Immobilization of Amino-site into a Pore-Partitioned Metal-Organic Framework for Highly Efficient Separation of Propyne/Propylene.

Adsorptive separation of propyne/propylene (C3H4/C3H6) is a crucial yet complex process, however, it remains a great difficulty in developing porous materials that can meet the requirements for practical applications, particularly with an exceptional ability to bind and store trace amounts of C3H4. Functionalization of pore-partitioned metal-organic frameworks (ppMOFs) is methodically suited for this challenge owing to the possibility of dramatically increasing binding sites on highly porous and confined domains. We here immobilized Lewis-basic (-NH2) and Lewis-acidic (-NO2) sites on this platform. Along with an integrated nature of high uptake of C3H4 at 1 kPa, high uptake difference of C3H4-C3H6, moderated binding strength, promoted kinetic selectivity, trapping effect and high stability, the NH2-decorated ppMOF (NTU-100-NH2) can efficiently produce polymer-grade C3H6 (99.95 %, 8.3 mmol ⋅ g-1) at room temperature, which is six times more than the NO2-decorated crystal (NTU-100-NO2). The in situ infrared spectroscopy, crystallographic analysis, and sequential blowing tests showed that the densely packed amino group in this highly porous system has a unique ability to recognize and stabilize C3H4 molecules. Moving forward, the strategy of organic functionalization can be extended to other porous systems, making it a powerful tool to customize advanced materials for challenging tasks.

Finely Tuning Metal Ion Valences of [Fe3-xMx(µ3-OH)(Carboxyl)6(pyridyl)2] Cluster-Based ant-MOFs for Highly Improved CO2 Capture Performances.

Solvothermal reactions of different trinuclear precursors and 5-(pyridin-4-yl)isophthalic acid (H2L) successfully led to four anionic ant topological MOFs as Fe3-xMx(µ3-OH)(CH3COO)2(L)2·(DMA+)·DMF [M = Mn(II), Fe(II), Co(II), x = 0, 1, 2 and 3], namely, NJTU-Bai79 [NJTU-Bai = Nanjing Tech University Bai's group, Mn3(µ3-OH)], NJTU-Bai80 [Fe2Mn(µ3-OH)], NJTU-Bai81 [Fe3(µ3-OH)], and NJTU-Bai82 [Fe2Co(µ3-OH)], which possess the narrow pores (2.5-6.0 Å). NJTU-Bai80-82 is able to be tuned to the neutral derivatives [NJTU-Bai80-82(-ox), ox = oxidized] with M2+ ions oxidized to M3+ ones in the air and the OH- ions coordinated on M3+ ions. Very interestingly, selective CO2/N2 adsorptions of NJTU-Bai80-82(-ox) are significantly enhanced with the CO2 adsorption uptakes more than about 6 times that of NJTU-Bai79. GCMC simulations further revealed that neutral NJTU-Bai80-82(-ox) supplies more open frameworks around the -CH3 groups at separate spaces to the CO2 gas molecules with relatively more pores available to them after the removal of counterions. For the first time, finely tuning metal ion valences of metal clusters of ionic MOFs and making them from electrostatic to neutral were adopted for greatly improving their CO2 capture properties, and it would provide another promising strategy for the exploration of high-performance CO2 capture materials.

Tuning Multiple Counter-Anions in Porous Coordination Polymers with lcy Topology for Acetylene/Ethylene Separation.

The efficient separation of acetylene (C2H2) and ethylene (C2H4) is an important and complex process in the industry. Herein, we report a new family of lcy-topologic coordination frameworks (termed NTU-90 to NTU-92) with Cu3MF6 (M = Si, Ti, and Zr) nodes. These charged frameworks are compensated by different counterbalanced ions (MF62-, BF4-, and Cl-), yielding changes in the size of the window apertures. Among these frameworks, NTU-92-a (activated NTU-92) shows good adsorption selectivity of C2H2/C2H4 and also significant ability in recovering both highly pure C2H4 (99.95%) and C2H2 (99.98%). Our work not only presents a potential alternative for energy-saving purification of C2 hydrocarbons but also provides a new approach for tuning the function of charged porous materials.

Exploring the impact of TGF-ß family gene mutations and expression on skin wound healing and tissue repair.

