Reversible single-crystal-to-single-crystal transition in Gd(III) metal-organic frameworks induced by heat and solvents with a significant magnetocaloric effect.

The design and synthesis of a Gd(III) metal-organic framework with the formula [Gd4(BTDI)3(DMF)4]n (JXUST-40, H4BTDI = 5,5'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)diisophthalic acid) are reported hererin. Interestingly, a reversible single-crystal-to-single-crystal transition between JXUST-40 and {[Gd4(BTDI)3(H2O)4]·6H2O}n (JXUST-40a) was achieved under the stimulation of heat and solvents. Both JXUST-40 and JXUST-40a exhibited good stability when soaked in common solvents and aqueous solutions with pH values of 1-12. Magnetic studies showed that JXUST-40a has a larger magnetocaloric effect with -ΔSmaxm = 26.65 J kg-1 K-1 at 2 K and 7 T than JXUST-40 due to its larger magnetic density. Structural analyses indicated that the coordinated solvent molecules play a crucial role in the coordination environment around the Gd(III) ions and the change in the framework, ultimately leading to the changes in the pore size and magnetism between JXUST-40 and JXUST-40a. In addition, both isomorphic [Dy4(BTDI)3(DMF)4]n (JXUST-41) and {[Dy4(BTDI)3(H2O)4]·6H2O}n (JXUST-41a) displayed slow magnetic relaxation behaviour.

A dinuclear CdII cluster-based stable luminescent metal-organic framework for the consecutive and visual detection of H2PO4- and OCN.

Due to their hazard to biological systems, it is urgent to develop materials that can rapidly and sensitively detect the concentration of H2PO4- and OCN- ions. In this work, a new CdII-based luminescent metal-organic framework with the formula [Cd(BTDB)(2,6-BBIP)]n (JXUST-47, H2BTDB = (benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzoic acid, 2,6-BBIP = 2,6-bis(benzimidazol-1-yl)pyridine) and sql topology was successfully synthesized using a mixed-ligand strategy. JXUST-47 shows good chemical and thermal stability. It also exhibits weak quenching and fluorescence blue shift for H2PO4- and red shift for OCN-, with the detection limits of 0.106 and 0.128 mM, respectively. In addition, considering the demand for H2PO4- and OCN- ion detection, by combining this with the functions of a smartphone, the chroma of photographs have been used to realize the consecutive visual detection of the concentration of these ions.

Fluorescence sensing and device fabrication with luminescent metal-organic frameworks.

Metal-organic frameworks (MOFs) are a novel class of hybrid porous multi-functional materials consisting of metal ions/clusters and organic ligands. MOFs have exclusive benefits due to their tunable structure and diverse properties. Luminescent MOFs (LMOFs) exhibit both porosity and light emission. They display abundant host and guest responses, making them conducive to sensing. Currently, LMOF sensing research is gaining more depth, with attention given to their device and practical applications. This work reviews recent advancements and device applications of LMOFs as chemical sensors toward ions, volatile organic compounds, biomolecules, and environmental toxins. Furthermore, the detection mechanism and the correlation between material properties and structure are elaborated. This analysis serves as a valuable reference for the preparation and efficient application of targeted LMOFs.

Highly Stable Rare Earth Metal-Organic Frameworks for Fluorescence Recognition of Folic Acid, Proton Conduction, and Magnetic Refrigeration.

Four new isostructural rare earth metal-organic frameworks (RE-MOFs) were synthesized and full characterized, namely, {[(CH)2NH2]3[RE2(BTDBA)2(HCOO)]·5H2O·2DMF}n (H4BTDBA = (4',4'''-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis([1,1'-biphenyl]-3,5-dicarboxylic acid); RE = Eu (JXUST-34), Gd (JXUST-35), Tb (JXUST-36), and Dy (JXUST-37)). The single-crystal structures analysis shows that JXUST-34-37 are chain-based three-dimensional structures. Importantly, JXUST-34 exhibits excellent water, organic solvents, and acid-base stability, which can be used as a fluorescence sensor for folic acid and Al3+ with detection limits of 0.02 mM and 0.05 µM, respectively. The presence of free [(CH)2NH2]+ cations in the channels can engage the proton carrier during proton conduction. JXUST-34-37 display good proton conductivity, and the conductivities vary with relative humidity and temperatures, among which JXUST-37 has the highest conductivity of 9.66 × 10-3 S·cm-1 at 60 °C and 98% RH. The magnetic studies show that the -ΔSm of JXUST-35 reaches 16.13 J kg-1 K-1 at 2 K and ΔH = 7 T. JXUST-34-37 show multifunctional properties of fluorescence sensing, high proton conductivity, and magnetic refrigeration, which provides a new clue for the development of fluorescent-responsive, magnetic-refrigerant, and proton-conductive RE-MOF materials.

