BDE-47 Induces Immunotoxicity in RAW264.7 Macrophages through the Reactive Oxygen Species-Mediated Mitochondrial Apoptotic Pathway.

Polybrominated diphenyl ethers (PBDEs) are classic and emerging pollutants that are potentially harmful to the human immune system. Research on their immunotoxicity and mechanisms suggests that they play an important role in the resulting pernicious effects of PBDEs. 2,2',4,4'-Tetrabrominated biphenyl ether (BDE-47) is the most biotoxic PBDE congener, and, in this study, we evaluated its toxicity toward RAW264.7 cells of mouse macrophages. The results show that exposure to BDE-47 led to a significant decrease in cell viability and a prominent increase in apoptosis. A decrease in mitochondrial membrane potential (MMP) and an increase in cytochrome C release and caspase cascade activation thus demonstrate that cell apoptosis induced by BDE-47 occurs via the mitochondrial pathway. In addition, BDE-47 inhibits phagocytosis in RAW264.7 cells, changes the related immune factor index, and causes immune function damage. Furthermore, we discovered a significant increase in the level of cellular reactive oxygen species (ROS), and the regulation of genes linked to oxidative stress was also demonstrated using transcriptome sequencing. The degree of apoptosis and immune function impairment caused by BDE-47 could be reversed after treatment with the antioxidant NAC and, conversely, exacerbated by treatment with the ROS-inducer BSO. These findings indicate that oxidative damage caused by BDE-47 is a critical event that leads to mitochondrial apoptosis in RAW264.7 macrophages, ultimately resulting in the suppression of immune function.

"Three-in-One" Structural-Building-Mode-Based Ti16-Type Titanium Oxo Cluster Entirely Protected by the Ligands Benzoate and Salicylhydroxamate.

Titanium oxo clusters (TOCs) with accurate molecular structures have potential applications in photocatalysis, such as photocatalytic degradation, hydrogen production, and water oxidation. The hydrolytic stability and light absorption ability of TOCs have important impacts on photocatalysis, where the selection of peripheral organic ligands plays a significant role. In this regard, salicylhydroxamic acid (abbreviated as H3L) attracts our attention, acting as a ligand for its multidentate and dye-functional features, which can increase the hydrolytic stability and broaden light absorption for TOCs. Herein, two TOCs were solvothermally synthesized and structurally characterized using H3L, formulated as [Ti8(µ2-O)2(µ3-O)2(OiPr)12(L)4]·2CH3CN (1) and [Ti16(µ2-O)10(µ3-O)4(PhCOO)14(L)6(HL)2]·4CH3CN·2iPrOH (2). Complex 2 was obtained by adding excessive benzoic acid over the reaction system of 1, resulting in enhanced hydrolytic stability via the replacement of all alkoxy ligands by multidentate ligands for protection. Interestingly, for the first time, the "three-in-one" structural building mode with {Ti6} + {Ti4} + {Ti6} by the common subunits in 2 was observed among all reported TOCs. Moreover, complex 2 can strongly absorb visible light reaching up to 700 nm and exhibit obvious activity for the photodegradation of methyl orange.

Ruthenium terpyridine complexes containing a pyrrole-tagged 2,2'-dipyridylamine ligand-synthesis, crystal structure, and electrochemistry.

Ruthenium(II) terpyridine complexes containing the pyrrole-tagged 2,2'-dipyridylamine ligand PPP (where PPP stands for N-(3-bis(2-pyridyl)aminopropyl)pyrrole with the general formula [Ru(tpy)(PPP)X](n+) (1, X = Cl(-); 2, X = H(2)O; 3, X = CH(3)CN; tpy = 2,2':6',2"-terpyridine) have been synthesized and characterized by (1)H NMR, IR, UV-vis, mass spectrometry, and elemental analysis. 1 and 2 have been structurally characterized by X-ray crystallography. Both 1 and 2 were successfully immobilized onto glassy carbon electrode via anodic oxidation of the pyrrole moiety on the PPP ligand to give stable and highly electroactive polymer films. Cyclic voltammetric studies of 1 in acetonitrile revealed a Ru(III)/Ru(II) couple at 0.4 V vs Cp(2)Fe(+/0) initially, but another redox couple resulting from chloride substitution by acetonitrile developed at E(1/2) = 0.82 V upon repetitive potential scan. This ligand substitution was induced by the acidic local environment caused by the release of protons during pyrrole polymerization. The electropolymerization of 2 in aqueous medium allowed the observation of the formation of Ru(IV)═O species in polypyrrole film. As the film grew thicker, the size of the Ru(III)/(/)Ru(II) couple (E(1/2) = 0.8 V vs SCE at pH 1) of poly[Ru(tpy)(PPP)(OH(2))](n+) increased accordingly, whereas the growth of the Ru(IV)/Ru(III) couple (E(1/2) = 0.89 V vs SCE at pH 1) leveled off after the film had reached a certain thickness. The Pourbaix diagram of the E(1/2) of the Ru(III) /Ru(II) and Ru(IV)/Ru(III) couples vs pH of the electrolyte medium has been obtained. The resulting poly[Ru(tpy)(PPP)(OH(2))](n+) film is electrocatalytically active toward the oxidation of benzyl alcohol.

