Enolate chelating N-heterocyclic carbene complexes of Fe(II): Synthesis, structure and their catalytic activity for ring-opening polymerization of ε-caprolactone

The reaction of anhydrous FeBr2 with two equivalents of anionic N-heterocyclic carbene (NaL1 and NaL2), which are generated in situ by the reaction of the corresponding salt [4-R-C6H4COCH2{CH- (NCHCHNiPr)}Br] (R = OCH3, H2L1Br, 1; R = F, H2L2Br, 2) with two equivalents of NaN(SiMe3)2, affords bis-ligand Fe(II) complexes of L12Fe (3) and L22Fe (4) in high yield, respectively. Attempt to synthesize mono-ligand Fe(II) bromide by the 1:1 molar ratio of NaL to FeBr2 is unsuccessful, and the same com- plexes of 3 and 4 were obtained. Both 3 and 4 have been depicted by elemental analysis and X-ray structure determination. Preliminary studies show that both 3 and 4 can be used as single-component catalyst for the ring-opening polymerization of ε-caprolactone, and the catalytic activity of 3 is higher than that of 4.     

An efficient and recyclable iron(III)-containing imidazolium salt catalyst for cross-coupling of aryl Grignard reagents with alkyl halides

1,3-Bis(2,6-diisopropylphenyl)imidazolium chloride, [DIPrim]Cl, was used to produce a novel iron(III)-containing imidazolium salt [DIPrim][FeCl 4 ], which included a N,N-diarylimidazolium cation (R = 2,6-diisopropylphenyl), [DIPrim] + , and tetrachloroferrate(III) anion, [FeCl 4 ]. This compound was an effective and easy-to-use catalyst for the cross-coupling of aryl Grignard reagents with primary and secondary alkyl halides bearing -hydrogens. After simply decanting the cross-coupling product in the ether layer, [DIPrim][FeCl 4 ] could be reused in at least four successive runs without significant loss of catalytic activity.     

Prediction of Enthalpies of Fusion for Divalent Rare Earth Halides Based on Modeling by Artificial Neural Networks and Pattern Recognition

The artificial neural network (ANN) and the pattern recognition were applied to study the correlation of enthalpies of fusion for divalent rare earth halides with their microstructural parameters,such as ionic radius and electronegativity. The model,represented by a back-propagation neural network, was trained with a 12 set of published data for divalent rare earth halides and then was used to predict the unknown ones. Also the criterion equations were presented to determine the enthalpies of fusion for divalent rare earth halides using pattern recognition in mis work. The results from the model in ANN and criterion equations are in very good agreement with reference data.     

Electronic structure and magnetism of RMn6Sn6 （R=Tb, Dy）

This article reports first-principles band structure calculations for RMn6Sn6 (R= Tb, Dy). The calculation uses the linear muffin-tin orbitals (LMTO) method in the atomic-sphere-approximation (ASA),and yields results showing that both TbMn6Sn6 and DyMn6Sn6 are ferrimagnetic compounds with antiparallel aligned moments of R and Mn atoms. In this research the 4f states of R atoms are treated as localized states,i. e., the hybridization of 4f states with other valence electrons is neglected. The moments of Mn in both compounds were determined to be 2.43μB and 2.38μB, respectively. The considerably small additional moments for Mn from the spin-orbit coupling indicates that the spin-orbital coupling is not dominated for Mn atoms. The total moments of Tb and Dy atoms are 10.28μB and 11.20μB. All the calculation findings accorded well with experimental results.     

Screening cervical lesions with Fourier transform infrared spectroscopy

The screening results were reported based on the Fourier transform infrared spectroscopy (FTIR) analysis of the samples of exfoliated cervical cells from 354 women. Their spectra can be sorted into two types based on the emerging or not of the absorption bands near 970 cm^-1 and 1 170 cm^-1: T1 (83.1%) type without emerging, and T2 (16.9%) type with obviously emerging. All of the samples assigned to T1 were cytologically diagnosed as normal or within normal limits (PapⅠ). 28.9% and 71.1% of samples exhibiting T2 profile, were cytologically evaluated as Pap Ⅰand abnormal respectively. 3 women in the abnormal group were diagnosed as to have cervical cells with changes associated with high grade of inflammation, cervical scar and cervical erosion. Furthermore, based on the progressive change of the relative intensities of the absorption bands, both T1 and T2 profiles can be categorized into 6 subtypes. The observed heterogeneous spectra and the progressive changes in the absorption frequencies and the relative intensities exhibit features suggestive of the progressive process of cervical lesion. The FTIR method has the potential to complement the cytological smear for large-volume screening of cervical lesions.     

