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Acid orange II (AO II), a typical azo pigment, is strictly controlled by legislation and prohibited in foodstuffs. Herein, we prepared gold nanoparticles decorated amino-functionalized Cr-based metal-organic frameworks [NH 2 -MIL-101(Cr)@Au] via an in-situ reduction method as a surface-enhanced Raman scattering (SERS) substrate for simultaneous adsorption and detection of AO II. Gold nanoparticles are uniformly dispersed on the surface of NH 2 -MIL-101(Cr) owing to its three-dimensional (3D) structure and the interaction between –NH 2 and Au ions, providing more SERS-active "hot spots". These NH 2 -MIL-101(Cr)@Au nanocomposites exhibited selective and high adsorption performance (419.85 mg g−1) for AO II, and could be used as superior SERS substrates for the detection of AO II with a low limit of detection (LOD) of 0.05 mg L−1 and wide detection range of 0.05–50 mg L−1 using portable Raman spectrometer. Furthermore, this SERS assay has been successfully used to determine AO II in orange juice and chili powder with good sensitivities. Image 1 • A versatile NH 2 -MIL-101(Cr) coated uniformly gold nanoparticles was fabricated. • A new method for simultaneous adsorption and detection of acid orange II (AO II) was developed. • The adsorption mechanism for AO II was systematically revealed. • Density functional theory was applied to optimize Raman spectra of AO II. • AO II in food samples was rapidly detected with a low limit of detection using SERS method. [ABSTRACT FROM AUTHOR]

Immunotherapeutic interventions represent a promising approach to treating cancer, with strategies such as immune checkpoint blockade (ICB), immunogenic sonodynamic therapy (SDT), and immune adjuvant T cell delivery having exhibited clinical promise. In this report, we describe the use of cancer cell membrane-coated triphenylphosphonium (TPP) decorated nano-metal–organic framework (nMOF) constructs [Zr-TCPP(TPP)/R837@M] that were used to generate homologous, mitochondria-targeted platforms with a high rate of sonosensitizer loading. This construct was utilized to simultaneously promote tumor antigen presentation via enhancing SDT while synergistically promoting dendritic cell (DC) maturation through the delivery of the Toll-like receptor agonist R837. In vitro, these functionalized nMOFs were readily internalized by homologous tumor cells in which they were efficiently targeted to the mitochondria, promoting DC activation through the induction of immunogenic cell death (ICD) following ultrasound exposure. Moreover, this nanoplatform was able to achieve in vivo synergy with anti-CTLA-4 ICB to reverse immunosuppression tumor microenvironment (TME), thus achieving more robust antitumor efficacy capable of suppressing metastatic disease progression and facilitating the development of durable antitumor memory responses. Together, these results highlight a promising approach to achieving enhanced SDT activity while overcoming an immunosuppressive TME, thereby achieving more robust antitumor immunity. [ABSTRACT FROM AUTHOR]

Five new polymers based on 5-(pyridine-3-yl)pyrazole-3-carboxylic acid (H 2 ppca), namely, [Cd 2 (ppca)(bix)(SO 4 )] n ( 1 ), {[Cd(Hppca) 2 ]·H 2 O} n ( 2 ), {[Mn(Hppca) 2 ]·H 2 O} n ( 3 ), [Zn 2 (ppca) 2 ] n ( 4 ) and [Cu(ppca)] n ( 5 ) have been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. Structural analyses reveal that polymer 1 possesses a 2-fold interpenetrating three-dimensional (3D) framework. Polymers 2 and 3 display 4-connected 2D frameworks, while polymer 4 features a (3,3)-connected topology with the Schläfli symbol (4·8·10). 5 exhibits a 2 D structure with the Schläfli symbol (4·8 2 ). Furthermore, the fluorescence properties of the five polymers are also investigated in the solid state, showing the fluorescence signal changes in comparing with that of free ligand mbbz. Polymer 5 with square pyramid geometry ( τ Cu1 , 0.069) implies that there is strong antiferromagnetic interactions between two adjacent Cu1C and Cu1, and the magnetic interactions are mainly transferred by the bridging N , N- triazole ligands. [ABSTRACT FROM AUTHOR]