[Changes of plasma uPA and TGF-beta1 in patients with preeclampsia].

OBJECTIVE: To study the roles of uPA and TGF-beta1 in the etiology of preeclampsia (PE). METHODS: The plasma uPA and TGF-beta 1 were determined with enzyme linked immunosorbent assay (ELISA) in 70 patients with PE, and compared with those with normal pregnancy (n = 40). RESULTS: 1) The patients with PE had lower levels of plasma uPA (436.39 +/- 29.57) pg/mL than those with normal pregnancy [(646.54 +/- 35.39) pg/mL, P < 0.01]. No significant difference was found in the levels of plasma uPA between the patients with severe PE (417.11 +/- 48.47) pg/mL and the patients with mild PE [(468.81 +/- 14.91) pg/mL, P > 0.05]. 2) The patients with PE had higher levels of plasma TGF-beta1 (14.32 +/- 4.37) ng/mL than those with normal pregnancy [(9.85 +/- 3.19) ng/mL, P < 0. 05]. No significant difference was found in the levels of plasma TGF-beta1 between the patients with severe PE (15.37 +/- 4.93) ng/mL and the patients with mild PE [(11.21 +/- 2.32) ng/mL, P > 0.05)]. 3) There was a negative correlation between plasma uPA and plasma TGF-beta1 in the patients with PE (r = -0.497, P < 0.01). CONCLUSION: The changes of uPA and TGF-beta1 are associated with the occurrence and development of PE.

A tricarbonyl rhenium(I) complex with a pendant pyrrolidinium moiety as a robust and recyclable catalyst for chemical fixation of carbon dioxide in ionic liquid.

A novel Re(I) complex covalently anchored with a pyrrolidinium moiety was successfully synthesized and used as an efficient and recyclable catalyst in the cycloaddition of CO2 with epoxides under mild reaction conditions to give excellent isolated yield and selectivity of cyclic carbonates in pyrrolidinium ionic liquid.

Second-order nonlinear optical switching with a record-high contrast for a photochromic and thermochromic bistable crystal.

Nonlinear optical (NLO) switchable materials are important for photonic and optoelectronic technologies. One important issue for NLO photoswitching, the most studied physical switching approach, is how to improve the switching contrast of second harmonic generation (SHG) in crystals, because the known values are generally below 3 times. Thermoswitching, as another approach, has shown impressive high SHG-switching contrasts (4-∞ times), but the fast decay of thermally induced states demands constant heat sources to maintain specific SHG intensities. We have synthesized a photochromic and thermochromic bistable acentric compound, ß-[(MQ)ZnCl3] (MQ+ = N-methyl-4,4'-bipyridinium), which represents the first crystalline compound with both photo- and heat-induced SHG-switching behavior and the first example of a thermoswitchable NLO crystal that can maintain its expected second-order NLO intensity without any heat source. The SHG-switching contrast can reach about 8 times after laser irradiation or 2 times after thermal annealing. The former value is the highest recorded for photoswitchable NLO crystals. This work also indicates that higher SHG-switching contrasts may be obtained through increasing electron-transfer efficiency, variation of permanent dipole moment, and self-absorption.

Microporous Lanthanide Metal-Organic Frameworks with Multiple 1D Channels: Tunable Colors, White-Light Emission, and Luminescent Sensing for Iron(II) and Iron(III).