A highly stable chain-based EuIII metal-organic framework as a turn-on and blue-shift luminescent sensor for dipicolinic acid.

The development of a rapid and selective method for the identification of dipicolinic acid (DPA), a specific biomarker in Bacillus anthracis spores, is of great importance for the avoidance of anthrax infection. Herein, a chain-based EuIII metal-organic framework with the formula {[Eu3(BTDB)3(µ3-OH)3(H2O)]·solvents}n (JXUST-38, H2BTDB = (benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzoic acid) was obtained using 2-fluorobenzoic acid as the pH regulator. JXUST-38 exhibits good chemical and thermal stability and can specifically recognize DPA in N,N-dimethylformamide solution through luminescence enhancement and blue-shift effects with a detection limit of 0.05 µM. Furthermore, the significant luminescence enhancement and blue shift under UV lamps are obviously observable by the naked eye. The luminescence sensing mechanism is attributed to absorbance-induced enhancement between JXUST-38 and DPA. Test paper and mixed-matrix membrane based on JXUST-38 are designed for DPA detection. In addition, the feasibility of using JXUST-38 in biosensing is discussed in detail.

Highly pH-Responsive Sensor Based on a EuIII Metal-Organic Framework with Efficient Recognition of Arginine and Lysine in Living Cells.

A lanthanide-based three-dimensional metal-organic framework with excellent water, acid/base, and solvent stability, namely {[(CH3)2NH2]0.7[Eu2(BTDBA)1.5(lac)0.7(H2O)2]·2H2O·2DMF·2CH3CN}n (JXUST-29, H4BTDBA = 4',4‴-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis([1,1'-biphenyl]-3,5-dicarboxylic acid), Hlac = lactic acid), has been synthesized and characterized. Since the N atoms of the thiadiazole group will not coordinate with lanthanide ions, JXUST-29 has a free basic N-site accessible to small H+ ions, which allows it to be used as a promising pH fluorescence sensor. Interestingly, the luminescence signal was significantly enhanced, with an approximately 54-fold enhancement in the emission intensity when the pH value was increased from 2 to 5, which is the typical behavior of pH probes. In addition, JXUST-29 can also be used as a luminescence sensor to detect l-arginine (Arg) and l-lysine (Lys) in an aqueous solution through fluorescence enhancement and the blue-shift effect. The detection limits were 0.023 and 0.077 µM, respectively. In addition, JXUST-29-based devices were designed and developed to facilitate detection. Importantly, JXUST-29 is also capable of detecting and sensing Arg and Lys in living cells.

Solvothermal synthesis and device fabrication of a Eu3+-based metal-organic framework as a turn-on and blue-shift fluorescence sensor toward Cr3+, Al3+ and Ga3.

A novel three-dimensional Eu3+-based metal-organic framework with the formula {[(CH3)2NH2][Eu(BTDI)]·H2O·DMF}n (JXUST-25) was prepared by solvothermal method based on Eu3+ and 5,5'-(benzothiadiazole-4,7-diyl)diisophthalic acid (H4BTDI) with benzothiadiazole (BTD) luminescent groups. Due to the presence of Eu3+ and organic fluorescence ligand, JXUST-25 displays turn-on and blue-shift fluorescence toward Cr3+, Al3+ and Ga3+ with limits of detection (LOD) of 0.073, 0.006 and 0.030 ppm, respectively. Interestingly, the alkaline environment can change the fluorescence of JXUST-25 toward Cr3+/Al3+/Ga3+ and the addition of HCl solution realizes the reversible change of the fluorescence of JXUST-25 toward Cr3+/Al3+/Ga3+. It is noteworthy that the fluorescent test paper and light-emitting diode lamp based on JXUST-25 can effectively detect Cr3+, Al3+ and Ga3+ by the visual changes. In addition, the turn-on and blue-shift fluorescence between JXUST-25 and M3+ ions may be caused by the host-guest interaction and the absorbance caused enhancement mechanism.