Luminescent metal organic frameworks (LMOFs) are considered to be a type of promising optical sensing material due to their designable and tunable functions, and stable pore structures. Therefore, the preparation of LMOFs has become a research hotspot in recent years. As we know, triazine carboxylic acid ligands are conducive for constructing LMOF materials due to their large π electron conjugated system. In this work, two crystalline materials [Cd3(TCPT)2]·0.5DMF·4H2O (1) and (H3O)[Zn2(TCPT)(μ2-OH)2]·0.5DMF·3H2O (2) were obtained by the reaction of the triazine carboxylic acid ligand 2,4,6-tris(4-carboxyphenoxy)-1,3,5-triazine (H3TCPT), as an extended carboxylate arm, and d10 transition metal salts. Their structures were determined by single crystal X-ray diffraction and characterized by infrared spectroscopy (IR), ultraviolet visible spectroscopy (UV-vis), fluorescence spectroscopy, powder X-ray diffraction (PXRD) and thermogravimetric analysis (TG). The experimental results showed that complexes 1 and 2 show excellent fluorescent emission behavior. Thus, we explored their fluorescence sensing properties. To our delight, the results showed that they both had the ability to sense small organic drug molecules and aromatic amine molecules containing o-phenylenediamine (OPD), m-phenylenediamine (MPD) and p-phenylenediamine (PPD). In general, the practical applications of a MOF material are usually limited because of the relatively harsh synthesis methods. In this aspect, we studied the synthesis method in detail to obtain the optimal reaction conditions for the large-scale synthesis of 1 and 2. The preparation of the two LMOF materials only required about 3 hours of heating time and they could be prepared on a large scale, which is significant for the practical applications of LMOFs. [ABSTRACT FROM AUTHOR]

The transmembrane diffusion of soluble lithium polysulfides (LiPS) is the main cause of capacity loss and negative electrode corrosion in lithium-sulfur (Li-S) batteries. In order to suppress the shuttle effect of LiPS, a selective permeability membrane was constructed by introducing functional materials with negative charge groups. Herein, a functional separator with high ion conductivity is obtained by casting the environmentally friendly MOF material sulfonic acid functionalized amino-MIL-101 (S-MIL-101) onto the separator. It is found that the functionalized sulfonic acid group not only accelerates the conduction of the lithium-ion but also repels the polysulfide anion through electrostatic interactions. With this functionalized separator, the initial capacity of batteries is 1444.6 mAh·g−1 at 0.2C and remains 990.4 mAh·g−1 after 100 cycles. Meanwhile, the batteries still deliver a high initial discharge capacity of 895.7 mAh·g−1 even with the high-sulfur-loading cathode (4.7 mg cm−2) at 0.2C. We designed and synthesized sulfonic acid functionalized Al-based MIL-101-NH 2 modified separator for lithium-sulfur batteries. The introduction of sulfonic acid groups can accelerate the conduction of Li+ and carry out electrochemical processes. Besides, negatively charged sulfonic acid groups can suppress the shuttle effect through electrostatic interaction. The lithium-sulfur batteries assembled with the S-MIL-101 separator have an initial discharge capacity of 895.7 mAh·g−1 at 0.2C with 4.7 mg cm−2. [Display omitted] • S-MIL-101 improves Li+ conductivity. • Modified separators inhibit shuttle effect. • Modified separators inhibit shuttle effect. [ABSTRACT FROM AUTHOR]

Improving proton conductivity and fabricating viable metal‐organic frameworks (MOFs) based proton exchange membranes (PEMs) are central issues exploiting electrolyte MOFs. We aim to design multivariate flexibility synergistic strategy to achieve Flexible MOFs (FMOFs) with high conductivity at a wide range of humidity. In situ powder X‐ray diffraction (PXRD) and temperature‐dependent Fourier transform infrared spectra (FT‐IR) prove the synergistic self‐adaption between dynamic torsion of alkyl sulfonic acid and dynamic breathing of FMOF, forming a continuous hydrogen‐bonding networks to maintain high conductivity. Based on the convincing proton conductivity, we construct a series of long‐term durable MOF‐based PEMs that serve as a bridge between MOF and fuel cell. Consequently, the membrane electrode assembly (MEA) of the flexible PMNS1‐40 exhibits a maximum single‐cell power density of 34.76 mW cm−2 and hopefully opens doors to evaluate the practical application of proton‐conducting MOFs in direct methanol fuel cells. [ABSTRACT FROM AUTHOR]

Improving proton conductivity and fabricating viable metal‐organic frameworks (MOFs) based proton exchange membranes (PEMs) are central issues exploiting electrolyte MOFs. We aim to design multivariate flexibility synergistic strategy to achieve Flexible MOFs (FMOFs) with high conductivity at a wide range of humidity. In situ powder X‐ray diffraction (PXRD) and temperature‐dependent Fourier transform infrared spectra (FT‐IR) prove the synergistic self‐adaption between dynamic torsion of alkyl sulfonic acid and dynamic breathing of FMOF, forming a continuous hydrogen‐bonding networks to maintain high conductivity. Based on the convincing proton conductivity, we construct a series of long‐term durable MOF‐based PEMs that serve as a bridge between MOF and fuel cell. Consequently, the membrane electrode assembly (MEA) of the flexible PMNS1‐40 exhibits a maximum single‐cell power density of 34.76 mW cm−2 and hopefully opens doors to evaluate the practical application of proton‐conducting MOFs in direct methanol fuel cells. [ABSTRACT FROM AUTHOR]