A new series of isostructural lanthanide-based metal-organic frameworks, [H3 O][HN(CH3 )3 ]2 [Ln3 L6 ] (Ln=Gd (1), Eu (2), and Tb (3); H2 L=1,3-benzenedicarboxylic acid), was prepared under solvothermal conditions. Single-crystal XRD studies reveal that these compounds are 3D microporous frameworks with 1D channels distributed in four different directions. The 1D channels contain protonated water molecules and trimethylammonium cations, which can be partially exchanged with different metal ions. Notably, these compounds do not contain any coordinated solvent molecules because the coordination sphere of the Ln3+ ion is fully occupied by chelating and bridging carboxylate oxygen atoms. Tunable colors and white-light emission can be achieved by encapsulating different molar ratios of Eu3+ and Tb3+ ions in the Gd framework through cation exchange. In addition, the Eu framework can act as a sensitive and selective luminescence sensor for both Fe2+ and Fe3+ .

Dinuclear macrocyclic polyamine zinc(II) complexes: syntheses, characterization and their interaction with plasmid DNA.

The syntheses, characteristics of dinuclear macrocyclic polyamine zinc complexes and their interaction with plasmid DNA are reported. The two cyclen (1,4,7,10-tetraazacyclododecane) moieties are bridged by rigid and flexible linkages. The crystal structures of Zn2C27H43N8O15Cl4 [5c.(ClO4)3.2H2O] and Zn2C30H43N10O13Cl3 [5e.(ClO4)3.H2O] have been determined. The complexes crystallize in the monoclinic space group C2/c and P2(1)/c with the following unit cell parameters: 5c.(ClO4)3.2H2O: a=32.568(4)A, b=14.8593(17)A, c=19.443(2)A, alpha=90.00 degrees , beta=119.435(4) degrees , gamma=90.00 degrees , Dc=1.551 mg/m3, FW=956.71, F(000)=3932; 5e.(ClO4)3.H2O: a=15.807(2)A, b=16.756(2)A, c=16.161(2)A, alpha=90.00 degrees , beta=97.062(4) degrees , gamma=90.00 degrees , Dc=1.546 mg/m3, FW=988.83, F(000)=2032. The distance between the two Zn(II) ions is about 4.0 A. The structures show that two zinc ions can synergistically interact with the substrate DNA. With this novel structural characteristics, the dinuclear macrocyclic polyamine Zn(II) complexes via the synergetic effect between the two zinc ions can catalyze the cleavage of plasmid DNA (pUC18) with unprecedented speed at physiological conditions.

Oxo-bridged metal carbene complexes. Synthesis, structure and reactivities of [[Os(Por)(CPh2)]2]O (Por = porphyrinato dianion).

Dinuclear mu-oxo osmium porphyrins containing terminal Os=CPh2 bonds with a linear C=Os-O-Os=C moiety were prepared, which are reactive toward pyridine to form [Os(Por)(CPh2)(py)] and are active catalysts for inter- and intra-molecular cyclopropanation of alkenes and for carbene insertion into saturated C-H bonds.

Synthesis and characterization of cobalt(III) complexes containing 2-pyridinecarboxamide ligands and their application in catalytic oxidation of ethylbenzene with dioxygen.

Four novel cobalt(III) complexes were found to have high catalytic activities and excellent selectivities in the oxidation of ethylbenzene to acetophenone using O2 as oxidant without need of solvent.

Highly efficient epoxidation of cyclic alkenes catalyzed by ruthenium complex.

The epoxidation of cyclic alkenes with molecular oxygen was efficiently completed in excellent epoxide yield using a novel ruthenium complex as catalyst under mild reaction conditions.

Intramolecular NMe2H Elimination and Fulvene Coupling Leading to Novel Allyl-Bridged Zirconocene and Hafnocene Complexes.

Deprotonation of the aminofulvene 1 with LiCH(SiMe3)2 provides 2, which reacts with MCl4 (M=Zr or Hf) by intramolecular NMe2H elimination and coupling of the fulvene moieties to form complex 3 or 4. This reaction is a useful synthetic pathway to allyl-bridged ansa-metallocenes, especially those with a conjugated 14 π electron system. R'=dimethylamino.

A dinuclear ruthenium catalyst with a confined cavity: selectivity in the addition of aliphatic carboxylic acids to phenylacetylene.

A dinuclear ruthenium catalyst with a rigid anthracene spacer shows excellent regio- and stereo-selectivity in the atom-economic addition of aliphatic carboxylic acids to phenylacetylene, producing exclusively anti-Markovnikov enol-esters with high E/Z ratios of the isomers.