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.

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.

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.

New rht-Type Metal-Organic Frameworks Decorated with Acylamide Groups for Efficient Carbon Dioxide Capture and Chemical Fixation from Raw Power Plant Flue Gas.

The combination of carbon dioxide capture and chemical fixation in a one-pot process is attractive for both chemists and governments. The cycloaddition of carbon dioxide with epoxides to produce cyclic carbonates is an atomic economical reaction without any side products. By incorporating acylamide to enhance the binding affinity toward CO2, new rht-type metal-organic frameworks (MOFs) with (3, 28) and (3, 24) connected units were constructed. Zn-NTTA with two types of dinuclear paddlewheel building blocks-{Zn2(OOC-)4} and {Zn2(OOC-)3}. The high uptake of CO2 (115.6 cm3·g-1) and selectivity over N2 (30:1) at 273 K indicated that these MOFs are excellent candidates for postcombustion CO2 isolation and capture. The MOFs feature high catalytic activity, rapid dynamics of transformation and excellent stability with turnover number (TON) values up to 110 000 per paddlewheel unit after 5 × 6 rounds of recyclability, demonstrating that they are promising heterogeneous catalysts for CO2 cyclo-addition to value-added cyclic carbonates. The cycloaddition of epoxides with wet gases demonstrated that the catalyst activity was not affected by moisture, and the indices of the PXRD patterns of the bulk samples filtered from the catalytic reaction revealed that the crystallinities were maintained. The combination of the selective capture and catalytic transformation in one-pot enables the use of a negative-cost feedstock-raw power plant flue gas without any separation and purification-revealing the broad prospects of such MOFs for practical CO2 fixation in industry.

Formation of a metal-organic framework with high surface area and gas uptake by breaking edges off truncated cuboctahedral cages.

Breaking edges off regular truncated cuboctahedra leads to a metal-organic framework (MOF) with polybenzene topology. This fully characterized MOF with lowest connectivity has the largest BET surface area among interpenetrated MOFs.