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The first ionothermal case of the heterometallic iodoplumbate, [CuPb2I2Br(OH)2] (1), was prepared using 1-ethyl-3-methyl imidazolium bromide as a solvent. It exhibits an unprecedented (4,12)-connected topology with [Pb4(OH)4] cubane as the joint points of the helices. [ABSTRACT FROM AUTHOR]

Solvothermal reaction of the flexible ligand 1,6-bi(benzotriazole)hexane (BBTH) with CuCl generated a 3-D hybrid solid, {[CuCl]2(BBTH)}n (1), which was investigated by elemental analysis, FT-IR, X-ray powder diffraction (XRPD), X-ray single-crystal diffraction, TG/DTA, and photoluminescence measurements. Compound 1 crystallizes in the tetragonal system, space group I4(1)/a, a = b = 17.636(2) Å, c = 13.5345(15) Å, V = 4209.6(9) Å3, Z = 8. The distorted tetrahedral geometry of Cu(I) is defined by two chlorides and two N donors from different BBTH ligands. Adjacent copper atoms are connected by μ2-Cl to give a 1-D zigzag inorganic chain, and further linked by BBTH ligands via μ4-bridging, forming the 3-D hybrid structure of 1. Cu(I) atoms and BBTH ligands can be regarded as two kinds of non-equivalent 4-connected nodes, which lead to an unusual topological network with Schlafli symbol of (32.8.92.10)2(32.82.92). Compound 1 exhibits high thermal stability and shows strong red fluorescence emission at 538 nm in the solid state at ambient temperature. [ABSTRACT FROM AUTHOR]

Abstract: A 3D metal–organic framework, namely, {[EMIM][In3(μ 3-OH)2(1,2,4,5-BTC)2∙2H2O]} n (1) (1,2,4,5-BTC=1,2,4,5-benzenetetracarboxylate), was synthesized by using 1-ethyl-3- methylimidazolium bromide ([EMIM]Br) ionic liquid as solvent. The 7-coordinated pentagonal bipyramidal In(1) and octahedral In(2) atoms are connected by the μ 3-OH groups to form an infinite [In3(μ 3-OH)2] n inorganic chain along the a-axis, which are further extended by 1,2,4,5-BTC ligands to generate the 3D anionic microporous framework of 1. The [EMIM]+ cations occupy the 1D channels acting as template and charge-balancing species. Compound 1 shows strong blue luminescence and remarkable photocatalytic degradation of methylthionine chloride. [Copyright &y& Elsevier]

Abstract: The solubilities, densities and refractive indices data for the four ternary systems ethylene glycol+MCl+H2O (M =Na, K, Rb, Cs) at different temperatures were measured, with mass fractions of ethylene glycol in the range of 0 to 1.0. In all cases, the presence of ethylene glycol significantly reduces the solubility of the salts in aqueous solution. The experimental data of density, refractive index and solubility of saturated solutions for these systems were correlated using polynomial equations as a function of the mass fraction of ethylene glycol. On the other hand, the refractive index and density of unsaturated solutions was also determined for the four ternary systems with varied unsaturated salt concentrations. Values for both the properties were correlated with the salt concentrations and proportions of ethylene glycol in the solutions. [Copyright &y& Elsevier]

Abstract: Solvothermal reactions of the flexible ligand 1,6-Bi(benzotriazole)hexane with CuI and KI or CuBr and KBr in ethanol generate two hybrid compounds, namely, {(HETA)[(Cu6I7)(ETA)2]} n (1) and {K(Cu6Br7)(BBTH)} n (2) (ETA=N-ethylbenzotriazole, HETA=protonated N-ethylbenzotriazole, BBTH=1,6-bi(benzotriazole)hexane). In 1, two [Cu3I4] vertex missing cubane-like subunits link each other by sharing one I atom to give a [Cu6I7] cluster, which further form novel 1D [Cu6I7] n n− anionic chain. Two in-situ generated ETA ligands finished the 4-coordinated environments of copper centers and another one discrete protonated ETA ligand keeps the charge neutrality for 1. In complex 2, bowl-shaped [Cu5Br4] clusters and rhomboid [Cu2Br2] dimers link each other to generate a [Cu6Br7] n n− 1D chain. BBTH ligands complete the tetrahedral spheres of Cu(I), and 7-coordinated K atoms further extend the 1D chain motifs to a 2D hybrid layer of 2. The UV–vis diffuse reflectance spectrum and luminescence measurements show that compound 1 and 2 both are potential semiconductor and photoluminescence materials. [Copyright &y& Elsevier]

Abstract: This work reports the results of a thermodynamic investigation of the ternary mixed-electrolyte system (CsCl+CaCl2 +H2O). The activity coefficients of this mixed aqueous electrolyte system have been studied with the electromotive force measurement (EMF) of the cell: Cs ion-selective electrode (ISE)|CsCl(m A), CaCl2(m B), H2O|Ag/AgCl at T = 298.15K and over total ionic strengths from (0.01 to 1.50)mol·kg−1 for different ionic strength fractions y B of CaCl2 with y B =(0, 0.2, 0.4, 0.6, and 0.8). The cesium ion-selective electrode (Cs-ISE) and the Ag/AgCl electrode used in this work were made in our laboratory and had a good Nernst response. The experimental results obey the Harned rule, and the Pitzer model can be used to describe this ternary system satisfactorily. The osmotic coefficients, excess Gibbs free energies and activities of water of the mixtures were also calculated. [Copyright &y& Elsevier]