Considering that cyclotriphosphazene polycarboxylic acid is a kind of organic ligand with fantastic structures and performances and the unique luminescence characteristics of rare earth ions, a series of porous lanthanide metal–organic frameworks (Ln-MOFs) (CH3)2NH2[Ln3(HCPCP)1.5(CH3COO)]·6DMA (Ln = Ce (1), Sm (2), Eu (3), Tb (4), HCPCP = hexa(4-carboxyphenoxy)cyclotriphosphazene, and DMA = N,N-dimethylacetamide) were synthesized with novel topological network structures. Compound 4 exhibited a sensitive recognition of –NO2, and had a fluorescence quenching phenomenon for seven kinds of nitro aromatic compounds (NACs). In particular, it showed the best fluorescence response to 2,4,6-trinitrophenol (TNP) and 2,4-dinitrophenol (DNP), and the KSV values were 2.86 × 105 M−1 and 8.21 × 104 M−1, and the limit of detection (LOD) values were 0.20 μM and 0.71 μM, respectively. At the same time, we successfully doped different concentrations of Eu3+ into compound 4 to obtain a series of doped Ln-MOF materials x%Eu3+@4 (x = 0.5, 2.5, 5, 7.5, 10, 15 and 20). With the increase of Eu3+ doping ratios, the characteristic peaks of Tb3+ and Eu3+ changed regularly, and the energy transfer from Tb3+ to Eu3+ ions occurred. By changing the excitation wavelength of the samples with different Eu3+ doping concentrations, a higher quality white light emitting material 7.5%Eu3+@4 (λex = 340 nm) was finally obtained, with a CIE coordinate of (0.3268, 0.3212). [ABSTRACT FROM AUTHOR]

The field of post‐synthesis modification has aroused widespread concern from diverse perspectives, including chemistry, biology, and material science. Post‐synthesis modification can introduce rich functionality into metal–organic frameworks (MOFs) without destroying the main structure of MOFs. Based on this research status, a series of lanthanide metal–organic frameworks ([Ln2(NH2‐BDC)2.5(CH3COO)(DMA)(H2O)]•DMA, Ln = Pr, Nd, Sm, Eu, Gd and Tb, NH2‐BDC = 2‐aminoterephthalic acid, DMA = N,N‐Dimethylacetamide) with 3D network structures, are synthesized by hydrothermal synthesis. Due to the presence of uncoordinated amino groups in the ligands, a series of post‐synthesis modified compounds are successfully synthesized through aldimine condensation reaction. Based on the good fluorescence properties and stable structure of coordination polymers and post‐synthesis modified compounds in water or organic solvents, they are able to be used as potential fluorescence sensor for the detection of Th4+, UO22+, and Cr2O72−, and the calculation result shows that the post‐synthesis modified compounds are more sensitive to the detection of analytes (Th4+, UO22+ and Cr2O72−) than coordination polymers. In addition, the MOF membrane prepared by self‐assembly of [Eu2(NH2‐BDC)2.5(CH3COO)(DMA)(H2O)]•DMA and ternary soap‐free copolymer (VAc‐AA‐BA) emulsion can be used first for detecting aldehyde vapors. [ABSTRACT FROM AUTHOR]

Herein, a spray pyrolysis strategy for synthesizing clustered metal chalcogenides embedded in the hollow N -doped carbon framework is reported. After thermally induced sulfurization processes, ZnS/CoS/CoS 2 @N-doped carbon was successfully prepared as a novel anode for lithium-ion battery. Electrochemical evaluation revealed that the mixture exhibits a high initial discharge capacity of 1273.8 mA h g−1 reversible capacity of 622.7 mA h g−1 in the 200th cycle at a current density of 100 mA g−1. In addition, ZnS/CoS/CoS 2 @N-doped carbon hybrid composites also showed excellent rate capability (586.8, 492.2, 399.3 and 293.6 mA h g−1 at 200, 500, 1000 and 2000 mA g−1, respectively). Such findings provide a new solution to address volume expansion/shrinkage during the lithiation/delithiation cycles, which holds a great future for the design and manufacturing of high performance lithium-ion batteries. Image 1 • Developing advanced ZnS/CoS/CoS 2 @N-doped carbon nanoparticles anodes via industrially-viable synthetic approach. • The synthesis of nanostructured ZnS/CoS/CoS 2 @N-doped carbon nanoparticles is realized and the scheme was explored. • ZnS/CoS/CoS 2 @N-doped carbon nanoparticles shows great cycling stability and excellent rate capability for Li+ storage. [ABSTRACT FROM AUTHOR]

Herein we report two new TPE‐based 3D MOFs, that is, Sr‐ETTB and Co‐ETTB (TPE=Tetraphenylethylene, H8ETTB=4′,4′′′,4′′′′′,4′′′′′′′‐(ethene‐1,1,2,2‐tetrayl)tetrakis(([1,1′‐biphenyl]‐3,5‐dicarboxylic acid))). Through tailoring outer shell electron configurations of SrII and CoII cations, the fluorescence intensity of the MOFs is tuned from high emission to complete non‐emission. Sr‐ETTB with strong blue fluorescence shows reversible fluorescence variations in response to pressure and temperature, which is directly related to the reversible deformation of the crystal structure. In addition, non‐emissive Co‐ETTB counterpart exhibits a turn‐on fluorescent enhancement under the stimulation of analyte histidine. In the process, TPE‐cored linkers in the MOFs are released through competitive coordination substitution and subsequently reassembled to perform aggregation‐induced luminescence behavior originated from the organic linkers. [ABSTRACT FROM AUTHOR]