Transforming Growth Factor-Beta (TGF-ß) signalling pathway is of paramount importance in the processes of wound healing, epidermal integrity maintenance and development of skin cancer. The objective of this research endeavour was to clarify the impact of gene mutations and variations in expression within TGF-ß family on mechanisms of tissue repair, as well as to identify potential targets for therapeutic purposes in non-melanoma skin cancer (NMSC). The methods utilized in this study involved obtaining RNA-seq data from 224 NMSC patients and paired normal skin tissues from the PRJNA320473 and PRJEB27606 databases. The purpose of the differential gene expression analysis was to identify genes whose expression had changed significantly. In order to evaluate the effects and interrelationships of identified gene variants, structural analysis with AlphaFold and PDB data and network analysis with the STRING database were both utilized. Critical gene expression was externally validated through the utilization of the GEPIA database. Tumour tissues exhibited a notable upregulation of genes associated with the TGF-ß pathway, specifically MMP1, MMP3, MMP9, EGF, COL3A1 and COL1A2, in comparison with normal tissues. As indicated by the central node status of these genes in the network analysis, they play a crucial role in the progression of NMSCs. The results of the structural analysis suggested that mutations might cause functional disruptions. External validation of the upregulation confirmed the expression trends and emphasized the biomarker potential of the upregulated genes. In conclusion, this research offered thorough examination of molecular modifications that occur in TGF-ß family genes, which are linked to cutaneous wound healing and NMSC. The modified expression of the identified hub genes may represent innovative targets for therapeutic intervention.

Delicate Softness in a Temperature-Responsive Porous Crystal for Accelerated Sieving of Propylene/Propane.

Soft nanoporous crystals with structural dynamics are among the most exciting recently discovered materials. However, designing or controlling a porous system with delicate softness that can recognize similar gas pairs, particularly for the promoted ability at increased temperature, remains a challenge. Here, we report a soft crystal (NTU-68) with a one-dimensional (1D) channel that expands and contracts delicately around 4 Å at elevated temperature. The completely different adsorption processes of propane (C3H8: kinetic dominance) and propylene (C3H6: thermodynamic preference) allow the crystal to show a sieving separation of this mixtures (9.9 min·g-1) at 273 K, and the performance increases more than 2-fold (20.4 min·g-1) at 298 K. This phenomenon is contrary to the general observation for adsorption separation: the higher the temperature, the lower the efficiency. Gas-loaded in situ powder X-ray analysis and modeling calculations reveal that slight pore expansion caused by the increased temperature provides plausible nanochannel for adsorption of the relatively smaller C3H6 while maintaining constriction on the larger C3H8. In addition, the separation process remains unaffected by the general impurities, demonstrating its true potential as an alternative sorbent for practical applications. Moving forward, the delicate crystal dynamics and promoted capability for molecular recognition provide a new route for the design of next-generation sieve materials.

Formation and fine-tuning of metal-organic frameworks with carboxylic pincers for the recognition of a C2H2 tetramer and highly selective separation of C2H2/C2H4.

Highly efficient ethylene (C2H4) and acetylene (C2H2) separation is a great challenge and an important process in current industries. Herein, we finely tune a new family of 6-c metal-organic frameworks (MOFs) with crab-like carboxylic pincers for the recognition of a C2H2 tetramer and afford NTU-72 with high adsorption C2H2/C2H4 selectivity (56-441, 298 K) as well as unprecedented recovery of both highly pure C2H4 (99.95%) and C2H2 (99.36%). Furthermore, the effective binding of a C2H2 tetramer by NTU-72's carboxylic pincers has been revealed by gas-loaded crystallography and Raman spectral studies. Our work provides a novel approach for the selective binding of a small molecular cluster for designing high-performance MOFs.

Confining Water Nanotubes in a Cu10O13-Based Metal-Organic Framework for Propylene/Propane Separation with Record-High Selectivity.

Energy-efficient separation of propylene (C3H6)/propane (C3H8) is in high demand for the chemical industry. However, this process is challenging due to the imperceptible difference in molecular sizes of these gases. Here, we report a continuous water nanotube dedicatedly confined in a Cu10O13-based metal-organic framework (MOF) that can exclusively adsorb C3H6 over C3H8 with a record-high selectivity of 1570 (at 1 bar and 298 K) among all the porous materials. Such a high selectivity originates from a new mechanism of initial expansion and subsequent contraction of confined water nanotubes (∼4.5 Å) caused by C3H6 adsorption rather than C3H8. Such unique response was further confirmed by breakthrough measurements, in which one adsorption/desorption cycle yields each component of the binary mixture high purity (C3H6: 98.8%; C3H8: >99.5%) and good C3H6 productivity (1.6 mL mL-1). Additionally, benefiting from the high robustness of the framework, the water nanotubes can be facilely recovered by soaking the MOF in water, ensuring long-term use. The molecular insight here demonstrates that the confining strategy opens a new route for expanding the function of MOFs, particularly for the sole recognition from challenging mixtures.

