2D Chiral Ag(I) Complexes with A-π-- and D-π--Type Dicarboxylic Acid Ligands: Presenting Significant Differences in Nonlinear Optical Responses.

Three two-dimensional (2D) chiral Ag(I) complexes with formulas [Ag(L)(5-nipa)] (), [Ag(L)(5-nipa)] (), and {[Ag(L)(5-hipa)]·2HO} () were prepared through the reactions of AgO with enantiopure -monodentate N-donors (L/L) and different dicarboxylic acids bearing A (acceptor)-π-- and D (donor)-π--type structural features, where / = (-)/(+)-2-(4'-pyridyl)-4,5-pinene-pyridine, 5-Hnipa = 5-nitroisophthalic acid, and 5-Hhipa = 5-hydroxyisophthalic acid. A study of their nonlinear optical responses reveals that chiral and enantiomeric pairs with the A-π--type dicarboxylic acid ligand simultaneously display second- and third-harmonic generation (SHG and THG) responses, while chiral containing the D-π--type dicarboxylic acid ligand only exhibits a very strong THG response. The THG intensity of is 451 × α-SiO, being about 27 and 24 times larger than those of and , respectively.

Assembly of Homochiral Magneto-Optical Dy Triangular Clusters by Fixing Carbon Dioxide in the Air.

A new hydrazone Schiff base bridging ligand (HL ()-'-((1-hydroxynaphthalen-2-yl)methylene)pyrazine-2-carbohydrazide) and /-proline were used to construct a pair of homochiral Dy cluster complexes, [Dy(CO)(-Pro)(L)(HL)]·5DMA·2HO (-, -HPro = -proline; DMA = ,-dimethylacetamide) and [Dy(CO)(-Pro)(L)(HL)]·5DMA·2HO (-, -HPro = -proline), which show a novel triangular Dy topology. Notably, the fixation of CO in the air formed a carbonato central bridge, playing a key role in assembling -/-. Magnetic measurements revealed that -/- displays intramolecular ferromagnetic coupling and magnetic relaxation behaviours.

Two pairs of chiral Yb enantiomers presenting distinct NIR luminescence and circularly polarized luminescence performances with giant differences in second-harmonic generation responses.

By introducing enantiomerically pure mono-bidentate N-donor ligands (L/L) into Yb(btfa)(HO) and Yb(dbm)(HO), respectively, two pairs of chiral Yb enantiomers, namely Yb(btfa)L/Yb(btfa)L (D-1/L-1) and [Yb(dbm)L]·[Yb(dbm)(CHOH)]/[Yb(dbm)L]·[Yb(dbm)(CHOH)] (D-2/L-2) were isolated, where btfa = 3-benzoyl-1,1,1-trifluoroacetonate, dbm = dibenzoylmethanate, and L/L = (-)/(+)-4,5-pinenepyridyl-2-pyrazine. D-1/L-1 possess mononuclear structures in which the Yb ions are eight-coordinated, while D-2/L-2 show cocrystal structures containing Yb(dbm)(L/L) and Yb(dbm)(CHOH) moieties in which the two Yb ions are eight and seven-coordinated, respectively. They not only feature different molecular structures but also present distinct linear and nonlinear optical performances.

A pair of ionic 1D Cu(II) chain enantiomers simultaneously displaying large second- and third-harmonic generation responses.

By employing enantiomerically pure mono-bidentate N-donors (L/L) as chiral bridging ligands to react with Cu(ClO)(HO) in CHCN-DMF mixed solvent, respectively, a pair of ionic one-dimensional (1D) Cu(II) chain enantiomers formulated as {[CuL(CHCN)(DMF)HO](ClO)}/{[CuL(CHCN)(DMF)HO](ClO)} (D-1/L-1) were isolated and structurally characterized, where L/L = (-)/(+)-4,5-pinenepyridyl-2-pyrazine. They crystallize in the noncentrosymmetric (NCS) 222 space group of an orthorhombic system due to the introduction of chiral L/L, and the ClO groups as counteranions reside in crystal lattices, thus leading to charge separation with large dipole moments in their molecular structures. Based on crystal samples, investigation on their nonlinear optical (NLO) behaviors showed that D-1 and L-1 display simultaneously much larger second- and third-harmonic generation (SHG and THG) responses than their analogues based on the same chiral N-donors (L/L) and Cu(NO)(HO) with NO acting as the coordination group to bind Cu(II) ions.