Abstract: Reaction of the N-tosyl-ethylenediamine and salicylaldehyde forms a new sulfonamide Schiff base N-[2-(2-hydroxybenzylideneamino)ethyl]-4-methyl-benzene-sulfonamide (H2L). Three novel complexes constructed from H2L, namely, [M(HL)2]· xH2O (M=Cu, x =0 for 1, M=Ni, x =0 for 2 and M=Zn, x =1 for 3) have been prepared and characterized via X-ray single-crystal diffraction, elemental analysis, X-ray powder diffraction (XRPD), FT-IR, UV–Vis, TGA and photoluminescence measurements. Complex hydrogen bonds, C–H···π and π–π stacking interactions lead 1–3 to present 1-D, 2-D and 3-D supramolecular architectures, respectively. [Copyright &y& Elsevier]

Abstract: A novel metal–organic coordination polymer, namely, {[K2(H2O)6][Cd3(1,2,4,5-BTC)2]} n (1) (1,2,4,5-BTC=1,2,4,5-benzenetetracarboxylate), was synthesized in an ionothermal reaction by using an ionic liquid 1-ethyl-3-methylimidazolium bromide ([EMIM]Br) as solvent. Complex 1 features a novel 3-D (4,8)-connected porous anionic architecture constructed by linking trinuclear Cd subunits with 1,2,4,5-BTC4− ligands, which are further filled with 1-D [K2(H2O)6] cationic chains. [Copyright &y& Elsevier]

Abstract: A novel 3D coordination polymer [Ag(dmtrz)] (dmtrz=3,5-dimethyl-1,2,4-triazole) (1) was prepared under solvothermal condition and structurally characterized. The crystal structure reveals that Ag(I) centers are firstly linked via dmtrz anions to form an infinite 21 helix, which is further interconnected to four neighboring anti-parallel helices to form a 3D framework with rare non-interpenetrating 8210-a topology. [Copyright &y& Elsevier]

• Ultrathin Ni 2 P nanomeshes on nickel foam (Ni 2 P-UNMs/NF) is successfully synthesized. • Ni 2 P-UNMs/NF has high specific surface area and sufficient active sites. • Ni 2 P-UNMs/NF shows high electroactivity for hydrogen evolution reaction. • Ni 2 P-UNMs/NF also shows high electroactivity for benzylamine oxidation reaction (BOR). • BOR boosted water-splitting gives a cost/energy-competitive method for H 2 production. In this work, ultra-thin Ni 2 P nanomeshes (1.9 nm thickness) on nickel foam (NF) substrate (denoted as Ni 2 P-UNMs/NF) are successfully achieved through phosphidation treatment using ultra-thin Ni(OH) 2 nanomeshes on NF substrate (denoted as Ni(OH) 2 -UNMs/NF) as reaction precursor. Because of the sufficient active sites in edge of the holes, high specific surface area, porous framework and high conductivity of NF substrate, Ni 2 P-UNMs/NF nanocomposites show the outstanding activity for both hydrogen evolution reaction (HER) and benzylamine oxidation reaction (BOR) in alkaline electrolyte. Importantly, Ni 2 P-UNMs/NF nanocomposites can directly act as a bifunctional electrocatalyst for the electrochemical water-splitting in two electrode system in the presence of benzylamine, which only requires an electrolysis voltage of 1.41 V to achieve the 10 mA cm-2 current density in alkaline electrolyte, accompanying with H 2 production at cathode and value-added benzonitrile production at anode. Obviously, the BOR boosted electrochemical water-splitting provides an energy-saving and cost-competitive H 2 production method. [ABSTRACT FROM AUTHOR]

A ternary luminescent cadmium-triazolate-carboxylate framework, [(CH 3) 2 NH 2 ][Cd(1245-BTC) 0.5 (3S-TRZ)] (SNNU-111, 1245-BTC ​= ​1245-benzenetetra- carboxylic acid, 3S-TRZ ​= ​3-mercaptotriazole) was successfully designed in this work. X-ray single crystal diffraction results show that Cd atoms are connected by 3S-TRZ ligands to form 2D wave-like layers, which are further extended by 1245-BTC linkers to generate the 3D pillar-layered architecture of SNNU-111. Solid-state and solution photoluminescence both showed that the emissions of SNNU-111 was ascribed to the intraligand charge transfer in 1245-BTC. Benefited from this process, SNNU-111 MOF can act as excellent fluorescence sensor to quantitatively detect involved nitroaromatics including nitrobenzene (NB), 1,2-dinitrobenzene (1,2-DNB), 1,3-dinitrobenzene (1,3-DNB), 2,4-dinitrotoluene (DNT), 2,4,6-trinitrotoluene (TNT), and 2,4,6-trinitrophenol (PA) through the fluorescence quenching. The corresponding quenching coefficient (K sv) values are of 1.0 ​× ​104-1.7 ​× ​104 ​M−1, which surpass the performance of many reported sensors. Specially, the K sv value of 1.2 ​× ​104 ​M−1 for NB is nearly the highest one among all MOF sensors up to now. On the other hand, SNNU-111 sensor also exhibits good sensitivity to nitroaromatics with the detection limits as low as 1.61–5.77 ​ppm. Overall, the definite pillar-layered structure, fast response and high sensitivity make SNNU-111 a promising fluorescent sensor to detect nitroaromatic compounds. Reported herein a robust pillar-layered Cd-MOF fluorescence sensor demonstrating very fast and high sensitive detection for multiple nitroaromatic compounds. Image 1 • Robust ternary pillar-layered metal-organic framework. • Continuous π···π stacking pillars. • Excellent fluorescence sensing performance. • Fast and high sensitive detection for multiple nitroaromatic compounds. [ABSTRACT FROM AUTHOR]