Enhanced Heterogeneous Catalytic Activity of Peroxymonosulfate for Rhodamine B Degradation via a CoII-Based Metal-Organic Framework.

A stable metal-organic framework with the formula {[Co(BBZB)(IPA)]·H2O}n (JXUST-23, BBZB = 4,7-bis(1H-benzimidazole-1-yl)-2,1,3-benzothiadiazole and H2IPA = isophthalic acid) was constructed by incorporating Co2+ ions and two conjugated ligands under solvothermal conditions. JXUST-23 takes a dinuclear cluster-based layer structure with a porosity of 2.7%. In this work, JXUST-23 was used to activate peroxymonosulfate (PMS) to degrade rhodamine B (RhB), a difficult-to-degrade pollutant in water. Compared with pure PMS or JXUST-23, the JXUST-23/PMS system displays the best degradation ability of RhB in neutral solution. When the mass ratio of JXUST-23 to PMS was 2:3, 99.72% of RhB (50 ppm) was removed within 60 min, and the reaction rate was 0.1 min-1. Furthermore, free radical quenching experiments show that SO4•- was the main free radical during the process of RhB degradation. In addition, JXUST-23 exhibits good reusability for the degradation of the organic dye RhB, making it a potential candidate for environmental remediation.

Controllable Synthesis of TbIII Metal-Organic Frameworks with Reversible Luminescence Sensing for Benzaldehyde Vapor.

Two novel lanthanide metal-organic frameworks (MOFs) with the formulas [Tb(bidc)(Hbidc)(H2O)]n (JXUST-20) and {[Tb3(bidc)4(HCOO)(DMF)]·solvents}n (JXUST-21) were synthesized based on 2,1,3-benzothiadiazole-4,7-dicarboxylic acid (H2BTDC) under solvothermal conditions. Interestingly, benzimidazole-4,7-dicarboxylic acid (H2bidc) was formed in situ using H2BTDC as the starting material. The self-assembly process of the targeted MOFs with different topological structures can be controlled by the solvents and concentration of the reactants. Luminescence experiments show that JXUST-20 and JXUST-21 exhibit strong yellow-green emission. JXUST-20 and JXUST-21 can selectively sense benzaldehyde (BzH) via a luminescence quenching effect with detection limits of 15.3 and 1.44 ppm, respectively. In order to expand the practical application of MOF materials, mixed-matrix membranes (MMMs) have been constructed by mixing targeted MOFs and poly(methyl methacrylate) in a N,N-dimethylformamide (DMF) solution, which can also be used for BzH vapor sensing. Therefore, the first case of MMMs derived from TbIII MOFs has been developed for the reversible detection of BzH vapor, providing a simple and efficient platform for the future detection of volatile organic compounds.

Selective recognition of Hg2+ ions in aqueous solution by a CdII-based metal-organic framework with good stability and vacant coordination sites.

A novel water-stable CdII-based metal-organic framework, namely {[Cd(BIBT)(TDC)]·2H2O}n (JXUST-28, BIBT = 4,7-bi(1H-imidazol-1-yl)benzo-[2,1,3]thiadiazole and H2TDC = 2,5-thiophenedicarboxylic acid), was synthesized using a mixed-ligand strategy. Structural analysis demonstrates that JXUST-28 exhibits a two-dimensional layer structure with 4-connected sql topology. Intriguingly, JXUST-28 presents good stability in boiling water (at least 5 days), common organic solvents and aqueous solutions with different pH values of 2-12 (more than 24 hours). Furthermore, fluorescence experiments revealed that JXUST-28 could sense Hg2+ ions in aqueous solution via a quenching effect with a detection limit of 0.097 µM. Meanwhile, JXUST-28 can also be regenerated at least 5 times to detect Hg2+ ions. In addition, light-emitting diode lamps, luminescent films, and test papers of JXUST-28 have been successfully developed for practical applications.

