Solvent- and pH-Stable Eu(III)-Based Metal-Organic Framework with Phosphate-Ratio Fluorescence Sensing and Significant Proton Conduction.

Lanthanide-based metal-organic frameworks show good potential for applications due to their unique structures and functional properties. A highly thermally and acid-base stable Eu-MOF was synthesized by a solvothermal method with the molecular formula {[(CH3)2NH2]2[Eu2(NDDP)2(H2O)2]·H2O}n (Eu-MOF, H4NDDP = 5,5'-(naphthalene-2,6-diyl)diisophthalic acid). Eu-MOF takes a three-dimensional (4,4,8)-connected topology. The water molecules involved in the coordination, free water molecules, and [(CH3)2NH2]+ cations in the pore can be used as proton carriers. The proton conductivity attains 1.25 × 10-4 S cm-1 at room temperature and 2.42 × 10-3 S cm-1 at 70 °C and 98% relative humidity. Combined with the dual-emission properties from the ligands and Eu(III) ions enables Eu-MOF to be used as a ratiometric fluorescent sensor for phosphate efficiently and rapidly, with a limit of detection of 0.12 µM in the Tris-HCl buffer solution. These results provide a new approach for the construction of MOFs with high proton conductivity and a ratiometric fluorescence response.

Synthesis and Structure of an Aqueous Stable Europium-Based Metal-Organic Framework with Ratiometric Fluorescence Sensing for Phosphate and Luminescence Quenching for Salicylaldehyde.

An aqueous stable europium-based metal-organic framework with properties of ratiometric fluorescence sensing, namely, {[(CH3)2NH2][Eu(TCPB)(H2O)2]·DMF}n (Eu-MOF; H4TCPB = 1,2,4,5-tetrakis(4-carboxyphenyl)-benzene), was synthesized under solvothermal conditions and structurally characterized. Crystal structure analysis shows that Eu-MOF is a three-dimensional porous crystal, in which the EuIII ion is an eight-coordinate square inverse prism with eight oxygen atoms. Fluorescence measurements show that Eu-MOF exhibits characteristic emission of the EuIII ion and ligand. Eu-MOF displays good selectivity and sensitivity as a ratiometric fluorescence sensor for phosphate anions with a low detection limit in Tris-HCl buffer solution. Furthermore, Eu-MOF also has a good ability to identify salicylaldehyde through fluorescence quenching with a detection limit of 0.095 ppm. Therefore, it is an excellent fluorescent sensing material for phosphate and organic salicylaldehyde.

Anionic lanthanide metal-organic frameworks with magnetic, fluorescence, and proton conductivity properties and selective adsorption of a cationic dye.

Two novel microporous anionic lanthanide metal-organic frameworks (Ln-MOFs), namely {[(CH3)2NH2][Ln(bptc)]·2H2O}n (Ln = Gd (1) and Dy (2), H4bptc = biphenyl-3,3',5,5'-tetracarboxylic acid) with a new 4,8-connected topology have been synthesized and structurally characterized. Ln-MOF 1 shows a significant magnetocaloric effect with -ΔSmaxm = 26.37 J kg-1 K-1 at 2 K for ΔH = 7 T, and a high proton conductivity of 1.02 × 10-4 S cm-1 at 323 K and 90% RH. Moreover, Ln-MOF 1 shows specific selective adsorption of the cationic dye Rhodamine B. Ln-MOF 2 exhibits field-induced slow magnetic relaxation with an energy barrier (Ueff) of 48.19 K, characteristic emission of Dy3+, and selective adsorption of Rhodamine B. Therefore, 2 is a multifunctional Ln-MOF with magnetic, fluorescence and selective adsorption properties.

The Antibacterial Properties of 4, 8, 4', 8'-Tetramethoxy (1,1'-biphenanthrene) -2,7,2',7'-Tetrol from Fibrous Roots of Bletilla striata.