The CO 2 /C2-hydrocarbons over CH 4 separation processes are important for the purification of methane fuel. Towards to this purpose, we have designed two isostructural indium-terephthalate metal-organic frameworks (MOFs) decorated with inorganic OH− anions and/or organic –OH Lewis basic groups, namely SNNU-120 and -121. One-dimensional (1D) [In(OH)(COO) 2 ] chains act as rod-shaped secondary building units (SBUs) linking adjacent four SBUs to form robust 3D rod-packing architecture with two types of 1D channels. Under 273 and 298 K, SNNU-120 and -121 have remarkable CO 2 , C 2 H 2 and C 2 H 4 uptakes but negligible CH 4 adsorption. IAST calculations indicate both of them can effectively separate CO 2 /C2-hydrocarbons from CH 4. The gas adsorption and separation performance of inorganic OH− and organic –OH group co-functionalized SNNU-121 MOF are superior to SNNU-120 only with inorganic OH− anions. Specially, the excellent IAST CO 2 /CH 4 (214.4) and C 2 H 4 /CH 4 (200) selectivity values for SNNU-121 are considered top-level among all rod-packing MOFs and also surpass the values of most famous MOF materials up to now. Two robust rod-packing In–OH-BDC metal-organic frameworks decorating with inorganic OH- anions and/or organic –OH Lewis basic groups show top-level CO 2 /C2-hydrocarbons over CH 4 seperation performance. Image 1 • Robust rod-packing indium-carboxylate frameworks. • Co-existence of ultramicroporous and microporous channels. • Top-level CO 2 /CH 4 and C 2 H 4 /CH 4 separation performance. [ABSTRACT FROM AUTHOR]

Hypertension is a prominent contributor to vascular injury. Deubiquinatase has been implicated in the regulation of hypertension-induced vascular injury. In the present study we investigated the specific role of deubiquinatase YOD1 in hypertension-induced vascular injury. Vascular endothelial endothelial-mesenchymal transition (EndMT) was induced in male WT and YOD1 -/- mice by administration of Ang II (1 μg/kg per minute) via osmotic pump for four weeks. We showed a significantly increased expression of YOD1 in mouse vascular endothelial cells upon Ang II stimulation. Knockout of YOD1 resulted in a notable reduction in EndMT in vascular endothelial cells of Ang II-treated mouse; a similar result was observed in Ang II-treated human umbilical vein endothelial cells (HUVECs). We then conducted LC-MS/MS and co-immunoprecipitation (Co-IP) analyses to verify the binding between YOD1 and EndMT-related proteins, and found that YOD1 directly bound to β-catenin in HUVECs via its ovarian tumor-associated protease (OTU) domain, and histidine at 262 performing deubiquitination to maintain β-catenin protein stability by removing the K48 ubiquitin chain from β-catenin and preventing its proteasome degradation, thereby promoting EndMT of vascular endothelial cells. Oral administration of β-catenin inhibitor MSAB (20 mg/kg, every other day for four weeks) eliminated the protective effect of YOD1 deletion on vascular endothelial injury. In conclusion, we demonstrate a new YOD1-β-catenin axis in regulating Ang II-induced vascular endothelial injury and reveal YOD1 as a deubiquitinating enzyme for β-catenin, suggesting that targeting YOD1 holds promise as a potential therapeutic strategy for treating β-catenin-mediated vascular diseases., (© 2024. The Author(s), under exclusive licence to Shanghai Institute of Materia Medica, Chinese Academy of Sciences and Chinese Pharmacological Society.)

Precise design of low-cost, efficient and definite electrocatalysts is the key to sustainable renewable energy. Herein, this work develops a targeted-anchored and subsequent spontaneous-redox strategy to synthesize nickel-iron layered double hydroxide (LDH) nanosheets anchored with monodispersed platinum (Pt) sites (Pt@LDH). Intermediate metal-organic frameworks (MOF)/LDH heterostructure not only provides numerous confine points to guarantee the stability of Pt sites, but also excites the spontaneous reduction for Pt II . Electronic structure, charge transfer ability and reaction kinetics of Pt@LDH can be effectively facilitated by the monodispersed Pt moieties. As a result, the optimized Pt@LDH that with the 5% ultra-low content Pt exhibits the significant increment in electrochemical water splitting performance in alkaline media, which only afford low overpotentials of 58 mV at 10 mA cm -2 for hydrogen evolution reaction (HER) and 239 mV at 10 mA cm -2 for oxygen evolution reaction (OER), respectively. In a real device, Pt@LDH can drive an overall water-splitting at low cell voltage of 1.49 V at 10 mA cm -2 , which can be superior to most reported similar LDH-based catalysts. Moreover, the versatility of the method is extended to other MOF precursors and noble metals for the design of ultrathin LDH supported monodispersed noble metal electrocatalysts promoting research interest in material design., (© 2023 Wiley-VCH GmbH.)