Fabrication and DFT Calculation of Amine-Functionalized Metal-Organic Framework as a Turn-On Fluorescence Sensor for Fe3+ and Al3+ Ions.

Due to their important role in biological systems, it is urgent to develop a material that can rapidly and sensitively detect the concentration of Fe3+ and Al3+ ions. In this work, a brand-new CdII-based metal-organic framework [Cd(BTBD)2(AIC)]n (JXUST-18, BTBD = 4,7-bis(1H-1,2,4-triazol-1-yl)-2,1,3-benzothiadiazole and H2AIC = 5-aminoisophthalic acid) with a 4-connected sql topology was designed and synthesized. The symmetrical CdII centers are linked by AIC2- ligands with µ3-η1:η1:η1:η1 coordination mode to form a [Cd2(COO)2] secondary building unit (SBU). The contiguous SBUs are further connected by BTBD ligands to form a two-dimensional (2D) layer structure. JXUST-18 can remain stable in aqueous solutions with pH values of 3-12 or in boiling water. Luminescent experiments suggest that JXUST-18 displays more than eightfold fluorescence enhancement in the presence of Fe3+ and Al3+ ions, and the detection limits for Fe3+ and Al3+ ions are 0.196 and 0.184 µM, respectively. Furthermore, the change in luminescence color is uncomplicatedly distinguishable with the naked eye under ultraviolet light at 365 nm. In addition, a series of devices based on JXUST-18 including fluorescence test strips, lamp beads, and composite films were developed to detect metal ions via visual changes in luminescence color. Significantly, JXUST-18 is a rare MOF-based turn-on fluorescence sensor for the detection of Fe3+ ions. The theoretical calculation suggests that the complexation of Fe3+/Al3+ ions and the -NH2 group contributes to fluorescence enhancement.

A pH-Stable TbIII-Based Metal-Organic Framework as a Turn-On and Blue-Shift Fluorescence Sensor toward Benzaldehyde and Salicylaldehyde in Aqueous Solution.

A new polydentate tetracarboxylic acid with a benzothiadiazole unit (4',4'''-(benzo[c][1,2,5]thiadiazole-4,7-diyl)bis([1,1'-biphenyl]-3,5-dicarboxylic acid), H4BTDBA) has been used to prepare a pH-stable three-dimensional TbIII-based metal-organic framework (MOF) with the formula {[(CH3)2NH2]0.7[Tb2(BTDBA)1.5(lac)0.7(H2O)2]·solvents}n (Hlac = lactic acid, JXUST-19). JXUST-19 exhibits a new (4,4,12)-connected topology based on tetranuclear [Tb4] clusters. JXUST-19 can remain stable when soaked in water for at least 1 week and in aqueous solutions with various pH values (2-12) for 24 h. Fluorescence study indicates JXUST-19 can be employed as a rare turn-on and blue-shift MOF sensor toward benzaldehyde (BZ) and salicylaldehyde (SA). To date, JXUST-19 represents the first TbIII-based turn-on MOF sensor toward salicylaldehyde in aqueous solution, and the fluorescence enhancement and naked-eye detection of BZ have been rarely reported. In addition, JXUST-19 based fluorescent test papers, light-emitting diode lamp beads, and portable composite films were developed to realize naked-eye detection of BZ and SA, which has great potential in practical applications.

Mechanical stretch aggravates vascular smooth muscle cell apoptosis and vascular remodeling by downregulating EZH2.

