Er3+单掺、Er3+/Yb3+共掺杂Ca12Al14O32F2的 制备及上转换发光性质

利用高温固相法成功制备了Er~(3+)单掺、Er~(3+)/Yb~(3+)共掺杂Ca_(12)Al_(14)O_(32)F_2上转换发光样品。在980 nm激光激发下,Er~(3+)单掺和Er~(3+)/Yb~(3+)共掺杂样品均呈现出较强的绿光(528,549 nm)和较弱的红光(655 nm)发射,分别归因于Er~(3+)离子的~2H_(11/2),~4S_(3/2)→~4I_(15/2)和~4F_(9/2)→~4I_(15/2)能级跃迁。随着Er离子浓度的增加,单掺杂样品上转换发光强度先增大后减小,最佳掺杂浓度为0.8%。共掺杂Yb~(3+)后,Er~(3+)的发光强度明显增大。还原气氛下合成的样品上转换发光强度增大约两倍,可能和笼中阴离子基团变化有关。发光强度和激发光功率的关系表明所得上转换发射为双光子吸收过程,借助Er~(3+)-Yb~(3+)体系能级结构详细讨论了上转换发射的跃迁机制。     

Radiolabelling of TiO<Subscript>2</Subscript> nanoparticles for radiotracer studies

Industrially manufactured titanium dioxide nanoparticles have been successfully radiolabelled with ⁴⁸V by irradiation with a cyclotron-generated proton beam. Centrifugation tests showed that the ⁴⁸V radiolabels were stably bound within the nanoparticle structure in an aqueous medium, while X-ray diffraction indicated that no major structural modifications to the nanoparticles resulted from the proton irradiation. In vitro tests of the uptake of cold and radiolabelled nanoparticles using the human cell line Calu-3 showed no significant difference in the uptake between both batches of nanoparticles. The uptake was quantified by Inductively Coupled Plasma Mass Spectrometry and high resolution γ-ray spectrometry for cold and radiolabelled nanoparticles, respectively. These preliminary results indicate that alterations to the nanoparticles’ properties introduced by proton bombardment can be controlled to a sufficient extent that their further use as radiotracers for biological investigations can be envisaged and elaborated.     

Well‐defined polyisoprene‐grafted silica nanoparticles via the RAFT process

The preparation of well‐defined polyisoprene‐grafted silica nanoparticles (PIP‐g‐SiO₂ NPs) was investigated. Surface initiated reversible addition fragmentation chain transfer (SI‐RAFT) polymerization was used to polymerize isoprene from the surface of 15 nm silica NPs. A high temperature stable trithiocarbonate RAFT agent was anchored onto the surface of particles with controllable graft densities. The polymerization of isoprene mediated by silica anchored RAFT with different densities were investigated and compared to the polymerization mediated by free RAFT agents. The effects of different temperatures, initiators, and monomer feed ratios on the kinetics of the SI‐RAFT polymerization were also investigated. Using this technique, block copolymers of polyisoprene and polystyrene on the surface of silica particles were also prepared. The well‐defined synthesized PIP‐g‐SiO₂ NPs were then mixed with a polyisoprene matrix which showed a good level of dispersion throughout the matrix. These tunable grafted particles have potential applications in the field of rubber nanocomposites. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1493–1501     

Sulfonated Condensed Polynuclear Aromatic (S-Copna) Resin Catalyzed Selective Oxidation of Sulfides to Sulfoxides or Sulfones Using Hydrogen Peroxide

Abstract

Sulfonated condensed polynuclear aromatic (S-COPNA) resin was found to be a highly efficient, environmentally friendly, recyclable heterogeneous catalyst for the oxidation of alkyl and aryl sulfides to the corresponding sulfoxides or sulfones, in good yields under mild reaction conditions using 30% hydrogen peroxide as an oxidant.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Synthesis of the S-COPNA resin catalyst. Spectroscopic data for compounds.     

