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)(0.5)] (2) (H(2)L1 = H(2)O(3)PCH(NH(2))C(6)H(5), H(3)L2 = 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. The two compounds show three-dimensional (3D) framework structure with infinite two-dimensional (2D) networks pillared by H(2)bdc. For compound 1, the {ZnO(4)} polyhedra are interconnected by phosphonate groups into a 2D layer, and the adjacent layers are further cross-linked via the bdc(2-) anions to generate a three-dimensional framework structure with two types of channel system along the c-axis. A notable feature of compound 1 is the presence of alternate left- and right-handed helical chains in the structure. In compound 2, the inorganic chains, composed of {Cd(1)O(7)}, {Cd(2)O(4)} and {CPO(3)} polyhedra, are linked by HL2(2-) ligands to form a double layer structure in the ab plane, and the adjacent layers are further linked by the bdc(2-) anions to form a 3D framework structure with one-dimensional channel systems along the a-axis. Luminescence properties of compounds 1 and 2 have also been studied.     

New photocatalyst BiOCl/BiOI composites with highly enhanced visible light photocatalytic performances

BiOCl/BiOI composites with a visible light response were prepared by a simple hydrothermal method. Even though both single BiOCl and BiOI show low photocatalytic activity, BiOCl/BiOI composites provide enhanced efficiency in decomposing organic compounds including Methyl Orange (MO) and Rhodamine B (RhB). Furthermore, the 20%BiOCl/BiOI composite shows the highest efficiency for decomposing MO, while the highest performance is observed for the degradation of RhB over 70%BiOCl/BiOI composite. A possible photocatalytic mechanism has been proposed based on the relative experiments and the band positions of BiOCl and BiOI.     

Synthesis, characterization, interaction with DNA, and cytotoxic effect in vitro of new mono- and dinuclear Pd(II) and Pt(II) complexes with benzo[d]thiazol-2-amine as the primary ligand

A series of novel Pd(II) and Pt(II) complexes, [PdL(2)Cl(2)]·DMF (1), [Pd(2)(L-H)(2)(bpy)Cl(2)]·(H(2)O)(2)·DMF (2), [Pd(2)(L-H)(2)(phen)Cl(2)]·2H(2)O (3), [PtL(2)Cl(2)]·H(2)O (4), [Pt(2)(L-H)(2)(bpy)Cl(2)]·2H(2)O (5), and [Pt(2)(L-H)(2)(phen)Cl(2)]·H(2)O (6), where bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline, and L = 1,3-benzothiazol-2-amine, have been synthesized and characterized. The competitive binding of the complexes to DNA has been investigated by fluorescence spectroscopy. The values of the apparent DNA binding constant, calculated from fluorescence spectral studies, were 3.8 × 10(6) (K(app)(4)), 2.9 × 10(6) (K(app)(1)), 2.4 × 10(6) (K(app)(6)), 2.0 × 10(6) (K(app)(5)), 1.2 × 10(6) (K(app)(3)), and 6.9 × 10(5) (K(app)(2)). The binding parameters for the fluorescence Scatchard plot were also determined. On the basis of the data obtained, it indicates that the six complexes bind to DNA with different binding affinities in the relative order 4 > 1 > 6 > 5 > 3 > 2. Viscosity studies carried out on the interaction of complexes with Fish Sperm DNA (FS-DNA) suggested that all complexes bind by intercalation. Gel electrophoresis assay demonstrates that all the complexes can cleave the pBR 322 plasmid DNA and bind to DNA in a similar mode. The cytotoxic activity of the complexes has been also tested against four different cancer cell lines. The results show that all complexes have activity against KB, AGZY-83a, Hep-G2, and HeLa cells. In general, the Pt(II) complexes were found to be more effective than the isostructural Pd(II) complexes. The mononuclear complexes exhibited excellent activity in comparison with the dinuclear complexes in these four cell lines. Moreover, on the KB cell line (the human oral epithelial carcinoma), the observed result seems quite encouraging for the six complexes with IC(50) values ranging from 1.5 to 8.6 μM. Furthermore, apoptosis assay with hematoxylin-eosin staining shows treatment with the six complexes results in morphological changes of KB cells. The results induce apoptosis in KB cells.     

Chromatographic characteristics of poly(1-vinylimidazole)-grafted silica in normal-phase HPLC

A stationary phase based on poly(1-vinylimidazole)-grafted silica has been prepared by the surface radical chain-transfer reaction. The stationary phase was characterized by infrared spectra, X-ray photoelectron spectroscopy and elemental analysis. Chromatographic characteristics of the stationary phase were investigated in normal-phase HPLC. The results showed that both weak polar compounds (polycyclic aromatic hydrocarbons, dialkyl phthalates) and polar compounds (anilines, phenols) could be successfully separated on this stationary phase, implying better separation performance than blank silica and conventional aminopropyl-bonded silica under the same conditions. The excellent performance can be attributed to multiple interactions between surface modifier and the analytes that might include dipole, hydrogen bonding, H-π, electrostatic and inductive interactions.     