BACKGROUND: Enhancer of zeste homolog 2 (EZH2) was recently found to play an important role in cardiovascular disease. However, the role of EZH2 in vascular remodeling induced by mechanical stretch is poorly understood. The aim of the present work was to investigate the role of EZH2 in regulating smooth muscle cell function through mechanical stretch assays and to explore the underlying mechanisms. METHODS: WT C57BL/6 J mice underwent sham surgery or abdominal aortic constriction. The level of EZH2 expression was determined by Western blotting and immunohistochemical staining. We demonstrated the thickness of vascular remodeling by HE staining. JASPAR was used to predict transcription factors that could affect EZH2. Chromatin immunoprecipitation was used to substantiate the DNAprotein interactions. Promoter luciferase assays were performed to demonstrate the activity of the transcription factors. RESULTS: We found that in vivo, AAC significantly reduced EZH2 protein levels in the thoracic aorta. Smooth muscle-specific overexpression of EZH2 was sufficient to attenuate the AAC-induced reduction in trimethylation of Lys-27 in histone 3 and thickening of the arterial media. Administration of GSK-J4 (an inhibitor of H3K27me3 demethylase) induced the same effects. In addition, we found that mechanical stretch regulated the expression of EZH2 through the Yes-associated protein (YAP)- transcriptional factor TEA domain 1 (TEAD) pathway. TEAD1 bound directly to the promoter of EZH2, and blocking the YAP-TEAD1 interaction inhibited EZH2 downregulation due to mechanical stretch. CONCLUSION: This study reveals that mechanical stretch downregulates EZH2 through the YAP-TEAD1 pathway, thereby aggravating smooth muscle cell apoptosis and vascular remodeling.

Dickkopf1 (Dkk1) Alleviates Vascular Calcification by Regulating the Degradation of Phospholipase D1 (PLD1).

Vascular calcification (VC) is a significant risk factor for cardiovascular mortality and morbidity in patients with atherosclerosis (AS), chronic kidney disease, and diabetes. Dickkopf1 (Dkk1) is a multifunctional secreted glycoprotein that has been explored as a novel potential antitumor target. Recently, Dkk1 was shown to be closely associated with AS development. However, the role of Dkk1 in VC remains elusive. In this study, we explored the role and molecular mechanisms of Dkk1 in VC based on a smooth muscle-specific Dkk1-knockout (Dkk1SMKO) mouse model. Our data indicated that Dkk1 expression was decreased under calcifying conditions and that Dkk1 overexpression alleviated high phosphate-induced vascular calcification. In vivo, smooth muscle Dkk1-specific knockout aggravated vascular calcification in mice. However, phospholipase D1 (PLD1) overexpression partially weakened the protective effect of Dkk1 against vascular calcification. Mechanistically, Dkk1 slowed vascular calcification by promoting the degradation of PLD1 via the regulating autophagosome formation and maturation. In conclusion, we found that Dkk1 could alleviate vascular calcification by regulating the degradation of PLD1.

Turn-on and blue-shift fluorescence sensor toward L-histidine based on stable CdII metal-organic framework with tetranuclear cluster units.

A novel CdII-based two-fold interpenetrated metal-organic framework (MOF), namely {[Cd2(BTDB)2(4,4-bpy)]·DMF}n (JXUST-14), (H2BTDB = 4,4'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzoic acid and 4,4-bpy = 4,4-bipyridine), has been prepared and characterized. Single-crystal structure determination reveals that JXUST-14 has a tetranuclear cluster based 6-connected pcu topological network with Schlafli symbol {412·63}. When soaked in common organic solvents and aqueous solutions with diverse pH values of 2-12 for 48 h, JXUST-14 remains stable. JXUST-14 is a highly selective and sensitive luminescent sensor for L-histidine (His) with a detection limit of 11.1 ppm. JXUST-14 is the first CdII-based MOF for the detection of His via turn-on and fluorescence blue-shift effects. Experimental study and theoretical calculation suggest that the sensing process can be mainly attributed to a charge transfer and energy transfer mechanism. More interestingly, LED lamps of JXUST-14 and JXUST-14@His were successfully developed, which endowed efficient sensitivity for His detection and thus provide great potential for future applications.

A Benzothiadiazole-Based Eu3+ Metal-Organic Framework as the Turn-On Luminescent Sensor toward Al3+ and Ga3+ with Potential Bioimaging Application.