Structure and properties of solid-state synthesiz ed poly (3,4-propylenedi oxythiophene) /nano-ZnO composite

Poly（3,4-propylenedioxythiophene）/nano-Zinic Oxide（PProDOT/ZnO） composites with the content of 3-7 wt%nano-ZnO were synthesized by the solid-state method with FeCl₃ as oxidant.The structure and morphology of the composites were characterized by Fourier transform infrared（FTIR）spectroscopy,ultraviolet-visible（UV-vis） absorption spectroscopy,X-ray diffraction（XRD） and transmission electron microscopy（TEM）.The electrochemical performances of the composites were investigated by galvanostatic charge-discharge,cyclic voltammetry and electrochemical impedance spectroscopy（EIS）.The photocatalytic activities of the composites were investigated by the degradation of methylene blue（MB） dyes in aqueous medium under UV light irradiation.The results from FTIR and UV-vis spectra showed that the PProDOT/ZnO composites were successfully synthesized by solid-state method,and nano-ZnO had great influences on the conjugation length and oxidation degree of the polymers.Furthermore,the PProDOT/5 wt%ZnO had the highest conjugation and oxidation degree among the composites.The results of XRD analysis indicated that there were some FeCl₄^- ions as doping agent in the PProDOT matrix,and the content of ZnO had no effect on diffraction pattern of PProDOT.Morphological studies revealed that the pure PProDOT and composites had similar morphological structure,and all the composites displayed an irregular sponge like morphology.The results of electrochemical tests showed that the PProDOT/5 wt%ZnO had a higher electrochemical activity with a specific capacitance value of 220 F g^-1 than others.The results from photocatalytic activities of the composites indicated that the PProDOT/5 wt%ZnO had better photocatalytic activity than other composites.     

Preparation of nano-TiO2/diatomite-based porous ceramics and their photocatalytic kinetics for formaldehyde degradation

Diatomite-based porous ceramics were adopted as carriers to immobilize nano-TiO₂ via a hydrolysis-deposition technique. The thermal degradation of as-prepared composites was investigated using thermogravimetric-differential thermal analysis, and the phase and microstructure were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and transmission electron microscopy. The results indicated that the carriers were encapsulated by nano-TiO₂ with a thickness of 300-450 nm. The main crystalline phase of TiO₂ calcined at 650℃ was anatase, and the average grain size was 8.3 nm. The FT-IR absorption bands at 955.38 cm-1 suggested that new chemical bonds among Ti, O, and Si had formed in the composites. The photocatalytic (PC) activity of the composites was investigated under UV irradiation. Furthermore, the photodegradation kinetics of formaldehyde was investigated using the composites as the cores of an air cleaner. A kinetics study showed that the reaction rate constants of the gas-phase PC reaction of formaldehyde were κ=0.576 mg·m-3·min-1 and K=0.048 m3.     

Synthesis of Hyperbranched Polymers and Its Effect on Water Vapor Permeability of Microfiber Synthetic Leather

A series of hyperbranched poly(amine-ester)polyols were synthesized by the polycondensation of N,N-diethylol-3-amine-methylpropionate(prepared by Michael addition reaction of methyl acrylate with diethanolamine)as an AB2-type monomer with trimethylol propane as the core moiety,proceeding in one-step procedure in the melt with p-toluenesulfonic acid as catalyst.The obtained monomer and polymers were characterized by FTIR and 1H-NMR spectroscopy.The solubility and surface activity in aqueous solution of the polymers were also examined.The gas permeability,water vapor permeability,and moisture absorption of microfiber synthetic leather treated by hyperbranched polymer were studied.The optimum conditions were that the dosage of dye and hyperbranched polymer was 5% and 10%,respectively.The water vapor permeability and moisture absorption of microfiber synthetic leather reached to 0.525 4 mg/(10 cm2·24 h)and 0.046 7 mg/(10 cm2·24 h).Compared with blank samples,they increased by 15% and 35%,respectively.However,the dosage of hyperbranched polymer has little influence on gas permeability of microfiber synthetic leather.SEM results show that the fiber of microfiber synthetic leather treated by hyperbranched polymer is incompact.     