Novel chemiluminescent assay for staphylococcal enterotoxin B

An enzyme-linked immunosorbent assay, a horseradish peroxidase-catalyzed fluorogenic reaction, and chemiluminescence (CL) analysis have been combined to develop a sandwich ELISA for Staphylococcal enterotoxin B (SEB) using monoclonal antibodies for different epitopes of SEB. The enzyme catalyzed reaction of 3-(4-hydroxyphenyl propionate) with the urea complex of hydrogen peroxide produced a fluorescent dimer which was detected by chemiluminescence analysis. The CL response to SEB is linear in the range from 6.0 to 564?pg?mL^?1 (r?=?0.9993), and the detection limit is 3.3?pg?mL^?1 (S/N?=?3). Intra- and interassay coefficients of variation are <7.0% at three concentrations (24, 96 and 384?pg?mL^?1). The method was applied to the analysis of SEB in serum, lake water and milk samples. The results compared well with those obtained by conventional ELISAs.

DFT/TDDFT study on the electronic structures and optoelectronic properties of several red-emitting osmium(II) complexes with different P^P ancillary ligands

The ground and excited state geometries of several red-emitting phosphors (N^N)(2)Os(P^P) [where N^N = 5-(1-isoquinolyl)-1,2,4-triazoles, P^P = bis(dimethylphosphino)methylene(dmpm) (1); P^P = cis-1,2-bis-(dimethylphosphino)ethene(dmpe) (2); P^P = 1,2-bis(dimethylphosphino)benzene(dmpb) (3); P^P = 1,2-bis(dimethylphosphino)naphthalene(dmpn) (4); P^P = 1,2-bis(dimethylphosphino)-4-cyano-benzene(dmpcb) (5)] have been investigated by using the density functional theory (DFT) methods. The calculated results indicate that, for the studied complexes, the electron-transporting performance is better than the hole-transporting performance. The alteration of cis-P^P ancillary ligands with different conjugation lengths and substituents has an impact on the optoelectronic properties of these complexes, especially the electron-withdrawing group -CN in 5. The calculated energy gaps are nearly the same for complexes 1 to 4 (3.34 eV), while for 5, the HOMO and LUMO energies are lowered and the energy gap increases (3.42 eV). The absorption of 1 is red shifted, while that of 5 is blue shifted compared with the absorptions of 2, 3, and 4, which have similar absorptions. Complexes 2, 3, and 4 have almost identical emission wavelength 699 nm, while 1 (715 nm) and 5 (735 nm) are red shifted. The calculated electron affinities and reorganization energies indicate that complex 5 is the easiest for electron injection and has the best electron-transporting performance.     

Polyoxygenated ergostane-type sterols from the liquid culture of Ganoderma applanatum

A new polyoxygenated ergostane-type sterol, 3β,5α,6β,8β,14α-pentahydroxy-(22E,24R)-ergost-22-en-7-one (1), has been isolated from the liquid culture of the basidiomycete Ganoderma applanatum together with four known sterols, 3β,5α,9α-trihydroxy-(22E,24R)-ergosta-7,22-dien-6-one (2), ergosterol peroxide (3), 6-dehydrocerevisterol (4) and cerevisterol (5). Two of these sterols (2, 4) are reported to have been isolated from this species for the first time. The structures of these compounds were determined by chemical and spectroscopic analyses, including 1D- and 2D-NMR, as well as by comparison of their spectroscopic data with those reported in the literature.     

Qualitative and quantitative analyses of Epimedium wushanense by high-performance liquid chromatography coupled with diode array detection and electrospray ionization tandem mass spectrometry

A new HPLC-DAD-ESI-MS(n) method was developed for rapid separation, characterization and quantitation of flavonoids in Epimedium wushanense, a popular Chinese herbal medicine. For qualitative identification, a total of 37 compounds were characterized from the underground and aerial parts of E. wushanense. Among them, 28 compounds were prenylated flavonoids, and 23 were confirmed by comparing with reference standards. For quantitative analysis, 12 major flavonoids including kaempferol glycosides, desmethylicaritin glycosides, and icaritin glycosides were simultaneously determined by HPLC/UV. Samples were separated on a Waters Symmetry C(18) column at 35 °C eluted with a gradient three-component mobile phase of acetonitrile, methanol, and water containing 0.03% v/v formic acid. All the flavonoids showed good linearity (r(2) ≥0.9997). The recoveries varied from 92.6 to 106.1% at three concentration levels. This method was applied to the determination of 20 samples of different geographical sources, harvesting time, and plant parts. Contents of the predominant flavonoid, epimedin C, ranged from 1.4 to 5.1% in aerial parts and 1.0 to 2.8% in underground parts. The methods established in this paper were simple and reliable and could be used for the quality control of E. wushanense.     

Synthesis of N-(2-pyridyl)indoles via Pd(II)-catalyzed oxidative coupling

Readily available Pd(II) chloride catalysts can catalyze selective and efficient oxidative coupling between N-aryl-2-aminopyridines and internal alkynes to yield N-(2-pyridyl)indoles. This process involves the ortho C-H activation of N-aryl-2-aminopyridines, and CuCl(2) was used as an oxidant. Compared to our previously reported Rh(III)-catalyzed synthesis of this class of product, this method is advantageous with a wider scope of alkynes and cost-effective Pd(II) catalysts. Molecular oxygen can be used as a terminal oxidant.