Two Chiral Yb Enantiomeric Pairs with Distinct Enantiomerically Pure N-Donor Ligands Presenting Significant Differences in Photoluminescence, Circularly Polarized Luminescence, and Second-Harmonic Generation.

Using enantiomerically pure bidentate and tridentate N-donor ligands (L/L and L/L) to replace two coordinated HO molecules of Yb(tta)(HO), respectively, two eight- and nine-coordinated Yb enantiomeric pairs, namely, Yb(tta)L/Yb(tta)L (/) and [Yb(tta)L]·CHCN/[Yb(tta)L]·CHCN (/), were isolated, in which Htta = 2-thenoyltrifluoroacetone, L/L = (-)/(+)-4,5-pinene-2,2'-bipyridine, and L/L = (-)/(+)-2,6-bis(4',5'-pinene-2'-pyridyl)pyridine. Interestingly, they not only present distinct degrees of chirality but also show large differences in near-infrared (NIR) photoluminescence (PL), circularly polarized luminescence (CPL), and second-harmonic generation (SHG). Eight-coordinated with an asymmetric bidentate L ligand has a high NIR-PL quantum yield (1.

Two temperature-induced 1D Cu chain enantiomeric pairs showing different magnetic properties and nonlinear optical responses.

At different reaction temperatures, using Cu(NO)·3HO to react with enantiomerically pure N-donor ligands (L/L), respectively, two pairs of chiral one-dimensional (1D) Cu chain enantiomers formulated as [Cu(μ-NO)(NO)(L)]/[Cu(μ-NO)(NO)(L)] (S-1-Cu/R-1-Cu, formed at 40 °C with an NO group as a sole bridging ligand) and [Cu(μ-L)(NO)]/[Cu(μ-L)(NO)] (S-2-Cu/R-2-Cu, formed at 25 °C with L or L as a bridging ligand) were prepared, where L/L = (+)/(-)-4,5-pinenepyridyl-2-pyrazine. Interestingly, such a disparity in bridging ligands leads not only to their distinct structural features but also to their completely different magnetic couplings together with a large difference in their nonlinear optical responses. S-1-Cu with a 1D helical structure shows weak ferromagnetic coupling between Cu ions, while S-2-Cu with a 1D stairway-like structure presents weak antiferromagnetic coupling.

Effects of Counterions, Coordination Anions, and Coordination Solvent Molecules on Single-Molecule Magnetic Behaviors and Nonlinear Optical Properties of Chiral ZnDy Schiff Base Complexes.

By changing the counterions (ClO and CFSO) and the coordination anions (Cl and Br), we investigated their influences on the structures and performances of a class of ZnDy chiral single-molecule magnets (SMMs), which are based on a pair of chiral Schiff bases ,-HL and ,-HL {,-HL = 2-(()-((1,2)-2-(()-2-hydroxy-3-methoxybenzylideneamino)cyclohexylimino)methyl)-6-methoxyphenol and ,-HL = 2-(()-((1,2)-2-(()-2-hydroxy-3-methoxybenzylideneamino)cyclohexylimino)methyl)-6-methoxyphenol}. Three pairs of chiral ZnDy Schiff base complexes were obtained by directed synthesis, which are [DyZn(,-)Cl(HO)](ClO)·0.5MeOH·0.

Modulating Two Pairs of Chiral Dy Enantiomers by Distinct β-Diketone Ligands to Show Giant Differences in Single-Ion Magnet Performance and Nonlinear Optical Response.