High storage capacity, high separation selectivity, and high structure stability are essential for an idea gas adsorbent. However, it is not easy to achieve all three at the same time, even for the promising metal-organic framework (MOF) adsorbents. We demonstrate herein that robust [Sc 3 O]-organic frameworks could be regulated by a micropore combination strategy for high-performance acetylene adsorption. Under the same solvent system with formic acid as a modulator, similar tritopic ligands extend [Sc 3 O(COO) 6 ] trigonal-prismatic clusters to generate SNNU-5-Sc and SNNU-150-Sc adsorbents. Notably, the two Sc-MOFs can keep their architectures over 24 h in water at different pH values (2-12) or at 90 °C. Modulated by the linker symmetry, the final stacking metal-organic polyhedral cages produce open window sizes of about 10 Å for SNNU-5-Sc and 5 Å + 7 Å for SNNU-150-Sc. Due to such micropore combinations, SNNU-5-Sc exhibits a top-level C 2 H 2 uptake of 211.2 cm 3 g -1 (1 atm and 273 K) and SNNU-150-Sc shows high C 2 H 2 /CH 4 , C 2 H 2 /C 2 H 4 , and C 2 H 2 /CO 2 selectivities of 80.65, 4.03, and 8.19, respectively, under ambient conditions. Dynamic breakthrough curves obtained on a fixed-bed column and grand canonical Monte Carlo (GCMC) simulations further support their prominent acetylene storage and purification performance. High framework stability, storage capacity, and separation selectivity make SNNU-5-Sc and SNNU-150-Sc ideal acetylene adsorbents in practical applications.

High-quality CoP nanorings (CoP NRs) are easily achieved using a phosphorating treatment of CoOOH nanorings, and reveal high activity towards the hydrogen evolution reaction and the nitrate electrocatalytic reduction reaction due to substantial coordinately unsaturated active sites, a high surface area, and available mass transfer pathways. Consequently, the CoP NRs can achieve a faradaic efficiency of 97.1% towards NO 3 - -to-NH 3 conversion and provide an NH 3 yield of 30.1 mg h -1 mg -1 cat at a -0.5 V potential.

High gas-uptake capacity is desirable for many reasons such as gas storage and sequestration. Moreover, ultrahigh capacity can enable a practical separation process by mitigating the selectivity factor that sometimes compromises separation efficiency. Herein, a single-walled nickel-organic framework with an exceptionally high gas capture capability is reported. For example, C 2 H 4 and C 2 H 6 uptake capacities are at record-setting levels of 224 and 289 cm 3 g -1 at 273 K and 1 bar (169 and 110 cm 3 g -1 at 298 K and 1 bar), respectively. Such ultrahigh capacities for both gases give rise to an excellent separation performance, as shown for C 2 H 6 /C 2 H 4 with breakthrough times of 100, 60 and 30 min at 273, 283 and 298 K and under 1 atm. This new material is also shown to readily remove ethylene released from fruits, and once again, its ultrahigh capacity plays a key role in the extraordinary length of time achieved in the preservation of the fruit freshness., Competing Interests: The authors declare no conflict of interest., (© 2021 The Authors. Advanced Science published by Wiley‐VCH GmbH.)

The high storage capacity versus high selectivity trade-off barrier presents a daunting challenge to practical application as an acetylene (C 2 H 2 ) adsorbent. A structure-performance relationship screening for sixty-two high-performance metal-organic framework adsorbents reveals that a moderate pore size distribution around 5.0-7.5 Å is critical to fulfill this task. A precise pore space partition approach was involved to partition 1D hexagonal channels of typical MIL-88 architecture into finite segments with pore sizes varying from 4.5 Å (SNNU-26) to 6.4 Å (SNNU-27), 7.1 Å (SNNU-28), and 8.1 Å (SNNU-29). Coupled with bare tetrazole N sites (6 or 12 bare N sites within one cage) as high-density H-bonding acceptors for C 2 H 2 , the target MOFs offer a good combination of high C 2 H 2 /CO 2 adsorption selectivity and high C 2 H 2 uptake capacity in addition to good stability. The optimized SNNU-27-Fe material demonstrates a C 2 H 2 uptake of 182.4 cm 3  g -1 and an extraordinary C 2 H 2 /CO 2 dynamic breakthrough time up to 91 min g -1 under ambient conditions., (© 2021 Wiley-VCH GmbH.)