Ligand-Functional Groups Induced Tuning MOFs' 2D into 1D Pore Channels for Pipeline Natural Gas Purification.

The solvothermal reactions of CoCl2 ⋅ 6H2 O, 3,5-pyridinedicarboxylic acid (H2 L) and isonicotinic acid (HL1 )/3-amino isonicotinic acid (HL2 )/3-chloro isonicotinic acid (HL3 ) successfully led to three tfz-d topological pillar-layer [Co4 (µ-F)2 (COO)6 (NC5 H4 )4 ] cluster-based MOFs, namely, [Co4 (µ-F)2 (L)2 (L1 )2 ⋅ 2DMA] ⋅ DMA ⋅ 2H2 O (SNNU-Bai76, SNNU-Bai=Shaanxi Normal University Bai's group), [Co4 (µ-F)2 (L)2 (L2 )2 ⋅ 2H2 O] ⋅ 2DMA ⋅ 2H2 O (SNNU-Bai77) and [Co4 (µ-F)2 (L)2 (L3 )2 ⋅ 2H2 O] ⋅ 2DMF ⋅ 2H2 O (SNNU-Bai78). With the 2D pore channels in SNNU-Bai76 and SNNU-Bai77 being tuned to the 1D pore channel in SNNU-Bai78, C3 H8 and C2 H6 adsorption uptakes are apparently improved and the IAST selectivities of C3 H8 /CH4 and C2 H6 /CH4 almost remain, which indicate that SNNU-Bai78 may be one potential separation material for the pipeline natural gas purification. These were further confirmed by the breakthrough experiments for the simulated pipeline natural gas (C3 H8 /C2 H6 /CH4 : 5/10/85 gas mixture) of three isostructural MOFs. Furthermore, GCMC simulations revealed that due to one of the pore channels blocked by Cl atoms in a couple of 3-chloro isonicotinic acid with the changed conformation as the pillar, the pore wall of the formed 1D pore channel in SNNU-Bai78 may interact with the adsorbed C3 H8 or C2 H6 molecule more strongly, for which more atoms of framework at the new adsorption site will interact with the adsorbed gas molecule by more intermolecular interactions. This was also evidenced by the increased binding energies, being consistent with the tuning of adsorption enthalpies for C3 H8 and C2 H6 gas molecules, and the reduced C3 H8 and C2 H6 gas diffusion coefficients in SNNU-Bai78. Very interestingly, this work is the first example of finely tuning the pore connectivity of MOFs toward strengthened host-guest interactions for the gas adsorption and separation.

Anion Regulates scu Topological Porous Coordination Polymers into the Acetylene Trap.

The development of efficient porous absorbents with high uptake and selectivity remains a great challenge, especially for the recovery of acetylene (C2H2) from its carbon dioxide (CO2)-containing mixtures. Here, we propose and report an anion-planting strategy for regulating the scu topological porous coordination polymers (PCPs) into the C2H2 trap. The three electronegative anions SiF62-, TiF62-, and ZrF62-, in addition to the ligand of 3,5-di(1H-imidazol-1-yl)benzoic acid (HL) and Cu2+ ion, were employed to construct highly porous PCPs (NTU-60, NTU-61, and NTU-62) with varied window aperture. Especially, due to a matching distance (dF-F) of 5.7 Å along the c-axis, the limited space that can be assigned as a single C2H2 trap enables NTU-61 to show optimal ability for C2H2 (van der Waals (vdW) parameters of the two H atoms: ∼5.72 Å) recognition, validated by Grand Canonical Monte Carlo (GCMC) calculations and Raman spectra. These characteristics allow the NTU-series to show higher C2H2 uptake, as well as excellent C2H2/CO2 separation performance under dynamic conditions. The molecular insight and strategy here not only permit balanced adsorption and separation in a single domain but also exhibit an opportunity to develop advanced adsorbents in nearly all frameworks with lattice or coordinated ions, which may act as the platforms for various selective guest trappings with on-demand time and/or spatial resolution.