Diversity and high nitrogenase activity of endophytic diazotrophs isolated from Oryza rufipogon Griff.

Diversity and nitrogenase activity of endophytic diazotrophs colonized in the wild rice Oryza rufipogon Griff grown in Boluo, Huilai County in Guangdong Province and Lingshui County in Hainan Province were studied. Thirty-seven isolates obtained from Oryza rufipogon were identified as putative endophytic nitrogen-fixing bacteria by ARA （acetylene reduction assay） test and further confirmed by PCR amplification of nifH gene fragments. All obtained strains have ARA activity and the same sized nifH gene fragments. Above the similarity level of 80%, the obtained isolates were assigned as Group Ⅰ to Ⅷ by the clustering of IS-PCR fingerprints. The SDS-PAGE whole-cell protein patterns were similar to those of IS-PCR fingerprints. Components and contents of fatty acid methyl esters （FAMEs） were used to differentiate the representative strains （Ls13, Ls8, BL1, BL12, HL6, Ls4） from Group Ⅰ to Group Ⅵ. The six representative strains showed significant difference in contents and components of cellular fatty acid methyl ester. 16S rDNA sequencing analysis showed that strains of Group Ⅰ to Ⅶ were located in Enterobacteraceae （y-proteobacteria）. Strains of Group Ⅰ and Group Ⅱ were closely related to Klebsiella sp.; Strain Ls8 of Group Ⅱ was a little far away from the genus of Pantoea （homology level 96% with Pantoea agglomerans）, which may represent a new species or genus in Enterobacteraceae; Strains of Groups Ⅳ and Ⅴ belonged to different Enterobacter sp.; Strain Ls4 and Ls 9 representing Group Ⅵ were close to Citrobacter amalonaticus with 98% sequence similarity; Strain Ls15 of Group Ⅶ showed 98% sequence identity with Pantoea sp.; Strains of Group Ⅷ were assigned to the genus Ideonella （β-proteobacteria）. Based on the above results, endophytic diazotrophs isolated from O. rufipogon showed great diversity and some diazotrophs showed high nitrogenase activity with 42.52 μmol/mL. h C2H4. Inoculation to rice tests indicated that the isolated endophytic diazotrophs significantly promoted the rice growth.     

Effect of light response on the photocatalytic activity of BiOCl x Br1−x in the removal of Rhodamine B from water

BiOClxBr1-x catalysts were synthesized through an alcoholysis method and characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM）, high-resolution transmission electron microscopy （HRTEM）, and diffuse reflectance spectroscopy （DRS）. The as-prepared photocatalysts were found to be tetragonal crystal structure and lamellar plate morphology. Their band gaps were between 3.44 and 2.83 eV. The effect of light response on the photocatalytic activity of BiOClxBrl-x was investigated by degradation of Rhodamine B （RhB）. Complete removal of RhB from water was realized under simulated sunlight irradiation for 50 min with BiOC10.5Br0.5. Mechanism studies showed that photo- generated holes and superoxide anion radicals played important roles in RhB photodegradation. The results of chemical oxygen demand （COD） confirmed RhB mineralization. The effect of light response on the activity of BiOClxBr1-x was further investigated under monochromatic light irradiation, and BiOCl0.5Br0.5 catalyst exhibited the highest activity. Furthermore, BiOC10.5Br0.5 exhibited high stability, suggesting its practical application for the removal of RhB pollutant from water.     

Reactions of [FeL2(CH3CN)2](PF6)2 (L = N-pyrimid-2-ylimidazol-ylidene) with N-, P-, O-, and S-donors and its catalytic activity

Reactions of [FeL2(CH3CN)2]2+(L = N-pyrimid-2-ylimidazolylidene) with various N-,P-,O-,and S-donors were investigated.By replacing the labile acetonitrile,various iron-NHC complexes containing additional N-,P-,O-,and S-ligands were prepared.All the iron-NHC complexes were fully characterized by NMR spectroscopy and X-ray crystallography.[FeL2(CH3CN)2]2+ could efficiently catalyze the coupling reactions of various Grignard reagents with heteroaryl bromides or chlorides.     