Herein we report two new TPE‐based 3D MOFs, that is, Sr‐ETTB and Co‐ETTB (TPE=Tetraphenylethylene, H8ETTB=4′,4′′′,4′′′′′,4′′′′′′′‐(ethene‐1,1,2,2‐tetrayl)tetrakis(([1,1′‐biphenyl]‐3,5‐dicarboxylic acid))). Through tailoring outer shell electron configurations of SrII and CoII cations, the fluorescence intensity of the MOFs is tuned from high emission to complete non‐emission. Sr‐ETTB with strong blue fluorescence shows reversible fluorescence variations in response to pressure and temperature, which is directly related to the reversible deformation of the crystal structure. In addition, non‐emissive Co‐ETTB counterpart exhibits a turn‐on fluorescent enhancement under the stimulation of analyte histidine. In the process, TPE‐cored linkers in the MOFs are released through competitive coordination substitution and subsequently reassembled to perform aggregation‐induced luminescence behavior originated from the organic linkers. [ABSTRACT FROM AUTHOR]

Herein, we developed a tri-functional MOF heterogeneous catalyst, MIL-IMAc-Br−, by a post-synthesis modification method for the first time. Due to the synergistic role of three functional sites, including Lewis acid sites, Brønsted acid sites and Br− anion sites, MIL-IMAc-Br− displayed an efficient catalytic performance for the cycloaddition reaction of CO2 and epoxides to form cyclic carbonates under mild and co-catalyst free conditions. [ABSTRACT FROM AUTHOR]

• MOF-based nanosonosensitizers was fabricated with defect-rich Ti-based MOF, platinum nanoparticles and the O 2 carrier PFOB. • MOF-based nanosonosensitizers produced high levels of 1O 2 and induced ICD. • MOF-based nanosonosensitizers enhanced sono-immunotherapy against both primary tumors and metastatic tumors. Sonodynamic therapy (SDT) has emerged as a promising strategy for treating tumors owing to its non-invasiveness and high tissue-penetrating depth. Improving the efficiency of electron-hole separation of sonosensitizers and alleviation of the hypoxic tumor microenvironment remain major challenges. Metal-organic frameworks (MOFs) have greatly potential in SDT application, however, exploring new sonosensitizers with high reactive oxygen species (ROS) generation and improving the efficacy through a synergistic effect in combination with other therapeutic modalities remain major challenges. Furthermore, the immunosuppressive tumor microenvironment (TME) is characterized by hypoxia, which limit the efficacy of O 2 -dependent cancer treatments including SDT and immunotherapy. Herein, we fabricated a defect-rich titanium-based MOFs using propionic acid-mediated self-templated hierarchical etching. Reductive platinum nanoparticles were embedded onto the surface of MOFs to enhance the spatial separation of electron-hole pairs and improve the quantum yield of ultrasound-generated singlet oxygen (1O 2). Finally, perfluorobromooctane was encapsulated in the MOFs to function as an oxygen carrier to develop an oxygen self-feeding nanosensitizer. In vitro and in vivo assays demonstrated that this nanoplatform could produce high levels of 1O 2 under ultrasound irradiation, which led to enhanced SDT. Moreover, this nanoplatform also relieved the immunosuppressive TME by overcoming hypoxia and enhancing immunogenic cell death to promote the infiltration of tumor-specific cytotoxic T cells into the immunologically "cold" tumor. Therefore, combination of nanoplatform-mediated SDT with anti-PDL1 antibodies effectively inhibited the primary tumors, as well as the metastatic tumors. This study provides an insightful strategy for improving SDT and broadens the application of MOF-based sonosensitizers for sono-immunotherapy. [ABSTRACT FROM AUTHOR]