Double-Walled Zn36@Zn104 Multicomponent Senary Metal-Organic Polyhedral Framework and Its Isoreticular Evolution.

Metal-organic polyhedral frameworks are attractive in gas storage and separation due to large voids with windows that can serve as traps for guest molecules. Introducing multivariant/multicomponent functionalities in them are ways of improving performances for certain targets. The high compatibility of organic linkers can generate multivariant MOFs, but by far, the diversity of secondary building units (SBUs) in a single metal-organic framework is still limited (no more than two in most cases). Here we report a new double-walled Zn36@Zn104 metal-organic polyhedral framework (HHU-8) with five types of topologically distinct SBUs and its isoreticular evolution to the Zn36@Zn136 counterpart (HHU-8s). Both MOFs are the first to be constructed with such high numbers of topologically distinct SBUs as well as topologically distinct nodes, and their formation and evolution provide new insight into SBU's controllability.

Tuning Open Metal Site-Free ncb Type of Metal-Organic Frameworks for Simultaneously High Gravimetric and Volumetric Methane Storage Working Capacities.

The design and synthesis of a single metal-organic framework (MOF) material with simultaneously high gravimetric and volumetric methane storage working capacities are still a great challenge. The open metal site (OMS) in MOFs is generally regarded as an advantage to enhance host-guest affinity. However, it is detrimental to the methane storage working capacity to some extent due to the resulting high low-pressure uptake. Moreover, the reported methane storage MOFs are predominately focusing on edge-transitive or low-connected mixed-linker networks. In contrast, high-connected mixed-linker MOFs have been less investigated for methane storage. Herein, three isoreticular nine-connected trinuclear iron-based Fe-ncb-MOFs without OMSs have been judiciously designed and successfully constructed by means of the mixed-linker approach associated with the fixing amide-functionalized pyridyl-carboxylate ligand LP (4-(pyridin-4-ylcarbamoyl)benzoate) and three differing sized dicarboxylate ligands. High-pressure methane adsorption measurements show that, with the isoreticular extension from BDC (1,4-benzenedicarboxylate) to BPDC (4,4'-biphenyldicarboxylate) and ABDC (azobenzene-4,4'-dicarboxylate), three Fe-ncb-MOFs exhibit gradually increasing not only gravimetric but also volumetric storage capacities because of their balancing gravimetric surface area and volumetric surface area, hierarchical pore system, and modest CH4 heats of adsorption. Among them, the Fe-ncb-ABDC demonstrates a rare combination of simultaneously high gravimetric and volumetric CH4 storage working capacities of 0.302/0.37 g g-1 and 196/240 cm3 (STP) cm-3 at 298/273 K and between 80 and 5 bar, respectively, which outperform the 8-c Fe-8T18-ABDC assembled from a shorter pyridyl-carboxylate ligand IN (isonicotinate) and ABDC, due to its limited pore volume, the presence of OMSs, and more confined pore spaces, and place Fe-ncb-ABDC among the best performing MOFs.

Formation of a N/O/F-Rich and Rooflike Cluster-Based Highly Stable Cu(I/II)-MOF for Promising Pipeline Natural Gas Upgrading by the Recovery of Individual C3H8 and C2H6 Gases.

Due to the ultralow amounts of C3H8 and C2H6 gases, to design and synthesize water-stable MOFs that are promising for real-world efficient pipeline natural gas (NG) upgrading by the recovery of individual C3H8 and C2H6 gases is still a great challenge. Here, a N/O/F heteroatom-rich and rooflike [Cu(II)4Cu(I)2(COO)4(tetrazolyl)6] cluster-based ultra-microporous tsi-MOF (SNNU-Bai68) was afforded as a multiple heteroatom-rich and curved-surface-shaped cluster-based ultra-microporous MOF and the first porous MOF based upon such rooflike [Cu(II)xCu(I)y(tetrazolyl)z](2x+y-z)+ cluster. In SNNU-Bai68, the rooflike cluster was further assembled into a 1D chain secondary building block (SBB), which led to a high density of accessible potential adsorptive sites. Very interestingly, it exhibited the most promising balance of high gas adsorption uptakes at 0.01, 0.03, and 0.05 bar, high C3H8/CH4, C3H8/C2H6, and C2H6/CH4 adsorption selectivities, moderate adsorption enthalpies, and high water and chemical stability for pipeline natural gas upgrading by the recovery of individual C3H8 and C2H6 gases, which was further confirmed by the breakthrough experiments of the gas mixtures with/without 74% RH. Furthermore, the SC-XRD and GCMC studies revealed that the successful separation of C3H8, C2H6, and CH4 gases in SNNU-Bai68 is due to different synergistic effects of H-bonds between the frameworks at three adsorptive sites around each rooflike cluster and those different gas molecules, which were initially described systematically by the number of H atoms from the gas molecules, the total number of H-bonds within the synergistic H-bonds, and the binding energy of the framework at an adsorption site toward the gas molecules. In addition, this work may provide a method for the construction of a multiple heteroatom-rich and curved-surface-shaped cluster-based ultra-microporous MOF as a novel approach to build MOFs with polar pore surfaces, suitable pore sizes, and unique pore shapes to maximize the synergistic H-bonds between the framework and guests.