Fabrication of high quality strained SiGe on Si substrate by RPCVD

In this study,the growth kinetics of SiGe in a reduced pressure chemical vapor deposition system using dichlorosilane(SiH2Cl2) and germane(GeH4) as the Si and Ge precursors were investigated.The SiGe growth rate and Ge content were found to depend on the deposition temperature,GeH4 flow and reactor chamber pressure.The SiGe growth rate escalates with increasing deposition temperature,while the Ge content is reduced.The SiGe growth rate accelerates with increasing GeH4 flow,while the Ge content increases more slowly.According to the experimental data,a new relationship between Ge content(x) and F(GeH4)/F(SiH2Cl2) mass flow ratio is deduced:x2.5/(1x) = nF(GeH4)/F(SiH2Cl2).The SiGe growth rate and Ge content improve with increasing reactor chamber pressure.By selecting proper precursor flows and reactor pressure,SiGe films with the same Ge content can be fabricated at various temperatures.However,the quality of the SiGe crystals is clearly dependent on the deposition temperature.At lower deposition temperature,higher crystalline quality is achieved.Because the growth rate dramatically drops with lower temperatures,the optimum growth temperature must be a compromise between the crystalline quality and the growth rate.X-ray diffraction,Raman scattering spectroscopy and atomic force microscopy results indicate that 650°C is the optimum temperature for fabrication of Si0.75Ge0.25 film.     

Effect of TiO<Subscript>2</Subscript> nanoparticles on hydrogen evolution reaction activity of Ni coatings

The electrocatalytic activity of electrodeposited Ni and Ni-TiO₂ coatings with regard to the alkaline hydrogen evolution reaction (HER) was investigated. The Ni coatings were electrodeposited from an acid chloride bath at different current densities, and their HER activities were examined in a 1.0-mol·L-1 KOH medium. The variations in the HER activity of the Ni coatings with changes in surface morphology and composition were examined via the electrochemical dissolution and incorporation of nanoparticles. Electrochemical analysis methods were used to monitor the HER activity of the test electrodes; this activity was confirmed via the quantification of gases that evolved during the analysis. The obtained results demonstrated that the Ni-TiO₂ nanocomposite test electrode exhibited maximum activity toward the alkaline HER. The surface appearance, composition, and the phase structure of all developed coatings were analyzed using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD), respectively. The improvement in the electrocatalytic activity of Ni-TiO₂ nanocomposite coating toward HER was attributed to the variation in surface morphology and increased number of active sites.     

Cellular fluorescent high-throughput screening assays of the ATP-gated P2X7 receptor

The P2X 7 receptor (P2X7R) is an important member of the P2X family of ligand-gated ion channels that respond to ATP as the endogenous agonist. Studies suggest that P2X7R plays a potentially pivotal role in a variety of physiological functions, including peripheral and central neuronal transmission, smooth muscle contraction, and inflammation. Thus, P2X7R may be a potential target for drug development. Here, we used a FlexStation to examine the function of recombinant P2X7R stably expressed in human embryonic kidney 293 cells and to compare three high-throughput screening assays: a membrane potential assay, an ethidium bromide uptake assay, and a calcium influx assay. We found that all three assays were suitable for the analysis of P2X7R, but the calcium influx assay was the most robust and is the best choice as a first high-throughput screening assay when embarking on a P2X7R drug discovery project.     

Synthesis and mesomorphic properties of fluorinated Schiff's base liquid crystals containing vinyl end groups

Three kinds of fluorinated Schiff's base esters, 4-allyloxy-2-X-6-X-benzoic acid 4-[(2, 3, 4-trifluorophenylimino)methyl]phenyl ester, where X=H or F, were synthesized and characterized. Their chemical structures were identified by Fourier transform infrared spectroscopy (FTIR) and 1H nuclear magnetic resonance (1H NMR). Their mesomorphic properties were studied by polarized optical microscopy (POM) and differential scanning calorimetry (DSC). It was found that all the three compounds exhibited enantiotropic nematic phases only. And their cleating point temperature and thermal range of mesophase decreased with the number of fluorine atoms on the rigid core of the compounds; while their melting point temperature showed no distinct regularity.     