The sluggish reaction kinetics of the anodic oxygen evolution reaction increases the energy consumption of the overall water electrolysis for high-purity hydrogen generation. In this work, ultrathin cobalt sulfide nanosheets (Co 3 S 4 -NSs) on nickel foam (Ni-F) nanohybrids (termed as Co 3 S 4 -NSs/Ni-F) are synthesized using cyanogel hydrolysis and a sulfurization two-step approach. Physical characterizations reveal that Co 3 S 4 -NSs with a 1.7 nm thickness have abundant holes, implying the big surface area, abundant active edge atoms, and sufficient active sites. Electrochemical measurements show that as-synthesized Co 3 S 4 -NSs/Ni-F have excellent electrocatalytic activity and selectivity for ethanol oxidation reaction and hydrogen evolution reaction. Due to their bifunctional property of Co 3 S 4 -NSs/Ni-F nanohybrids, a symmetric Co 3 S 4 -NSs/Ni-F∥Co 3 S 4 -NSs/Ni-F ethanol electrolyzer can be effectively constructed, which only requires a 1.48 V electrolysis voltage to reach a current density of 10 mA cm -2 for high-purity hydrogen generation at the cathode as well as value-added potassium acetate generation at the anode, much lower than the electrolysis voltage of traditional electrochemical water splitting (1.64 V).

Both methane (CH 4 ) and acetylene (C 2 H 2 ) are important energy source and raw chemicals in many industrial processes. The development of an energy-efficient and environmentally friendly separation and purification strategy for CH 4 and C 2 H 2 is necessary. Ultramicroporous metal-organic framework (MOF) materials have shown great success in the separation and purification of small-molecule gases. Herein, the synergy effect of tritopic polytetrazolate and ditopic terephthalate ligands successfully generates a series of isoreticular ultramicroporous cadmium tetrazolate-carboxylate MOF materials (SNNU-13-16) with excellent CH 4 and C 2 H 2 purification performance. Except for the uncoordinated tetrazolate N atoms serving as Lewis base sites, the pore size and pore surface of MOFs are systematically engineered by regulating dicarboxylic acid ligands varying from OH-BDC (SNNU-13) to Br-BDC (SNNU-14) to NH 2 -BDC (SNNU-15) to 1,4-NDC (SNNU-16). Benefiting from the ultramicroporous character (3.8-5.9 Å), rich Lewis base N sites, and tunable pore environments, all of these ultramicroporous MOFs exhibit a prominent separation capacity for carbon dioxide (CO 2 ) or C2 hydrocarbons from CH 4 and C 2 H 2 . Remarkably, SNNU-16 built by 1,4-NDC shows the highest ideal adsorbed solution theory CO 2 /CH 4 , ethylene (C 2 H 4 )/CH 4 , and C 2 H 2 /CH 4 separation selectivity values, which are higher than those of most famous MOFs with or without open metal sites. Dynamic breakthrough experiments show that SNNU-16 can also efficiently separate the C 2 H 2 /CO 2 mixtures with a gas flow rate of 4 mL min -1 under 1 bar and 298 K. The breakthrough time (18 min g -1 ) surpasses most best-gas-separation MOFs and nearly all other metal azolate-carboxylate MOF materials under the same conditions. The above prominently CH 4 and C 2 H 2 purification abilities of SNNU-13-16 materials were further confirmed by the Grand Canonical Monte Carlo (GCMC) simulations.

The construction of superstable metal-organic frameworks (MOFs) for selective gas uptake is urgently demanded but remains a great challenge. Herein, a unique bifunctional deformed [Ga 3 O(COO) 6 ] inorganic secondary building unit (SBU) generated from the desymmetrical evolution of typical triangular prismatic trinuclear cluster was first introduced, which was extended by an isosceles triangular organic linker to produce a robust Ga-MOF ( SNNU-63 ). Remarkably, SNNU-63 can stabilize in water at 25 °C for 96 h and at 80 °C for more than 24 h, which surpasses nearly all other Ga-MOFs. The combined effects of open metal sites and hydrophobic pore environment provided by deformed [Ga 3 O] SBUs render SNNU-63 with high C 2 H 2 storage capacity and efficient C 2 H 2 and natural gas purification performance. The ideal adsorbed solution theory calculation, column breakthrough tests, and grand canonical Monte Carlo simulations demonstrate that SNNU-63 is a potential material for addressing the challenge of C 2 H 2 /CO 2 and C 2 H 2 /CH 4 mixture separation under ambient conditions.

The separation of a mixture of C 2 H 2 and CO 2 is a great challenge due to their similar molecular sizes and shapes. Al-based metal-organic frameworks (Al-MOFs) have great promise for gas separation applications due to their light weight, high stability, and low cost. However, the cultivation of suitable Al-MOF single crystals is extremely difficult and has limited their explorations up to now. Since In, Ga, and Al are all 3p-block metal elements, a systematic application of the periodic law to investigate 3p-MOFs will undoubtedly help in the understanding and development of worthy Al-MOF materials. Herein, we report the design of a robust 3p metal-organic framework platform (SNNU-150) and the systematic regulation of C 2 H 2 /CO 2 separation by open 3p-block metal sites. X-ray single-crystal diffraction analysis reveals that SNNU-150 is a 3,6-connected 3D framework consisting of [M 3 O(COO) 6 ] trinuclear secondary building units (SBUs) and tritopic nitrilotribenzoate (NTB) linkers. Small {[M 3 O(COO) 6 ] 4 (NTB) 6 } tetrahedral cages and extra-large {[M 3 O(COO) 6 ] 10 (NTB) 14 } polyhedral cages connect with each other to generate a hierarchically porous architecture. These 3p-MOFs present very high water, thermal, and chemical stability, especially for SNNU-150-Al, which can maintain its framework at 85 °C in water for 24 h and in a room-temperature environment for more than 30 days. IAST calculations, breakthrough experiments, and GCMC simulations all show that SNNU-150 MOFs have top-level C 2 H 2 /CO 2 separation performance and follow the order Al-MOF > Ga-MOF > In-MOF.