Highlights • MOF nanoparticles are assembled on the bacterial cellulose by weak interaction. • MOF aerogels with hierarchical structures are flexible and lightweight. • BC@ZIF-8 demonstrates an excellent adsorption performance of heavy metal ions. • BC@UiO-66@PDA interlayer can improve the performance of Li-S batteries. Abstract Flexible metal-organic framework (MOF) aerogels with practical macroscopic shapeability and hierarchical porosity were prepared through in-site growth of MOF nanoparticles, i.e. zeolitic imidazolate framework-8 (ZIF-8) and University of Oslo-66 (UiO-66), on bacteria cellulose (BC). The yielded composite aerogels inherit high porosities from feedstock MOFs and mechanical flexibility from BC template. BC template offers high porosity, mechanical flexibility to the composite aerogels, which significantly suppresses the aggregation of individual MOF nanoparticles. Owing to the structural characteristics of MOF and BC, BC@ZIF-8 composite aerogel sponges exhibit a low density below 0.03 g cm−3, hierarchical porosity, large surface area, high mass transfer efficiency and superior adsorption performance of heavy metal ions. After 24 h adsorption in simulated industrial waterwastes, removal efficiency of the composite aerogels reaches up to 81% with respect to Pb2+ ion pollutants, which is 1.2 times higher than that of original ZIF-8 nanoparticle counterparts. BC@UiO-66 composite aerogel film, as a flexible lithium-sulfur battery interlayer, demonstrates a high reversible capacity of 631 mAh g−1 at 0.5C over 100 cycles, which is attributed to its selectivity for Li+ ions and efficient inhibition to the soluble polysulfide ions. In addition, the presence of polydopamine (PDA) coating on BC@UiO-66 nanofibers in BC@UiO-66@PDA composite aerogel films increases reversible capacity up to 739 mAh g−1 at 0.5 C over 100 cycles. This work provides a feasible solution to process MOF powders into a flexible and tailorable form, and holds a new promise to rational design and manufacturing of MOF monoliths with a great structural diversity as advanced multifunctional materials. [ABSTRACT FROM AUTHOR]

Abstract A novel microporous Cu-MOF [Cu 3 (L) 2 (DMF)]·(H 3 O) 2 ·3DMF, 1 , with dual functionalities of open metal sites (OMSs) and Lewis basic sites (LBSs) based on a V-shaped organic ligand 5,5'-azanediyldiisophthalate was synthesized by hydrothermal method. The framework contains two types of 1D channels with BET surface areas 419 m2 g−1 and pore volume 0.23 cm3 g−1. It shows moderately high adsorption selectivity for C 2 H 2 /CH 4 and C 2 H 2 /N 2 at room temperature, the selectivity is 122 and 7.8 (50% and 50%), 181 and 165.7 (5% and 95%). Graphical abstract Acetylene purification material: by using novel V-shaped tetracarboxylic ligand, a microporous Cu metal-organic framework 1 with dual functionalities of OMSs and LBSs has successfully synthesized for acetylene purification purpose. The framework contains two types of 1D intersecting channels with BET surface areas 628 m2g−1 and pore volume 0.23 cm3g−1. The active sample shows moderately high selective separation of C 2 H 2 over CH 4 and N 2 at room temperature. fx1 [ABSTRACT FROM AUTHOR]

Two new isostructural 3D lanthanide-organic frameworks [H2N(Me)2] [Ln3(OH)(bpt)3(H2O)3] (DMF)2⋅(H2O)4 ( 1-Ln; Ln=Sm and Eu) with a 1D channel (25 Å) have been successfully assembled from the rare trinuclear [Ln3(OH)(COO)9] clusters and biphenyl-3,4′,5-tricarboxylic acid (H3bpt) and exhibit high stability towards water in the pH range 3-10. MOF 1-Eu is a promising luminescent probe for sensing Fe3+ in aqueous solution and is also selective towards rhodamine B (RhB) with a superior adsorption capacity of 735 mg g−1, which is the highest among the reported Ln-MOFs for RhB removal so far. Periodic DFT calculations further confirmed the selective adsorption of rhodamine B over other dyes. [ABSTRACT FROM AUTHOR]

A metal-organic framework (MOF) based on (bpy)Re(CO)3Cl-containing elongated dicarboxylate ligands and Zr6(µ3-O)4(µ3-OH)4 clusters was synthesized and used as an effective single-site catalyst to photochemically reduce carbon dioxide to carbon monoxide and formate and to provide mechanistic insights into the photocatalytic CO2 reduction process. [ABSTRACT FROM AUTHOR]

Inorganic pyrophosphate (P 2 O 7 4−, PPi) plays a vital role in a variety of metabolic processes, therefore, the development of a highly sensitive and selective detection method for PPi is of great significance. In this work, a fluorescence sensor based on luminescence metal-organic frameworks (LMOFs) via covalent post-synthetic modification (PSM) was prepared and applied to the fluorescence detection of PPi. The sensor with high fluorescence quantum yield was synthesized based on Schiff base reaction between 2-pyridinecarboxaldehyde (2-PC) and TMU-17-NH 2. It was designed according to the strong binding affinity between metal ion and PPi, and Cu2+ was selected as the mediating ion in this experiment. The fluorescence of TMU-PC is quenched by Cu2+ through photoelectron transfer (PET) mechanism, and the quenched fluorescence can be restored after adding PPi, forming an "on-off-on" fluorescence sensor, which can realize the sequential detection of Cu2+ and PPi. TMU-PC sensor has the advantages of fast response time, wide linear range, high sensitivity, and high specificity for PPi detection, and can be constructed as a fluorescence IMPLICATION logic gate. This work is the first attempt to prepare LMOFs via PSM for fluorescence detection of PPi, which has excellent application prospects for the clinical detection of related diseases. [Display omitted] • It is the first attempt to prepare LMOFs via PSM for PPi fluorescence detection. • An "on-off-on" fluorescence platform was designed based on the mediating ion Cu2+. • The detection was completed within 30 s with high specificity for PPi. • The sensor was used to detect PPi in human urine and synovial fluid samples. [ABSTRACT FROM AUTHOR]

