Dual-Functional Eu-Metal-Organic Framework with Ratiometric Fluorescent Broad-Spectrum Sensing of Benzophenone-like Ultraviolet Filters and High Proton Conduction.

The construction of attractive dual-functional lanthanide-based metal-organic frameworks (Ln-MOFs) with ratiometric fluorescent detection and proton conductivity is significant and challenging. Herein, a three-dimensional (3D) , namely, [Eu(HL)(SBA)(HO)]·9HO, has been hydrothermally synthesized with a dual-ligand strategy, using (4-carboxypiperidyl)--methylenephosphonic acid (HL = HOPCH-NCH-COOH) and 4-sulfobenzoic acid monopotassium salt (KHSBA = KOSCHCOOH) as organic linkers. showed ratiometric fluorescent broad-spectrum sensing of benzophenone-like ultraviolet filters (BP-like UVFs) with satisfactory sensitivity, selectivity, and low limits of detection in water/ethanol (1:1, v/v) solutions and real urine systems.

The gp130/STAT3-endoplasmic reticulum stress axis regulates hepatocyte necroptosis in acute liver injury.

Aim: To investigate the effect of the gp130/STAT3-endoplasmic reticulum (ER) stress axis on hepatocyte necroptosis during acute liver injury.

Methods: ER stress and liver injury in LO2 cells were induced with thapsigargin, and in BALB/c mice with tunicamycin and carbon tetrachloride (CCl4). Glycoprotein 130 (gp130) expression, the degrees of ER stress, and hepatocyte necroptosis were assessed.

Two Stable Cd-MOFs as Dual-Functional Materials with Luminescent Sensing of Antibiotics and Proton Conduction.

Construction and investigation of dual-functional metal-organic frameworks (MOFs) with luminescent sensing and proton conduction provide widespread applications in clean energy and environmental monitoring fields. By selecting a phosphonic acid ligand 4-pyridyl-CHN(CHPOH) (HL) and coligand 2,2'-biimidazole (Hbiim), two cadmium-based MOFs [Cd(HL)(Hbiim)] () and (Hbiim)·[Cd(L)(Hbiim)Cl] () with different structures and properties have been hydrothermally synthesized by controlling reaction temperature. Based on the excellent thermal and chemical stabilities, and good luminescent stabilities in water solution, and can serve as luminescent sensors of chloramphenicol (CAP) with different quenching constant () values and detection limits (LODs) in water, simulated environmental system, and real fish water system.

Intracellular alpha-fetoprotein mitigates hepatocyte apoptosis and necroptosis by inhibiting endoplasmic reticulum stress.

Background: Endoplasmic reticulum (ER) stress contributes to the pathogenesis of chronic liver diseases, but how hepatocytes respond to ER stress has not been clarified. Alpha-fetoprotein (AFP) is secreted by hepatoma cells and elevated levels of serum AFP are associated with development of liver malignancies.

Aim: To investigate whether and how AFP could regulate ER stress and hepatocyte injury.

Dual-Functional Metal-Organic Framework for Luminescent Detection of Carcinoid Biomarkers and High Proton Conduction.

It remains a challenge to exploit dual-functional metal-organic frameworks (MOFs) for applications, including luminescence detection and proton conduction. With the deliberate selection of the bifunctional organic ligand 5-sulfoisophthalic acid monosodium salt (NaHbts), and the phosphonic acid ligand ,'-piperazine (bismethylenephosphonic acid; HL), a robust three-dimensional (3D) noninterpenetrating dual-functional MOF, [Tb(HL)(Hbts)(HO)]·HO (), has been synthesized hydrothermally. On the basis of the excellent thermal and chemical as well as superior luminescence stabilities in water and solutions with different pHs, can serve as the simple, rapid, and highly selective and sensitive luminescence detection of the carcinoid biomarkers 5-hydroxytryptamine (HT) and its metabolite 5-hydroxyindole-3-acetic acid (HIAA) with detection limits of nanomolar magnitude in water and in simulated blood plasma and urine systems.

Alpha-fetoprotein/endoplasmic reticulum stress signaling mitigates injury in hepatoma cells.