New Reticular Chemistry of the Rod Secondary Building Unit: Synthesis, Structure, and Natural Gas Storage of a Series of Three-Way Rod Amide-Functionalized Metal-Organic Frameworks.

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 Zn6(H2O)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 -CH3), 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.

Ligand-Conformer-Induced Formation of Zirconium-Organic Framework for Methane Storage and MTO Product Separation.

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 H3 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 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.

Modifying a partial corn-sql layer-based (3,3,3,3,4,4)-c topological MOF by substitution of OH- with Cl- and its highly selective adsorption of C2 hydrocarbons over CH4.

Modifying VNU-18 (a MOF with a partial cone-sql layer pillared by the chains of pillars decorated with OH-) by substitution of OH- with Cl-, a new isoreticular structure, [Cu6(L)5·(Cl-)2·H2O·4DMF]·4DMF·6(H2O) (SNNU-Bai67, SNNU-Bai = Shaanxi Normal University Bai's group), has been successfully synthesized. Furthermore, we deeply investigated the selective C2 hydrocarbon separation properties of SNNU-Bai67 and VNU-18 by single-component gas adsorption experiments, breakthrough experiments and simulation studies. They exhibit highly selective adsorption for C2 hydrocarbons over CH4 compared to many reported MOFs for the separation of C2 hydrocarbons from CH4, due to the suitable pore sizes of the partial corn sql-layer built from the isophthalic acid analogy and Cu-paddlewheel units. Interestingly, with the counterion of OH- in VNU-18 tuned by Cl- in SNNU-Bai67, the adsorption uptake values of C2 hydrocarbons were apparently improved by 15.0% for C2H2, 20.4% for C2H4 and 25.3% for C2H6, respectively, while the IAST selectivities of C2 hydrocarbons/CH4 were still nearly the same, which may be because the synergistic effect of interactions of HC2/1OCOO, HC2/1N/CPy, HPyCC2, ππ or HC2CC2 between the gas molecules and the framework is enhanced by the weaker polarity of Cl- decorating the framework.

A low symmetry cluster meets a low symmetry ligand to sharply boost MOF thermal stability.

A new approach in which a low symmetry cluster meets a low symmetry ligand to sharply boost the thermal stability of a MOF via additional inter-linker interactions is presented for the first time, leading to the successful synthesis of a novel binuclear Co-based MOF, {[Co2(L1)2DMF]·1.5DMF·0.75MeOH·1.5H2O}∞ (H2L1 = 5-(pyridin-3-yl) isophthalic acid, NJU-Bai62: NJU-Bai for Nanjing University Bai group), with exceptional thermal stability of up to 450 °C. This work may open up a new avenue for constructing robust MOFs from abundant, unstable, and low symmetry binuclear clusters, which have usually been ignored by most MOF chemists.

Single-Crystal Synthesis and Diverse Topologies of Hexanuclear CeIV-Based Metal-Organic Frameworks.

CeIV6-based metal-organic frameworks (MOFs) have gained increasing attention recently because of their diverse potential applications and similarity to prominent Zr-MOFs, e.g., the UiO-66 series. However, the reported CeIV6-based MOFs were all structurally determined by means of the powder X-ray diffraction technique, indicative of less practice and convenience. Herein, four single-crystalline CeIV6-based MOFs were successfully isolated and characterized by single-crystal X-ray diffraction, disclosing two series of topologically distinct isoreticular nets accompanied by nine-coordinated central CeIV ions, i.e., 8-connected hex and 12-connected fcu, respectively, in contrast to the previously reported sole fcu topology based on the combination of linear dicarboxylate ligands and a CeIV6 cluster associated with eight-coordinated central CeIV ions according to the UiO-66 structural model. Moreover, all four single-crystalline compounds exhibit permanent microporous porosities and a certain amount of gas uptake toward CO2, CH4, and H2.