It is well-known that the formation of ferroalloy with the addition of the second or third metal during the steel-making process usually can improve the performance of the iron. Inspired by ferroalloy materials, it is speculated that the pore environment, framework charge, and catalytic properties of metal-organic frameworks (MOFs) could be optimized dramatically via the introduction of ferroalloy-like inorganic building blocks. However, different to ferroalloy, the accurate integration of different metals into one MOF platform is still challenging. Herein, taking advantages of the good compatibility for metals in trigonal prismatic trinuclear cluster, a series of Fe-based alloy-like [M 3 O(O 2 C) 6 ] motifs (M 3 = Fe 3 , Fe 1.5 Ni 1.5 , Fe 1.5 Co 1.5 , Fe 1.5 Ti 1.5 , FeCoNi, and FeTiCo) are successfully generated, which further lead to a robust Fe-MOF material family (SNNU-5s). These multicomponent MOFs not only provide a good chance to explore the impact of pore environment on gas adsorption/separation but also offer an opportunity to the efficient electrocatalytic reaction directly. Accordingly, compared with the SNNU-5-Fe parent structure, the pore characters of heterometallic SNNU-5 MOFs are clearly regulated by the type of alloy-like building blocks. SNNU-5-FeTi displays more superior gas separation performance for CO 2 /CH 4 , C 2 H 2 /CH 4 , C 2 H 4 /CH 4 , and C 2 H 2 /CO 2 gas mixtures. What is more, benefited from the multimetallic active sites and their catalytic synergy, FeCoNi-ternary alloy-like cluster-based SNNU-5 MOF material exhibits an exceptional oxygen evolution reaction activity in aqueous solution at pH = 13, which delivers a low overpotential (η j =10 = 317 mV), a fast reaction kinetics (Tafel slope = 37 mV dec -1 ), and excellent catalytic stability. This facile multialloy-like building block strategy holds promise to accurately design and improve the performance of MOFs, as well as open an avenue to understand the related mechanisms.

Evaluating the effect of ligand substitution on metal ions and/or clusters during the MOF growth process is conducive to rational design of isoreticular MOFs with improved performance. Through topological direction and ligand substitution strategy, we herein constructed two Sc-soc-MOFs ( Sc-EBTC and Sc-ABTC ) based on two similar rectangular-planar diisophthalate ligands, linear-shaped H 4 EBTC (1,1'-ethynebenzene-3,3',5,5'-tetracarboxylic acid) and zigzag-shaped H 4 ABTC (3,3',5,5'-azobenzenetetracarboxylic acid), under solvothermal conditions with formic acid as a modulator. {Sc[(Sc 3 O)(H 2 O) 3 ] 3 (EBTC) 6 } ( Sc-EBTC ) possesses two distinct clusters as SBUs, trinuclear [Sc 3 O(CO 2 ) 6 ] (SBU1) and mononuclear cluster [ScO 6 ] (SBU2), which maintain the soc-topology except for the mononuclear [ScO 6 ] instead of the corresponding trinuclear [Sc 3 O(CO 2 ) 6 ] in Sc-ABTC ({(Sc 3 O)(H 2 O) 3 (ABTC) 1.5 (NO 3 )}). Notably, Sc-EBTC represents a rare soc-MOF with two distinct clusters as SBUs. Due to similar pore spaces, the two Sc-soc-MOF materials both exhibit enhanced and comparable gas sorption and selectivity performances. Specially, their remarkable C 2 H 2 , C 2 H 4 , and CO 2 storage capacity along with prominent CO 2 /CH 4 and C 2 -hydrocarbons/CH 4 separations indicate that these Sc-soc-MOFs are promising adsorbents for natural gas purification under ambient conditions.