Biphenanthrene compound, 4, 8, 4', 8'-tetramethoxy (1, 1'-biphenanthrene)-2, 7, 2', 7'-tetrol (LF05), recently isolated from fibrous roots of Bletilla striata, exhibits antibacterial activity against several Gram-positive bacteria. In this study, we investigated the antibacterial properties, potential mode of action and cytotoxicity. Minimum inhibitory concentrations (MICs) tests showed LF05 was active against all tested Gram-positive strains, including methicillin-resistant Staphylococcus aureus (MRSA) and staphylococcal clinical isolates. Minimum bactericidal concentration (MBC) tests demonstrated LF05 was bactericidal against S. aureus ATCC 29213 and Bacillus subtilis 168 whereas bacteriostatic against S. aureus ATCC 43300, WX 0002, and other strains of S. aureus. Time-kill assays further confirmed these observations. The flow cytometric assay indicated that LF05 damaged the cell membrane of S. aureus ATCC 29213 and B. subtilis 168. Consistent with this finding, 4 × MIC of LF05 caused release of ATP in B. subtilis 168 within 10 min. Checkerboard test demonstrated LF05 exhibited additive effect when combined with vancomycin, erythromycin and berberine. The addition of rat plasma or bovine serum albumin to bacterial cultures caused significantly loss in antibacterial activity of LF05. Interestingly, LF05 was highly toxic to several tumor cells. Results of these studies indicate that LF05 is bactericidal against some Gram-positive bacteria and acts as a membrane structure disruptor. The application of biphenanthrene in the treatment of S. aureus infection, especially local infection, deserves further study.

New Insights Into the Antibacterial Mechanism of Cryptotanshinone, a Representative Diterpenoid Quinone From Salvia miltiorrhiza Bunge.

The rapid rise of antibiotic resistance causes an urgent need for new antimicrobial agents with unique and different mechanisms of action. The respiratory chain is one such target involved in the redox balance and energy metabolism. As a natural quinone compound isolated from the root of Salvia miltiorrhiza Bunge, cryptotanshinone (CT) has been previously demonstrated against a wide range of Gram-positive bacteria including multidrug-resistant pathogens. Although superoxide radicals induced by CT are proposed to play an important role in the antibacterial effect of this agent, its mechanism of action is still unclear. In this study, we have shown that CT is a bacteriostatic agent rather than a bactericidal agent. Metabolome analysis suggested that CT might act as an antibacterial agent targeting the cell membrane. CT did not cause severe damage to the bacterial membrane but rapidly dissipated membrane potential, implying that this compound could be a respiratory chain inhibitor. Oxygen consumption analysis in staphylococcal membrane vesicles implied that CT acted as respiratory chain inhibitor probably by targeting type II NADH:quinone dehydrogenase (NDH-2). Molecular docking study suggested that the compound would competitively inhibit the binding of quinone to NDH-2. Consistent with the hypothesis, the antimicrobial activity of CT was blocked by menaquinone, and the combination of CT with thioridazine but not 2-n-heptyl-4-hydroxyquinoline-N-oxide exerted synergistic activity against Staphylococcus aureus. Additionally, combinations of CT with other inhibitors targeting different components of the bacterial respiratory chain exhibit potent synergistic activities against S. aureus, suggesting a promising role in combination therapies.

Phenanthrene Antibiotic Targets Bacterial Membranes and Kills Staphylococcus aureus With a Low Propensity for Resistance Development.

New classes of antibiotics with different mechanisms of action are urgently required for combating antimicrobial resistance. Blestriacin, a dihydro-biphenanthrene with significant antibacterial activity, was recently isolated from the fibrous roots of Bletilla striata. Here, we report the further characterization of the antimicrobial potential and mode of action of blestriacin. The phenanthrene compound inhibited the growth of all tested clinical isolates of Staphylococcus aureus including methicillin-resistant S. aureus (MRSA). The minimum inhibitory concentrations (MICs) of blestriacin against these pathogens ranged from 2 to 8 µg/mL. Minimum bactericidal concentration (MBC) tests were conducted, and the results demonstrated that blestriacin was bactericidal against S. aureus. This effect was confirmed by the time-kill assays. At bactericidal concentrations, blestriacin caused loss of membrane potential in B. subtilis and S. aureus and disrupted the bacterial membrane integrity of the two strains. The spontaneous mutation frequency of S. aureus to blestriacin was determined to be lower than 10-9. The selection and whole genome sequencing of the blestriacin -resistant mutants of S. aureus indicated that the development of blestriacin resistance in S. aureus involves mutations in multi-genes. All these observations can be rationalized by the suggestion that membrane is a biological target of blestriacin.