Two microporous complexes, [Zn(TATAB)(OCH3)] ⋅2 H3O+ ( 1; TATAB=4,4′,4′′-[(1,3,5-triazine-2,4,6-triyl)tris(azanediyl)]tribenzoic acid), [Cu1.5(μ2-O)TATAB*] ( 2; TATAB*=4,4′-{[6-(dimethylamino)-1,3,5-triazine-2,4-diyl]bis(azanediyl)}dibenzoic acid) have been synthesized and characterized by elemental analysis, IR spectroscopy, UV absorption spectroscopy, and thermogravimetric analysis, and by powder XRD and single-crystal XRD analysis. Structural analyses revealed that complex 1 possesses a 3D porous framework with uncoordinated water molecules trapped in the pores; the dimensions of the channels are approximately 29.2×12.3 Å2. Complex 2 has a 3D microporous network structure. In addition, the surface photovoltage and photocatalytic activities were also studied. The photocatalytic properties of the two complexes were investigated by the decomposition of methylene blue under UV and visible-light irradiation. The results revealed that 2 possessea a higher photocatalytic activity than 1 under UV or visible-light irradiation. The potential semiconductor and dye degradation properties of complexes 1 and 2 may be widely applied in the fields of chemical semiconductors and environmental protection in the future. [ABSTRACT FROM AUTHOR]

Two novel lanthanide metal organic frameworks [Eu4(bpt)4(DMF)2(H2O)6]·(DMF)5·(H2O)4 (1) and [Tb4(bpt)4(DMF)2(H2O)8]·(DMF)5·(H2O)3 (2) were synthesized under hydrothermal conditions, forming a three-dimensional structure (H3bpt = biphenyl-3,4′,5-tricarboxylate). Single crystal X-ray diffraction reveals that compounds 1 and 2 are heteromorphic and have different topologies due to the change of metal ions with different radii and coordination steric hindrance. The unique luminescence properties of Eu3+ and Tb3+ ions motivated us to dope different amounts of Tb3+ into a single host to obtain light tunable materials. The tunable multicolor emissions, including red, red-orange, orange, yellow and green, can be readily achieved from the doped Ln-MOFs 3–6 by increasing the concentration of Tb3+. In addition, compounds 5 and 6 also exhibit different temperature-dependent luminescence behaviors when the concentration of Eu3+ is low, generating new Ln-MOF thermometers. [ABSTRACT FROM AUTHOR]

In this work, we illustrate a template strategy to create extra pores in microporous carbon for enhancing ambient-pressure CO2 uptake, as exemplified in the context of carbonizing the silicon-containing POP, PPN-4, followed by removal of the silicon template. The resultant PPN-4/C600 demonstrates a remarkable enhancement of CO2 uptake capacity at 295 K and 1 bar by a factor of 2.3 compared to the parent PPN-4. [ABSTRACT FROM AUTHOR]

The introduction of the combination of open metal site (OMS) and π-complexation into MOF has led to very high ethylene–ethane adsorption selectivity at 318 K, as illustrated in the context of MIL-101–Cr–SO3Ag. The interactions with ethylene from both OMS and π-complexation in MIL-101–Cr–SO3Ag have been investigated by in situ IR spectroscopic studies and computational calculations, which suggest that π-complexation contributes dominantly to the high ethylene–ethane adsorption selectivity. [ABSTRACT FROM AUTHOR]

A series of 4f-5f heteronuclear metallic complexes were synthesized by a hydrothermal route from mixtures of uranyl acetate, lanthanide nitrate, and 1,2,4,5-benzenetetracarboxylic acid (H4BTA) in an aqueous system. Single-crystal X-ray analysis revealed that the thirteen UO2-Ln-BTA complexes ([(UO2)1.5Ln(C10O8H2)1.5(H2O) x]⋅ y H2O; Ln=La ( 1), Ce ( 2), Pr ( 3), Nd ( 4), Sm ( 5), Eu ( 6), Gd ( 7), Tb ( 8), Dy ( 9), Ho ( 10), Er ( 11), Tm ( 12), Yb ( 13); x=6 for 1- 4, x=5 for 5- 13; y=0 for 4, y=1 for 3, y=2 for 2, y=3 for 5, 9, 10, 12, 13, y=4 for 1, 6, 7, 8, 11) are isomorphous with three-dimensional structures. For the purpose of developing potential applications of the UO2-Ln-BTA complexes, we investigated their surface photovoltage and photocatalytic properties. In addition, the thermogravimetric analysis and photoluminescent properties of these complexes were also studied in detail. [ABSTRACT FROM AUTHOR]