A strategy called ultramicroporous building unit (UBU) is introduced. It allows the creation of hierarchical bi-porous features that work in tandem to enhance gas uptake capacity and separation. Smaller pores from UBUs promote selectivity, while larger inter-UBU packing pores increase uptake capacity. The effectiveness of this UBU strategy is shown with a cobalt MOF (denoted SNNU-45) in which octahedral cages with 4.5 Å pore size serve as UBUs. The C 2 H 2 uptake capacity at 1 atm reaches 193.0 cm 3  g -1 (8.6 mmol g -1 ) at 273 K and 134.0 cm 3  g -1 (6.0 mmol g -1 ) at 298 K. Such high uptake capacity is accompanied by a high C 2 H 2 /CO 2 selectivity of up to 8.5 at 298 K. Dynamic breakthrough studies at room temperature and 1 atm show a C 2 H 2 /CO 2 breakthrough time up to 79 min g -1 , among top-performing MOFs. Grand canonical Monte Carlo simulations agree that ultrahigh C 2 H 2 /CO 2 selectivity is mainly from UBU ultramicropores, while packing pores promote C 2 H 2 uptake capacity., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The concept of high-performance excited-state intramolecular proton transfer (ESIPT)-based fluorescent metal-organic framework (MOF) probes for Al 3+ is proposed in this work. By regulating the hydroxyl groups on the organic linker step by step, new fluorescent magnesium-organic framework (Mg-MOF) probes for Al 3+ ions were established based on the ESIPT fluorescence mechanism. It is observed for the first time that the number of intramolecular hydrogen bonds between adjacent hydroxyl and carboxyl groups can effectively adjust the ESIPT process and lead to tunable fluorescence sensing performance. Together with the well-designed porous and anionic framework, the Mg-TPP-DHBDC probe decorating with a pair of intramolecular hydrogen bonds exhibits extra-high quantitative fluorescence response to Al 3+ through an unusual turn-off (0-1.2 μM) and turn-on (4.2-15 μM) luminescence sensing mechanism. Notably, the 28 nM limit of detection value represents the lowest record among all reported MOF-based Al 3+ fluorescent sensors up to now. Benefited from the unique turn-off-on ESIPT fluorescence detection process, the Mg-TPP-DHBDC MOF sensor exhibits single Al 3+ detection compared with other 16 common metal ions including Ga 3+ , In 3+ , Fe 3+ , Cr 3+ , Ca 2+ , and Mg 2+ . Impressively, such an Al 3+ selective sensing process can even be fulfilled by the reusable MOF test paper detected by naked eyes. Overall, the quantitative Al 3+ detection, together with the extraordinary sensitivity, selectivity, fast response, and good reusability, strongly supports our concept of ESIPT-based fluorescent MOF Al 3+ probes and makes Mg-TPP-DHBDC one of the most powerful Al 3+ fluorescent sensors.

During the formation of magnesium-organic frameworks, the coordination sphere of magnesium tends to be partially occupied by O-containing solvent molecules such as amides, which will dramatically decrease the symmetry of Mg-organic frameworks and thus lead to low stability. It is noted that up to now, most reported Mg-metal-organic frameworks (MOFs) (>80%) crystallize in the space groups whose symmetry is lower than that of a tetragonal system. In this work, we demonstrate that acetate (Ac) may act as modulator to eliminate the influence of amide solvent and improve the symmetry of Mg-organic frameworks. Two novel Mg-MOFs, namely, {[(CH 3 )NH 3 ] 4 [Mg 3 (BTB) 8/3 (Ac) 2 (H 2 O)]} n (SNNU-35, H 3 BTB = 4',4'',4'''-benzene-1,3,5-tribenzoic acid) and {[(CH 3 ) 2 NH 2 ][Mg 2 (FDA) 2 (Ac)]} n (SNNU-36, H 2 FDA = 2,5-furandicarboxylic acid) were successfully designed, which crystallize in rhombohedral R-3 and tetragonal I4 /mmm space groups, respectively. Four independent BTB ligands link three unique Mg cations and generate superlarge [Mg 21 BTB 17 ] nanocages, which interlock each other by strong π···π stacking to give a two-fold interpenetrating architecture of SNNU-35. On the other hand, carboxylate and acetate groups chelate Mg atoms to form one-dimensional chains, which are extended by FDA to produce the rod-packing framework of SNNU-36. Two microporous Mg-MOFs both exhibit notable CO 2 and H 2 uptakes. H 3 BTB and H 2 FDA ligands both have emission features, and Mg ions usually can enhance the fluorescent intensity, which lead to a strong solid-state luminescence emission property of SNNU-35 and -36. Importantly, two Mg-MOFs both show fast and quantative sensing performance for nitrocompounds. Among three selected models of substrate, SNNU-35 and -36 can eliminate the interference of nitromethane (NM) and exhibit high sensitivity to nitrobenzene (NB) and o-nitrotoluene (2-NT) with large k sv values (>10 5 M -1 ). Especially, the fluorescence quenching efficiency of NB (5000 ppm) and 2-NT (8000 ppm) can reach 96.3% and 89.5% and 85.0% and 83.7% for SNNU-35 and -36, respectively. This work offers not only an effective route to improve the symmetry of magnesium-organic frameworks but also two potential fluorescence sensors for nitroaromatic compounds.

Presented herein is a magnesium-organic framework (SNNU-88) incorporated with active hydroquinone groups, which exhibits not only remarkable semiconductor sensing for traces of ammonia vapor (5-100 ppm), but also extra-high fluorescence response to liquid NH3·H2O through an unusual turn-off (0-1.5 ppm) and turn-on (3.0-100 ppm) luminescence sensing mechanism at room temperature. Such bifunctional quantitative ammonia detection together with the extraordinary sensitivity and selectivity, fast response, and good reusability makes SNNU-88 one of the most powerful ammonia sensors.

A porous MOF platform (SNNU-65s) formed by creatively combining paddle-wheel-like [Cu 2 (COO) 4 ] and trigonal prismatic [M 3 (μ 3 -O)(COO) 6 ] building blocks was designed herein. The mixed and high-density open metal sites and the OH-functionalized pore surface promote SNNU-65s to exhibit ultra-high C 2 H 2 uptake and separation performance. Impressively, SNNU-65-Cu-Ga stands out for the highest C 2 H 2 /CO 2 (18.7) and C 2 H 2 /CH 4 (120.6) selectivity among all the reported MOFs at room temperature.