Alpha-fetoprotein (AFP) and endoplasmic reticulum (ER) stress play multiple roles in hepatocellular carcinoma. Here, we analyzed the crosstalk between AFP and ER stress in human hepatoma cells. We induced ER stress in human hepatoma cell lines (HepG2 and SK-Hep1 cells) with thapsigargin (TG, an ER stress inducer), and mitigated ER stress with 4-phenylbutyrate acid (4-PBA, an ER stress inhibitor).

Assembly of tetra-nuclear Yb-containing selenotungstate clusters: synthesis, structures, and magnetic properties.

Two tetra-nuclear Yb-incorporated selenotungstate clusters, Keggin (CHN)Na[YbSeWO(HO)]·40HO (1) and Wells-Dawson (CHN)Na[YbSeWO(OH)(HO)]·38HO (2), have been isolated through a pH-controlled assembly, which exhibit the first Yb-containing polyoxotungstates with selenium heteroatoms. Their assemblies rely on the structure-directing effects of SeO anion templates to give rise to available Se-containing Keggin-/Wells-Dawson-type motifs. Both compounds were characterized by single-crystal X-ray diffraction, IR spectroscopy, power X-ray diffraction (XRD), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) as well as electrospray ionization mass spectrometry (ESI-MS).

Inhibition of eIF2 Dephosphorylation Protects Hepatocytes from Apoptosis by Alleviating ER Stress in Acute Liver Injury.

Objectives: Protein kinase R-like ER kinase (PERK)/eukaryotic initiation factor 2 alpha (eIF2) is an important factor along the main pathways for endoplasmic reticulum (ER) stress-mediated apoptosis. In this study, we investigated the effects of eIF2 phosphorylation on hepatocyte apoptosis and the ER stress mechanisms in acute liver injury.

Methods: eIF2 phosphorylation and apoptosis under ER stress were monitored and measured in male BALB/c mice with acute liver injury and human hepatocyte line LO2 cells.

A Mixed-Valence {Fe } Cluster Exhibiting Metal-to-Metal Charge-Transfer-Switched Spin Crossover.

It is promising and challenging to manipulate the electronic structures and functions of materials utilizing both metal-to-metal charge transfer (MMCT) and spin-crossover (SCO) to tune the valence and spin states of metal ions. Herein, a metallocyanate building block is used to link with a Fe -triazole moiety and generates a mixed-valence complex {[(Tp )Fe (CN) ] [Fe (trz-ph) ]}⋅[Ph PMe] ⋅[(Tp )Fe (CN) ] (1; trz-ph=4-phenyl-4H-1,2,4-triazole). Moreover, MMCT occurs between Fe and one of the Fe sites after heat treatment, resulting in the generation of a new phase, {[(Tp )Fe (CN) ][(Tp )Fe (CN) ] [Fe Fe (trz-ph) ]}⋅ [Ph PMe] ⋅[(Tp )Fe (CN) ] (1 a).

Self-Assembly of Nanoscale Lanthanoid-Containing Selenotungstates: Synthesis, Structures, and Magnetic Studies.

The reaction of mid-lanthanide (Ln) ions with the preformed {SeW} precursor under reasonably acidic aqueous conditions in the presence of organic amine cations results in an unprecedented nanoscale lanthanide-functionalized polyoxotungstate family, which are rare examples of mid-lanthanide-containing selenotungstates. (CHNO)Na[DySeWO(HO)]·22HO () and (NH)(CHN)Na[DySeWO(HO)(OH)]·18HO () reveal a trimeric Keggin assembly and a cyclic {SeW}-based chain, respectively, whereas (NH)Na[GdSeWO(HO)(OH)]·21HO () and (NH)(CHN)Na[LnSeWO(HO)(OH)]·58HO (; Ln = Gd, Tb, or Dy) are a few examples of polyoxometalates consisting of both classical Keggin and Wells-Dawson building blocks, and (NH)(CHN)Na[LnSeWO(HO)(OH)]·40HO (; Ln = Gd, Tb, or Dy; = 12 for Gd and Tb and 10 for Dy) features the largest "pure" Wells-Dawson selenotungstate {SeW} bearing a length of 3.73 nm.

