deprotonated TATAB linker in spe-MOF exhibits two distinct conformers, concomitant with popular O h and rare S 6 symmetrical Zr 6 molecular building blocks, generating an unprecedented (3,3,12,12)-c nondefault topology. Specifically, the spe-MOF exhibits structurally higher complexity, hierarchical micropores, open metal sites free and rich electronegative groups on the pore surfaces, leading to relatively high methane storage capacity without considering the missing-linker defects and efficient MTO product separation performance., (© 2021 Wiley-VCH GmbH.)