• A composite material Cu-BTC@H4TBAPy assembled by Cu-BTC and H4TBAPy. • Superior luminescence property shows potential applications in fluorescence sensing. • A role of fluorescent sensor switch in recognition of Al3+ and Fe3+. A kind of metal organic framework composite material was prepared by encapsulating chemical chromophore the 1,3,6,8-tetrakis(p-benzoic acid)pyrene (H 4 TBAPy) in Cu-BTC which has the large square-shaped pores, a reasonable degree of thermal stability and a capacity for chemical functionalization of the channel linings. Cu-BTC@H 4 TBAPy has superior luminescence performance than framework material Cu-BTC (H 3 BTC = 1, 3, 5-trimellitic acid). Base on its luminescence property, we performed fluorescence sensing experiments on heavy metal ions. The results show that the metal ion Fe3+ has a significant turn-off effect on Cu-BTC@H 4 TBAPy, while Al3+ has a significant turn-on effect on Cu-BTC@H 4 TBAPy. This indicates that Cu-BTC@H 4 TBAPy can play a role of fluorescent sensor switch in recognition of different ions. [Display omitted] [ABSTRACT FROM AUTHOR]

Three MM-MOFs based on the reaction of H 6 TTHA ligand, Ln(NO 3) 3 ·6H 2 O (Ln=Eu, Sm, Dy) and Zn(NO 3) 2 ·6H 2 O under hydrothermal conditions. Complex 1 had the fluorescence sensing abilities for metal ions, anions, and organic nitro compounds. It was worth noting that complex 1 showed prominent sensitivity for TNP, the detection limit was as low as 1.14 μM. [Display omitted] Metal-organic frameworks composed of two metals in the structure are called mixed-metal metal organic frameworks (MM-MOFs). In this work, we constructed three MM-MOFs, namely [Zn 3 Eu 2 (TTHA) 2 (H 2 O) 6 ]·6H 2 O (1), [Zn 3 Sm 2 (TTHA) 2 (H 2 O) 6 ]·2H 2 O (2) and [ZnDy(HTTHA)(H 2 O) 4 ]·2H 2 O (3) by the reaction of H 6 TTHA ligand (H 6 TTHA = 1, 3, 5-triazine-2, 4, 6-triamine hexaacetic acid), Ln(NO 3) 3 ·6H 2 O (Ln = Eu, Sm, Dy) and Zn(NO 3) 2 ·6H 2 O under hydrothermal conditions. The complexes 1 – 2 were a 3D microporous structure and complex 3 formed a 3D network structure. Furthermore, complex 1 exhibited excellent fluorescence properties. We explored the fluorescence sensing abilities of complex 1 for metal ions, anions, and organic nitro compounds. The experimental results showed that complex 1 could sensitively and efficiently detect Fe3+, Cr 2 O 7 2- ions and 2,4,6-trinitrophenol (TNP). It was worth noting that complex 1 showed prominent sensitivity for TNP, the detection limit was as low as 1.14 μM. [ABSTRACT FROM AUTHOR]

Highlights: [•] Uranyl complexes constructed by 1, 2, 4, 5-benzenetetracarboxylic acid. [•] Disscussing the surface photovoltage spertra. [•] Disscussing the photocatalytic property and the impact factors of the property. [Copyright &y& Elsevier]

Two cadmium-organic frameworks were synthesized, namely, [Cd(dptz)2]·{Cd[(NH2)2CS]4}·(NO3)4 (1, dptz=3,6-di-(pyridin-4-yl)-1,2,4,5-tetrazine) and Cd(dpmtz)2 (2, dpmtz=3,6-di-(pyridin-4-yl)-1,2-dihydro-1-mercapto-1,2,4,5-tetrazine). Compound 1 was obtained by the self-assembly of dptz, Cd(SPh)2 and thiourea under solvothermal conditions. Compound 2 was prepared through an in situ ligand reaction in which generated a new ligand dpmtz only by changing reaction temperature. Compound 1 and 2 were characterized by single-crystal X-ray structure determination, thermogravimetric analysis and powder X-ray diffraction studies. The adsorption behavior shows that compound 2 has selective adsorption capacities of CO2 over N2. [ABSTRACT FROM AUTHOR]

Reducing the level of sulfur content in fuel oils has long been desired for environmental reasons. Polyoxometalates (POMs) can act as catalysts to remove sulfur-containing heterocyclic compounds by the process of oxidative desulfurization under mild conditions. However, one key obstacle to the development of POM-based catalysts is the poor solubility of POMs in the overall nonpolar environment. We report a novel strategy for the introduction of catalytically active POMs into nonpolar reaction systems by encapsulating the inorganic catalyst within the pores of a metal-organic framework structure in which the organic ligands act as hydrophobic groups. The nanocrystalline catalysts, obtained rapidly and conveniently by both solution and mechanochemical synthesis, showed remarkable activities in catalytic oxidative desulfurization reactions in both a model diesel environment and in real diesel wherein dibenzothiophene was converted rapidly and quantitatively into dibenzothiophene sulfone. [ABSTRACT FROM AUTHOR]