Effect of Intermolecular Interactions on Metal-to-Metal Charge Transfer: A Combined Experimental and Theoretical Investigation.

Understanding the effects of intermolecular interactions on metal-to-metal charge transfer (MMCT) is crucial to develop molecular devices by grafting MMCT-based molecular arrays. Herein, we report a series of solvent-free {Fe Co } compounds sharing the same cationic tetranuclear {[Fe(PzTp)(CN) ] [Co(dpq) ] } (PzTp =tetrakis(pyrazolyl)borate, dpq=dipyrido[3,2-d:2',3'-f]quinoxaline) square units but having anions with different size, including BF , PF , OTf , and [Fe(PzTp)(CN) ] . Intermolecular π⋅⋅⋅π interactions between dpq ligands, which coordinate to cobalt ions in the {[Fe(PzTp)(CN) ] [Co(dpq) ] } units, can be modulated by introducing different counterions, regulating the distortion of the CoN octahedron and ligand field around the cobalt ions.

Terbium Oxalatophosphonate as Efficient Multiresponsive Luminescent Sensors for Chromate Anions and Tryptophan Molecules.

A stable 2D terbium oxalatophosphonate with green luminescence, namely, [Tb(HL)(CO)(HO)]·2HO (), has been hydrothermally obtained by using (4-carboxypiperidyl)--methylenephosphonic acid (HL) and oxalate ligand. The luminescent investigation indicates that the emission behavior of compound shows high water and pH stabilities. It can be applied as a multiresponsive luminescent probe with high selectivity, high sensitivity, recycling capability, and fast sensing of CrO , CrO anions and tryptophan (Trp) molecules in aqueous solution through the luminescence quenching effect.

A Series of Linear {Fe Fe } Complexes with Paramagnetic Building-Block-Modified Spin Crossover Behaviors.

Tuning of the spin crossover (SCO) behavior through paramagnetic building blocks with different steric hindrance effects is of great interest in terms of the synergy between SCO and magnetic interactions. Herein, the steric effect of specified Fe building blocks is modified, from the large Tp* (hydridotris(3,5-dimethylpyrazol-1-yl)borate) analogue to a small Tp (hydrotris(pyrazolyl)borate) derivative; the Fe SCO unit and Fe paramagnetic ions are incorporated into three well isolated trinuclear complexes featuring thermally induced and light-induced SCO properties. Reanalysis of the structures reveals that π-π stacking interactions play a key role in the thermal hysteresis and anomalous octahedral distortion parameter Σ around the Fe ion.

Photo- and Electronically Switchable Spin-Crossover Iron(II) Metal-Organic Frameworks Based on a Tetrathiafulvalene Ligand.

A major challenge is the development of multifunctional metal-organic frameworks (MOFs), wherein magnetic and electronic functionality can be controlled simultaneously. Herein, we rationally construct two 3D MOFs by introducing the redox active ligand tetra(4-pyridyl)tetrathiafulvalene (TTF(py) ) and spin-crossover Fe centers. The materials exhibit redox activity, in addition to thermally and photo-induced spin crossover (SCO).

12-Metal 36-membered ring based W(V)-Co(II) layers showing spin-glass behavior.

The present study describes the designed synthesis, X-ray structures, and magnetic properties of two 2D cyano bridged heterobimetallic W(V)-Co(II) networks, {[W(CN)8]2[Co(phpy)4]3}·2CH3OH·2H2O (1) and {[W(CN)8]2[Co(4-spy)4]3}·6H2O (2) (phpy = 4-phenylpyridine, 4-spy = 4-styrylpyridine). Both compounds consist of cyano-bridged 12-metal 36-membered ring units, Co6W6(CN)12, joined by organic linkers into a 2D plane. The layer presents a corrugated configuration in compound 1 and a plane configuration in compound 2 due to different π-π stacking interactions.

Single-molecule magnet behavior in three cyano-bridged heterometallic Fe(III)-Ni(II) clusters.

One trinuclear and two tetranuclear cyanide-bridged Fe(III)-Ni(II) complexes were synthesized via treatment of a tricyanometallate with divalent Ni salts in the presence of 1-butylimidazole, 2,2-bipyrimidyl and 1,10-phenanthroline, respectively. Magnetic property studies demonstrated that the three complexes exhibit single-molecule magnet behavior as a result of strong intracluster ferromagnetic coupling and weak intercluster magnetic interactions.