Using Dy(dbm)(HO) and Dy(btfa)(HO) to react with enantiopure -donors, (-)/(+)-4,5-pinenepyridyl-2-pyrazine (L/L), respectively, two pairs of chiral Dy enantiomers, Dy(dbm)L/Dy(dbm)L (/) and Dy(btfa)L/Dy(btfa)L (/) were obtained, wherein one of the benzene rings of dbm (dibenzoylmethanate) in / is displaced by the -CF group of btfa (4,4,4-trifluoro-1-phenyl-1,3-butanedionate) in /. Interestingly, this substitution results not only in giant differences in their single-ion magnetic (SIM) performances but also in their completely different nonlinear optical (NLO) responses. presents a large effective energy barrier ( = 265.

Multifunctional Dy Enantiomeric Pairs Showing Enhanced Photoluminescences and Third-Harmonic Generation Responses through the Coordination Role of Homochiral Tridentate -Pincer Ligands.

By utilizing Dy(hfac)(HO) to react with enantiomerically pure tridentate -pincer ligands, namely (-)/(+)-2,6-bis(4',5'-pinene-2'-pyridyl)pyridine (L and L), respectively, homochiral Dy enantiomeric pairs formulated as Dy(hfac)L/Dy(hfac)L (/) (hfac = hexafluoroacetylacetonate) were achieved and structurally characterized. Meanwhile, their magnetic, photoluminescent (PL), and chiroptical properties were probed. The PL test results indicate that the precursor Dy(hfac)(HO) only shows very weak emission, while exhibits characteristic Dy f-f transition emission bands at room temperature.

Two homochiral Eu and Sm enantiomeric pairs showing circularly polarized luminescence, photoluminescence and triboluminescence.

Two homochiral EuIII and SmIII tris(β-diketonate) enantiomeric pairs, based on fluorinated β-diketone (Hbtfa) and enantiopure asymmetric N,N'-donor ligands (LR and LS), Λ-Eu(btfa)3LR (R-1-Eu)/Δ-Eu(btfa)3LS (S-1-Eu) and Λ-Sm(btfa)3LR (R-2-Sm)/Δ-Sm(btfa)3LS (S-2-Sm) (btfa- = 4,4,4-trifluoro-1-phenyl-1,3-butanedionate and LR/LS = (-)/(+)-4,5-pineno-2,2'-bipyridine) were synthesized. The electronic circular dichroism (ECD) spectra confirmed their enantiomeric nature. R-1-Eu/S-1-Eu and R-2-Sm/S-2-Sm exhibit intense characteristic emissions of EuIII (red) and SmIII (orange-red) ions both in the solid state and in DCM with long lifetimes and high luminescence quantum yields.

A pair of 2D chiral Ag(i) enantiomers with dual chiral elements: syntheses, structures, and photoluminescent and chiroptical properties.

In this work, two new enantiopure bis-monodentate -donor chiral ligands, namely (-)/(+)-2-(4'-pyridyl)-4,5-pinene-pyridine (L /L ), have been designed and synthesized. Using L and L as bridging ligands to react with AgClO, a pair of novel 2D chiral Ag(i) enantiomers formulated as [Ag(L )(ClO)] (-1) and [Ag(L )(ClO)] (-1) were isolated and characterized. In -1 and -1, each Ag(i) ion is bonded by two N atoms from two different chiral L or L ligands, leading to the formation of 1D right- or left-handed -L-Ag(i)-L- helical chains.

Safety and complications of medical thoracoscopy in the management of pleural diseases.

Background: Medical thoracoscopy is considered an overall safe procedure, whereas numbers of studies focus on complications of diagnostic thoracoscopy and talc poudrage pleurodesis. We conduct this study to evaluate the safety of medical thoracoscopy in the management of pleural diseases and to compare complications in different therapeutic thoracoscopic procedures.

Methods: A retrospective study was performed in 1926 patients, 662 of whom underwent medical thoracoscopy for diagnosis and 1264 of whom for therapeutic interventions of pleural diseases.

Syntheses, structures and catalytic properties of Evans-Showell-type polyoxometalate-based 3D metal-organic complexes constructed from the semi-rigid bis(pyridylformyl)piperazine ligand and transition metals.