Luminescent metal-organic frameworks (LMOFs) have become an important class of fluorescence sensing materials, whereas direct applications of LMOFs for identifying analytes still remain a challenge. Post synthetic modification (PSM) is an effective strategy to improve the performance of LMOFs. In this work, PSM of UiO-66-NH 2 was achieved with 4-carboxyphenylboronic (4-CPBA), based on which a fluorescence sensor, UiO-CPBA, was designed. The sensor was synthesized in the off state utilizing the photo-induced electron transfer (PET) process caused by the introduction of 4-CPBA and applied to the recognition of sialic acid (SA). The interaction between the boric acid group and the triol side chain of SA interrupted the PET process and turned on the fluorescence, thus fluorescence detection of SA was realized. This method exhibited a linear range of 1–100 μM and a limit of detection (LOD) of 0.15 μM for SA determination. The analysis of human serum verified the practicability of UiO-CPBA for SA, giving a new way for the construction of SA sensing platforms toward complex real samples. [Display omitted] • A turn-on fluorescence sensor was designed by PSM of MOFs with 4-CPBA. • PSM-MOFs were used for the fluorescence detection of sialic acid for the first time. • The sensor exhibited high sensitivity and specificity toward sialic acid. [ABSTRACT FROM AUTHOR]

1 A new Ln-BTC-Ac-FM framework intelligent materials 2 High sensitivity and selectivity to UO 2 2+ in aqueous solution. 3 Better adsorption effects on Coomassie Brilliant Blue (CBB) and Eosin The unique fluorescence properties of rare earth ions and subtle interactions with organic ligands make the target lanthanide metal-organic frameworks show potential development prospects in many fields. Based on this situation, a series of new lanthanide metal-organic frameworks Ln-BTC-AC-FM: (CH 3) 2 NH 2 [Ln 2 (BTC)(AC) 3 (FM)], (Ln=Pr (1), Ce (2), Nd (3), Eu (4), Sm (5), Gd (6), Tb (7), Ho (8), Er (9) and Yb (10), H 3 BTC=1,3,5-benzenetricarboxylic acid) were synthesized through the reaction of triangular polycarboxylic acid ligand (H 3 BTC) and rare earth nitrate Ln(NO 3) 3 ·6H 2 O with mixed formic acid (FM) and glacial acetic acid (AC) system. Due to this new type of Ln-BTC-AC-FM MOFs have unique and excellent fluorescence properties, we selected (CH 3) 2 NH 2 [Eu 2 (BTC)(AC) 3 (FM)] (4) to explore its detection performance for UO 2 2+ in aqueous solution. The study found that 4 is a high-efficiency fluorescent probe, which has a good quenching effect on uranium solution, and the quenching rate can reach 98.01%. At the same time, 4 has a good fluorescent response to UO 2 2+, with a higher K SV value of 8.56 × 103 M−1 and a lower detection limit of 4.12 μM. In addition, we also studied the adsorption properties of this series of Ln-BTC-AC-FM MOFs for dyes because of their novel three-dimensional microporous structures. The results showed that 4 has a good adsorption effect on Coomassie Brilliant Blue (CBB) and Eosin. Moreover, it was found that the dye adsorption process was proved to be a suitable pseudo-second-order kinetic model. [Display omitted] [ABSTRACT FROM AUTHOR]

SYNOPSIS A novel tetraphenylethylene-containing Bi-MOF has been synthesized and characterized, which exhibits turn off/on sensing behavior. The photophysical process was analyzed by TRES. The sensor not only displays quenching effect towards Fe3+ detection in the interference of Fe2+, but also can be used for the quantitative determination of Fe3+ in serum. Discussion of biological activity provides a great possibility for the practical application in clinical detection • A novel tetraphenylethylene-containing Bi-MOF were synthesized, which exhibits turn off/on sensing behavior. • The photophysical processes was studied by TRES. • It has low toxicity and demonstrates quenching effect towards Fe3+ detection in the interference of Fe2+ and in serum, which will provide a possibility for application in clinical detection. A novel MOF Bi-TCBPE ([Bi(TCBPE)(H 2 O)]·(Me 2 NH 2 +)) based on 4′,4‴,4″‴,4‴‴-(ethene-1,1,2,2-tetrayl)tetrakis(([1,1′-biphenyl]-4-carboxylic acid)) has been synthesized and characterized by elemental analysis, powder X-ray diffraction, IR, UV–vis spectroscopy and thermogravimetry analysis, which exhibits strong emission (Φ F = 76.96%) in methanol suspension.The photophysical process was analyzed by TRES. Structural analysis revealed that Bi-TCBPE showed a novel two-fold interpenetrated packing framework. Luminescence measurements indicate that the Bi-TCBPE sensor shows sensing behavior with "turn off" towards Fe3+ and "turn on" towards Cysteine (Cys) significantly. Bi-TCBPE as a luminescent sensor displays quenching effect towards Fe3+ detection in the interference of Fe2+. It also can be used for the quantitative determination of Fe3+ in serum. The results will provide a great possibility for the practical application of luminescent metal organic frameworks (LMOFs) in clinical detection. [ABSTRACT FROM AUTHOR]