Lanthanide(III) oxalatophosphonates: syntheses, crystal structures and luminescence properties.

By the introduction of oxalate as the second ligand, five new lanthanide oxalatophosphonate hybrids with a 2D layered structure, namely, [Ln(H2L)(C2O4)(H2O)]·2H2O [Ln = Nd (1), Sm (2), Eu (3), Tb (4), Dy (5), H3L = H2O3PCH2NCH2(CH2CH2OPO2H)], have been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction, X-ray powder diffraction, infrared spectroscopy, elemental analysis and thermogravimetric analysis. Compounds 1-5 are isostructural and exhibit a 2D layer formed by the interconnection of a 1D zigzag chain of {Ln(C2O4)}(+) with the phosphonate ligands. The effect of lanthanide contraction induces the decrease of the lattice parameters and crystal size from Nd to Dy.

Two novel lead(II) carboxyphosphonates with a layered and a 3D framework structure: syntheses, crystal structures, reversible dehydration/hydration, and luminescence properties.

Two novel lead(II) carboxyphosphonates with a layered and a 3D framework structure, namely, [Pb2Cl3(H2L)]·H2O (1) and [Pb2(HL)(HBTC)] (2) (H3L = H2O3PCH2-NC5H9-COOH, H3BTC = 1,3,5-benzenetricarboxylic acid), have been synthesized under hydrothermal conditions and structurally characterized. For compound 1, the interconnection of Pb(1)O2Cl3, Pb(2)O2Cl3, and CPO3 polyhedra via corner- and edge-sharing forms a 1D chain. The adjacent chains connect with each other by sharing the chloride anion, thereby generating a 2D layered structure in the ab-plane.

A series of novel lanthanide carboxyphosphonates with a 3D framework structure: synthesis, structure, and luminescent and magnetic properties.

By introduction of 1,4-benzenedicarboxylic acid as the second organic ligand, a series of novel lanthanide carboxyphosphonates with a 3D framework structure, namely, [Ln(3)(H(2)L)(HL)(2)(bdc)(2)(H(2)O)]·7H(2)O (Ln = La (1), Ce (2), Pr (3), Nd (4), Sm (5), Eu (6), Gd (7), Tb (8); H(3)L = H(2)O(3)PCH(2)NC(5)H(9)COOH; H(2)bdc = HOOCC(6)H(4)COOH) have been synthesized under hydrothermal conditions. Compounds are isostructural and feature a 3D framework in which Ln(III) polyhedra are interconnected by bridging {CPO(3)} tetrahedra into 2D inorganic layers parallel to the ab plane. The organic groups of H(2)L(-) are grafted on the two sides of the layer.

Hydrothermal synthesis, crystal structures, and luminescent properties of a series of new lanthanide oxalatophosphonates with a layer architecture.

Eleven new lanthanide oxalatophosphonate hybrids with a 2D layered structures, namely, [Ln(H(3)L)(C(2)O(4))]·2H(2)O (Ln = La-Dy, Er and Y, H(4)L = C(6)H(5)CH(2)N(CH(2)PO(3)H(2))(2)), have been synthesized under hydrothermal conditions and structurally characterized by X-ray single-crystal diffraction, X-ray powder diffraction, infrared spectroscopy, elemental analysis and thermogravimetric analysis. Compounds 1-11 are isomorphous and they exhibit a 2D framework structure. Two {LnO(8)} polyhedra and four {CPO(3)} tetrahedra are interconnected into a unit via corner-sharing, and the so-built units are bridged by the oxalate anions into a layer.

Hydrothermal synthesis, structures, and luminescent properties of zinc(II) and cadmium(II) phosphonates with a 3D framework structure using terephthalate as second linkers.

By introduction of 1,4-benzenedicarboxylic acid as a second organic ligand, two new divalent metal(II) phosphonates with a 3D framework structure, namely, [Zn(HL1)(bdc)(0.5)] (1) and [Cd(1.5)(HL2)(bdc)(0.