Herein, two novel Evans-Showell-type polyoxometalate (POM)-based metal-organic complexes, namely, {[Cu(L)(H2O)3][Cu(L)0.5(H2O)][Cu(L)0.5(H2O)4][Co2Mo10H4O38]}·5H2O (1) and [(H2L)0.

Evans-Showell-type polyoxometalate-based metal-organic complexes with novel 3D structures constructed from flexible bis-pyrazine-bis-amide ligands and copper metals: syntheses, structures, and fluorescence and catalytic properties.

Two new Evans-Showell-type polyoxometalate (POM)-based metal-organic complexes, namely {Cu3(L1)1.5(H2O)5[Co2Mo10H4O38]}·5H2O (1), {[Cu(L2)0.5(H2O)2]2[Co2Mo10H4O38]}·6H2O (2) (L1 = N,N'-bis(2-pyrazinecarboxamide)-1,4-butane, L2 = N,N'-bis(2-pyrazinecarboxamide)-1,6-hexane), were successfully synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis, IR spectroscopy, powder X-ray diffraction (PXRD) and thermogravimetric analyses (TGA).

Inhibition of invasion by N-trans-feruloyloctopamine via AKT, p38MAPK and EMT related signals in hepatocellular carcinoma cells.

N-trans-feruloyloctopamine (FO) isolated from Garlic skin was identified as the primary antioxidant constituents, however, the effect of which on HCC invasion is still unclear. Herein, the FO was synthesized and its antitumor activities were evaluated in HCC cell lines. Cellular functional analyses have revealed that the reformed FO owns strong abilities of inhibiting cell proliferation and invasion in HCC cells.

A pair of dinuclear Re(I) enantiomers: synthesis, crystal structures, chiroptical and ferroelectric properties.

The reaction of enantiomeric bis-bidentate bridging ligands (+)/(-)-2,5-bis(4,5-pinene-2-pyridyl)pyrazine (L(S)/L(R)) with [Re(CO)5Cl] yielded a pair of dinuclear Re(I) enantiomers formulated as [Re2(L(S)/L(R))(CO)6Cl2]·4CH2Cl2 (R-1 and S-1, the isomers containing the respective L(R) and L(S) ligands). They were characterized by elemental analyses, IR spectra and X-ray crystallography. Circular dichroism spectra verified their chiroptical activities and enantiomeric nature.

Anion-controlled self-assembly of two NLO-active dinuclear and molecular square Cu(II) enantiomeric pairs: from antiferromagnetic to ferromagnetic coupling.

Two second-order nonlinear optically (NLO)-active dinuclear and square Cu(II) enantiomeric pairs were obtained via the self-assemblies of enantiopure linear bis-bidentate ligands with different copper(II) salts under the identical reaction conditions. Their magnetic properties are switched from antiferromagnetic to ferromagnetic coupling.

Simultaneous blockage of epidermal growth factor receptor and cyclooxygenase-2 in a human xenotransplanted lung cancer model.

The effects of erlotinib combined with celecoxib in a lung cancer xenograft model were here explored with a focus on possible mechanisms. A xenotransplanted lung cancer model was established in nude mice using the human lung cancer cell A549 cell line and animals demonstrating tumour growth were randomly divided into four groups: control, erlotinib, celecoxib and combined (erotinib and celecoxib). The tumor major axis and short diameter were measured twice a week and after 40 days tissues were collected for immunohistochemical analyses of Bcl-2 and Bax positive cells and Western-blotting analyses for the epidermal growth factor recepto (EGFR), P-EGFR, and cyclooxygenase-2 (COX-2).

Luminescent, magnetic and ferroelectric properties of noncentrosymmetric chain-like complexes composed of nine-coordinate lanthanide ions.