Formation of a mixed-valence Cu(i)/Cu(ii) metal-organic framework with the full light spectrum and high selectivity of CO2 photoreduction into CH4.

Based upon the hetero-N,O ligand of pyrimidine-5-carboxylic acid (Hpmc), a new semiconductive Cu(i)/Cu(ii) mixed-valence MOF with the full light spectrum and a novel topology of {43·612·86}2{43·63}2{63}6{64·82}3, {(Cu4I4)2.5[Cu3(µ4-O) (µ3-I) (pmc)3(Dabco)3]·2.5DMF·2MeCN}∞ (NJU-Bai61, NJU-Bai for Nanjing University Bai group; Dabco = 1,4-diazabicyclo [2.2.2] octane), was synthesized stepwise. NJU-Bai61 exhibits good water/pH stabilities and a relatively large CO2 adsorption capacity (29.82 cm3 g-1 at 1 atm, 273 K) and could photocatalyze the reduction of CO2 into CH4 without additional photosensitizers and cocatalysts and with a high CH4 production rate (15.75 µmol g-1 h-1) and a CH4 selectivity of 72.8%. The CH4 selectivity is the highest among the reported MOFs in aqueous solution. Experimental data and theoretical calculations further revealed that the Cu4I4 cluster may adsorb light to generate photoelectrons and transfer them to its Cu3OI(CO2)3 cluster, and the Cu3OI(CO2)3 cluster could provide active sites to adsorb and reduce CO2 and deliver sufficient electrons for CO2 to produce CH4. This is the first time that the old Cu(i) x X y L z coordination polymers' application has been extended for the photoreduction of CO2 to CH4 and this opens up a new platform for the effective photoreduction of CO2 to CH4.

The Quality of Spontaneous Adverse Drug Reaction Reports in China: A Descriptive Study.

Pharmacovigilance is important to monitor the safety of drugs. There are, however, problems with the quality of adverse drug reaction reports in China. This study aimed to analyze the quality of adverse drug reaction reports in China, identify the factors affecting it, and propose measures to improve it. In our study, the western province of Shaanxi, the central province of Hubei and the eastern province of Jiangsu were chosen as typical, and adverse drug reaction reports from these three provinces from 2015 to 2017 were systematically sampled. The sampling reports were scored and graded to assess their quality. The results showed that only 10.18% were considered high quality in a total of 3429 reports. There were statistically significant differences in quality by year, province, report type, report source, and occupation of the reporter (p < 0.001). Reports from Shaanxi were slightly poorer quality, and "new" and "serious" reports and those from pharmacists were higher quality. Five indicators were particularly poor quality: patient information, adverse drug reaction, reporter information, drug information and vigilance. In conclusion, the quality of adverse drug reaction reports in China still needs improvement. Factors affecting quality included timing, location, report type, report source, and reporter's occupation. It may be helpful to publicize the importance of monitoring adverse drug reactions and improve the knowledge of reporters.

Solvents-Dependent Formation of Three MOFs from the Fe3O Cluster and 3,3',5,5'-Diphenyltetracarboxylic Acid and Their Selective CO2 Adsorption.

On the basis of the [Fe3(µ3-O)(COO)6] cluster and 3,3',5,5'-diphenyltetracarboxylic acid (H4BPTC), three novel metal-organic frameworks (MOFs), NJU-Bai25, NJU-Bai26, and NJU-Bai27 (NJU-Bai for Bai's group at Nanjing University ) with different (4,4,4,6)-, (4,4,4,4,4,6)-, and (4,4,6)-connected nets were obtained in different solvent systems, in which due to the steric hindrance of the coordinated solvents the conformations of BPTC gradually change from the planar to the torsional; thus, the pore sizes of those MOFs were also gradually narrowed. Interestingly, the MOFs show high thermal/chemical stabilities and selective CO2 adsorption: NJU-Bai27 exhibits larger CO2 uptake (5.0 and 13.8 wt %) at 298 K under 0.15 and 1 bar, whereas NJU-Bai26 has a higher selectivity for CO2/N2 (366).