Crystal structures,antibacterial activity and thermal decomposition kinetics of lanthanide complexes with 4-chloro-2-methoxybenzoic acid and 1,10-phenanthroline

A series of lanthanide complexes [Ln(4-Cl-2-MOBA)3phen]2(Ln=Sm(1), Nd(2), Ho(3), Eu(4), Dy(5), and Tb(6); 4-Cl-2-MOBA=4-chloro-2-methoxybenzoate, phen=1,10-phenanthroline) were synthesized and characterized. The single-crystal X-ray diffraction demonstrates that 1–3 are isomorphous, which present dimeric structures with four 4-Cl-2-MOBA anions function as bridging ligands. Complexes 1 and 4–6 display their characteristic luminescence emission bands of central Ln3?ions. The heat capacities, the thermodynamic functions and the thermogravimetry–Fourier transform infrared spectra of gaseous products of complexes 1–6 were investigated.Their non-isothermal kinetics of the second decomposition stage was studied by the integral isoconversional non-linear method and Stark method. Furthermore, 1–6 exhibited excellent antibacterial activity against Candida albicans,Escherichia coli and Staphylococcus aureu.     

Electrochemical and spectroscopic study of interfacial interactions between chalcopyrite and typical flotation process reagents

Comparative voltammetry and differential double-layer capacitance studies were performed to evaluate interfacial interactions between chalcopyrite (CuFeS₂) and n-isopropyl xanthate (X) in the presence of ammonium bisulfite/39wt% SO₂ and caustic starch at different pH values. Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, contact angle measurements, and microflotation tests were used to establish the type and extent of xanthate adsorption as well as the species involved under different mineral surface conditions in this study. The results demonstrate that the species that favor a greater hydrophobicity of chalcopyrite are primarily CuX and S0, whereas oxides and hydroxides of Cu and Fe as well as an excess of starch decrease the hydrophobicity. A conditioning of the mineral surface with ammonium bisulfite/39wt% SO₂ at pH 6 promotes the activation of surface and enhances the xanthate adsorption. However, this effect is diminished at pH ≥ 8, when an excess of starch is added during the preconditioning step.     

Synthesis and characterization of silica mesoporous material produced by hydrothermal continues pH adjusting path way

Mesoporous silica molecular sieves MCM-41 were synthesized under hydrothermal conditions. For this purpose, a solution with a molar coefficient of water, cetyltri-methyl ammonium bromide surfactants as template and sodium silicate as the source of SiO₂ are used. Phase formation, morphology and gas absorption properties were investigated by XRD and BET analysis, respectively. The results showed that silica mesoporous material has been successfully synthesized. A favorable special surface and porosity volume together with regular arrangement of nano metric-hexagonal porosities were obtained from this synthesis. Thickness of the wall and average diameter of the pores are 0.8 nm and 4 nm, respectively.     

Synthesis and characterization of organometallic macrocyclic rhodium (Ⅲ) complex with pyrazine ligands

The synthesis and structure research of organometal-lic macrocyclic complexes has been a very active field of modern chemistry [1—3]. In this field, Pd2+, Pt2+ complexes were first used as the building block, connected by het-erocyclic ligands, to construct metal macrocyclic com-pound[4,5]. The fac-Re(CO)5X (X = Cl, Br) fragment, for example, was shown to be a versatile building block for the synthesis of metallamacrocycles[6]. Some of this kind of molecule have been found applications in…     

Effect of TiO_2 nanoparticles on hydrogen evolution reaction activity of Ni coatings

The electrocatalytic activity of electrodeposited Ni and Ni–TiO_2 coatings with regard to the alkaline hydrogen evolution reaction(HER) was investigated. The Ni coatings were electrodeposited from an acid chloride bath at different current densities, and their HER activities were examined in a 1.0-mol·L~(-1) KOH medium. The variations in the HER activity of the Ni coatings with changes in surface morphology and composition were examined via the electrochemical dissolution and incorporation of nanoparticles. Electrochemical analysis methods were used to monitor the HER activity of the test electrodes; this activity was confirmed via the quantification of gases that evolved during the analysis. The obtained results demonstrated that the Ni–TiO_2 nanocomposite test electrode exhibited maximum activity toward the alkaline HER. The surface appearance, composition, and the phase structure of all developed coatings were analyzed using scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS), and X-ray diffraction(XRD), respectively. The improvement in the electrocatalytic activity of Ni–TiO_2 nanocomposite coating toward HER was attributed to the variation in surface morphology and increased number of active sites.