Reaction of the chiral ligand (-)-4,5-pinenepyridyl-2-pyrazine (L) with Ln(hfac)3·2H2O precursors [hfac(-) = 1,1,1,5,5,5-hexafluoroacetylacetonate, Ln = Sm(3+) (1), Eu(3+) (2), Tb(3+) (3) and Dy(3+) (4)] in methanol solution led to the formation of four noncentrosymmetric lanthanide complexes with the general formula [Ln(hfac)3L]n·H2O. The single-crystal X-ray diffraction analyses revealed that they are isostructural and take a one-dimensional (1D) chain structure based on the Ln(hfac)3L repeating units, in which the nine-coordinate Ln(3+) ions reside in a tricapped trigonal prism (TTP) environment never reported in previous 1D chain lanthanide complexes. The investigations of their photophysical properties showed that complexes 1, and 3 exhibit characteristic emissions of Sm(3+), Eu(3+) and Tb(3+) ions with respective luminescent lifetime values of 0.

Endostatin, an angiogenesis inhibitor, ameliorates bleomycin-induced pulmonary fibrosis in rats.

Background: Recent evidence has demonstrated the role of angiogenesis in the pathogenesis of pulmonary fibrosis. Endostatin, a proteolytic fragment of collagen XVIII, is a potent inhibitor of angiogenesis. The aim of our study was to assess whether endostatin has beneficial effects on bleomycin (BLM)-induced pulmonary fibrosis in rats.

First one-dimensional homochiral stairway-like Cu(II) chains: crystal structures, circular dichroism (CD) spectra, ferroelectricity and antiferromagnetic properties.

The reactions of enantiopure chiral ligands (+)/(−)-4,5-pinenepyridyl-2-pyrazine (LS/LR) with CuCl2·2H2O in CH3OH/CH2Cl2 solution led to the formations of one-dimensional homochiral enantiomeric pairs with the formula [Cu(LR/S)Cl2]n·2H2O (R-1 and S-1, the isomers containing the LR and LS ligands, respectively). The circular dichroism (CD) spectra verified their chiroptical activities and enantiomeric natures. Their structures have been determined by X-ray single-crystal analyses, showing stairway-like and mirror-symmetric features, which represent the first examples of homochiral metal complexes with stairway-like structures.

Modulation of homochiral Dy(III) complexes: single-molecule magnets with ferroelectric properties.

Homochiral Dy(III) complexes: by changing the ligand-to-metal ratio, enantiomeric pairs of a Dy(III) complex of different nuclearity could be obtained. The mono- and dinuclear complexes exhibit characteristics of single-molecule magnets and different slow magnetic relaxation processes. In addition, the dinuclear complexes exhibit ferroelectric behavior, thus representing the first chiral polynuclear lanthanide-based single-molecule magnets with ferroelectric properties.

Two mono- and dinuclear Eu(III) enantiomeric pairs based on chiral bis-bidentate bridging ligands: synthesis, structures, luminescent and ferroelectric properties.

Using the enantiomeric bis-bidentate bridging ligands (+)/(-)-2,5-bis(4,5-pinene-2-pyridyl)pyrazine (L(S)/L(R)) and depending on the ratio control of reactants, two mono- and dinuclear Eu(III)-based enantiomeric pairs with the formulae Eu(dbm)(3)L(R/S)·2H(2)O (L(R) in R-1, L(S) in S-1 and dbm = dibenzoylmethanato) and Eu(2)(dbm)(6)L(R/S)·H(2)O (L(R) in R-2 and L(S) in S-2) have been stereoselectively synthesized and structurally characterized. The circular dichroic (CD) spectra confirmed their chiroptical activities and enantiomeric natures. The homochiral dinuclear species represents the first example of a polynuclear lanthanide β-diketonate complexes with circular dichroic and crystallographic evidences.

Effect of disorder on the magnetic properties of a partially filled skutterudite.

The magnetic properties of the partially filled skutterudite Eu(0.5)Co(4)Sb(12) are investigated by a model Hamiltonian, with special emphasis on the effect of ordering and disordering occupancy of the filler atoms Eu on the magnetic properties. The magnetization, magnetic specific heat and entropy are calculated within the mean-field approximation.