By regulating the tetratopic carboxylate ligands, two robust Fe-MOFs (MOF=Metal-organic framework) comprising trigonal prismatic building blocks under a DMA/DMSO/HBF 4 solvent system, namely, [(CH 3 ) 2 NH 2 ][Fe II 3 (OH)(BPTC) 1.5 (DMSO) 3 ] (SNNU-60) and [Fe III Fe II 2 (OH)(ABTC) 1.5 (DMSO) 3 ] (SNNU-61) (BPTC=3,3',5,5'-biphenyltetracarboxylic acid, ABTC=3,3',5,5'-azobenzenetetracarboxylic acid, SNNU=Shaanxi Normal University) have been successfully synthesized. The torsions between the benzene groups of the ligands result in two MOFs exhibiting completely different (4,6)-connected frameworks, which represent the only two MOF types constructed by [M 3 (O/OH)(COO) 6 ] trimeric building units and quadrilateral tetratopic carboxylate linkers until now. The robust Fe-MOFs SNNU-60 and SNNU-61 both exhibit high thermal/chemical stability, permanent microporosity, and excellent gas uptake capability for H 2 , CO 2 , C 2 H 2 , and C 2 H 4 under 1 bar. SNNU-60 in particular displays very high C 2 H 2 capture under low pressure (85 cm 3  cm -3 at 0.15 bar and 298 K), which is among the top C 2 H 2 uptake MOF materials. Also, these two Fe-MOFs display high separation for CO 2 and C 2 -hydrocarbons over CH 4 . Significantly, thanks to the high stability, suitable pore size, open Fe sites, and ion skeleton, SNNU-60 has extremely high C 2 H 2 /CH 4 selectivity (83.6, 298 K), which surpasses most MOFs reported so far under the same conditions., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The synthetic design of new porous open-framework materials with pre-designed pore properties for desired applications such as gas adsorption and separation remains challenging. We proposed one such class of materials, rod metal-organic frameworks (rod MOFs), which can be tuned by using rod secondary building units (rod SBUs) with different geometrical and chemical features. Our approach takes advantage of the readily accessible metal-triazolate 1-D motifs as rod SBUs to combine with dicarboxylate ligands to prepare target rod MOFs. Herein we report three such metal-triazolate-dicarboxylate frameworks (SNNU-21, -22 and -23). During the formation of these three MOFs, Cd or Zn ions are firstly connected by 1,2,4-triazole through the N1,N2,N4-mode to form 1-D metal-organic ribbon-like rod SBUs, which further joint four adjacent rod SBUs via eight BDC linkers to give 3-D microporous frameworks. However, tuned by the different NH 2 groups from metal-triazolate rod SBUs, different space groups, pore sizes and shapes are observed for SNNU-21-23. All of these rod MOFs show not only remarkable CO 2 uptake capacity, but also high CO 2 over CH 4 and C 2 -hydrocarbons over CH 4 selectivity under ambient conditions. Specially, SNNU-23 exhibits a very high isosteric heat of adsorption (Q st ) for C 2 H 2 (62.2 kJ mol -1 ), which outperforms the values of all MOF materials reported to date including the famous MOF-74-Co.

Reported herein is a novel porous metal-organic framework (MOF) exhibiting unique nanoscale cages derived from the 3-fold self-interpenetration of chiral eta networks based on trifurcate {Zn2(CO2)3} building blocks and 1,3,5-tris(4-carboxyphenyl)benzene ligands. The attractive self-interpenetrated structural features contribute to the highest CO2 uptake capacity and CO2 binding ability among the interpenetrated MOFs.

Chloroperoxidase (CPO) from Caldariomyces fumago was optimally covalently immobilized on chitosan membranes pretreated with 0.8 M glutaraldehyde at pH 3.5 to give 3.18 mg CPO g(-1) support. Using monochlorodimedone (MCD) as assay substrate, the immobilized-CPO retained 40% activity at 50 degrees C after 40 min whereas free CPO retained only 0.02%. The residual activity for immobilized-CPO was 99 and 58% compared with 68 and 43% for free CPO in the presence of 1.5 M urea and 300 microM H(2)O(2), respectively, after 20 h.

In this paper, the Raman and difference FTIR spectra of NTO crystal, NTO solutions at different pH and saturated aqueous solution of Rb(NTO) x H2O have been studied. The determined structure of crystal suggests that the metal ion with oxygen and nitrogen atoms of [chemical structure see text] C-N, [chemical structure see text] C-NO2, [chemical structure see text] C=O and H2O formed bonds. The highest characterization peaks of Raman and FTIR spectra show that [chemical structure see text] C-NO2, [chemical structure see text] C=O and [chemical structure see text] C-N of NTO- formed week coordination bonds. The vibration spectra of saturation solution basically accord with those of the crystal. The bonds of saturation solution of the coordination compound have not changed. Therefore, the different vibration spectra of the saturation water solution of Rb (NTO) x H2O can be explicated by the formation of the bonds in crystal. The coordination compound formation mechanism of metal ion with NTO in alkali aqueous solution is discussed.