The design and preparation of novel multifunctional lanthanide metal-organic frameworks (Ln-MOFs) have been arisen widespread attention. In particular, Ln-MOFs have shown great luminescence potential in chemical sensing. Herein, a new benzothiadiazole-based Eu-MOF {[(CH3)2NH2][Eu(BTDB)2]·2H2O}n (JXUST-11) was obtained based on 4,4'-(benzo[c][1,2,5]thiadiazole-4,7-diyl)dibenzoic acid (H2BTDB), which exhibits a chain-based three-dimensional framework. Moreover, JXUST-11 is considered as a photoluminescent sensor to identify Al3+ and Ga3+ ions by fluorescence enhancement with the detection limits of 2.9 and 10.2 ppm, severally. Importantly, Al3+ and Ga3+ can be discerned with the naked eye by color change under a natural lamp. In addition, a portable MOF film based on JXUST-11 was developed for Al3+ and Ga3+ detection. This is the first Ln-MOF that can be employed as a naked-eye fluorescent probe to identify Ga3+. Interestingly, JXUST-11 is also capable of detecting Al3+ and Ga3+ in living cells.

Dickkopf-1 promotes Vascular Smooth Muscle Cell proliferation and migration through upregulating UHRF1 during Cyclic Stretch application.

Dickkopf-1 (DKK1) was recently shown to play an important role in cardiovascular disease. The aim of this work was to assess the role of DKK1 in the regulation of smooth muscle cell function by mechanical stretch and the mechanisms underlying this process. Methods: Wild-type C57BL/6J mice were subjected to sham or abdominal aortic constriction (AAC) surgery. The expression level of DKK1 was examined by immunohistochemical staining and Western blotting. Analyses of DKK1 function in vascular smooth muscle cell (VSMC) proliferation and migration were performed. Transcriptome sequencing analysis was performed to identify the differentially expressed genes and pathways regulated by DKK1. Smooth muscle-specific Dkk1 knockout mice were used to confirm the function of DKK1 in vivo. Chromatin immunoprecipitation (ChIP) was used to confirm DNA-protein interactions. Promoter luciferase analysis was used to detect transcription factor activity. Results: We found that AAC significantly increased DKK1 protein levels in the thoracic aorta and coronary artery in vivo. In vitro, high-level stretch (18%) induced the expression of DKK1 in VSMCs. Knocking down DKK1 inhibited VSMC proliferation and migration under high-level stretch (18%). We identified ubiquitin-like containing PHD and RING finger domains 1 (UHRF1) as a target gene of DKK1. Knockdown of UHRF1 with small interfering RNAs partially reversed the regulatory effect of recombinant DKK1 on VSMCs. Specific deletion of DKK1 in VSMCs was sufficient to attenuate the AAC-induced upregulation of UHRF1, thickening of arterial media and increase in VSMC proliferation. Furthermore, we found that DKK1 regulated UHRF1 expression through the YAP-TEAD pathway. TEAD1 and TEAD4 bound directly to the promoter of UHRF1, and blocking the YAP-TEAD interaction inhibited UHRF1 upregulation due to DKK1. Conclusions: This study reveals that DKK1 mediates the mechanical stretch regulation of smooth muscle cell function by modulating UHRF1 expression through the YAP-TEAD pathway.

Turn-On Luminescent Sensor toward Fe3+, Cr3+, and Al3+ Based on a Co(II) Metal-Organic Framework with Open Functional Sites.

A novel Co-based metal-organic framework (MOF) with the formula of {[Co3(BIBT)3(BTC)2(H2O)2]·solvents}n (JXUST-2, where JXUST denotes Jiangxi University of Science and Technology, BIBT = 4,7-bi(1H-imidazol-1-yl)benzo-[2,1,3]thiadiazole, and H3BTC = 1,3,5-benzenetricarboxylic acid) has been solvothermally prepared, which takes 3D structure with a rare 3,4,6-c topology and contains intramolecular hydrogen bonds. Interestingly, the sensing investigations suggest that JXUST-2 could be considered as a multifunctional fluorescence sensor toward Fe3+, Cr3+, and Al3+ via a turn-on effect with good reusability and detection limits of 0.13, 0.10, and 0.10 µM, respectively. The turn-on effect of JXUST-2 could be ascribed to an absorbance caused enhancement (ACE) mechanism. Notably, JXUST-2 is the first turn-on MOF fluorescent sensor for Fe3+, Cr3+, and Al3+ simultaneously.