SYNTHESIS OF NEW BENZOSULFOXIDE MACROCYCLIC COMPOUNDS

Bis(dibenzosulfoxo)-27,30,35,38-tetramethyl-24-crown-6, bis(dibenzosulfoxo)-21,24,29,32-tetramethyl-18-crown-4, dibenzosulfoxo-15,18-dimethyl-12-crown-3 and dibenzosulfoxo-12,15-dimethyl-9-crown-2 macrocycles are synthesized by the reaction of 2,2′-sulfinyl-bis(4-methyl phenol)and 1,2-dibromoethane and diethyleneglycol di-p-toluenesulfonate.     

A novel covalent functionalisation of poly (styrene-alt-maleic anhydride) with 4-amino benzo-9-crown-3 ether

The grafting of 4-amino benzo-9-crown-3 ether to poly (styrene-alt-maleic anhydride) has been described. The covalent grafting of crown ether has led to a considerable increase in the solubility of polymer in organic solvents such as dimethyl sulphoxide, dimethylformamide and tetrahydrofuran. The highest solubility was attained in DMF and DMSO. The covalently bonded 4-benzo-9-crown-3 ether allowed the hosting of Li⁺. The covalently grafted crown ether to polymer was identified by infrared spectroscopy and thermogravimetric analysis methods.     

Cup-shaped E,E-stilbenophane: synthesis,crystal structure and supramolecular chemistry

A new E,E-stilbenophane was synthesised and characterised. The crystal structure of this cyclophane shows that this molecule has a cup-shaped structure, which hosts a phenyl ring of neighbouring molecule as guest in its cavity with a π–π distance of about 3.7 Å. Moreover, the NMR spectra and theoretical analysis (gauge-independent atomic orbitals (GIAO) and quantum theory of atoms in molecules (QTAIM)) suggest that the silver recognition by E,E-stilbenophane host molecules is based on cation–π interactions in which the π-electrons of the double bonds play a major role.     

Thermoanalytical study of linkage isomerism in coordination compounds

The non-isothermal differential scanning calorimetry (DSC) experiments revealed that linkage isomerization of both pure trans-[Co(en)₂(ONO)₂]PF₆ (dinitrito isomer) and trans-[Co(en)₂(NO₂)₂]PF₆ (dinitro isomer) occurs in the solid state at elevated temperatures. The process was found to be exothermic for the dinitrito isomer and endothermic for dinitro isomer. The pure isomers could be considered to be in metastable states at ambient temperatures which would be converted to an equilibrium mixture of both isomers (stable state) upon heating. Since the isomerization of both isomers may be described as a two stages process, the corresponding DSC peaks have been resolved into two peaks by means of nonlinear curve fitting tools of PeakFit^® software. The resolution of the peaks helped us to determine enthalpy changes of stepwise isomerization of both isomers. A first-order initial rate and Kissinger methods have been employed to estimate kinetic parameters of the stepwise isomerization reactions. The Kissinger method provided more reliable kinetic results. The high activation energy and positive entropy changes of isomerization of both isomers are considered as indication of a dissociative mechanism in solid state.     

SMFs-supported Pd nanocatalysts in selective acetylene hydrogenation:Pore structure-dependent deactivation mechanism

In the present study,CNFs,ZnO and Al2O3 were deposited on the SMFs panels to investigate the deactivation mechanism of Pd-based catalysts in selective acetylene hydrogenation reaction.The examined supports were characterized by SEM,NH3-TPD and N2adsorption-desorption isotherms to indicate their intrinsic characteristics.Furthermore,in order to understand the mechanism of deactivation,the resulted green oil was characterized using FTIR and SIM DIS.FTIR results confirmed the presence of more unsaturated constituents and then,more branched hydrocarbons formed upon the reaction over alumina-supported catalyst in comparison with the ones supported on CNFs and ZnO,which in turn,could block the pores mouths.Besides the limited hydrogen transfer,N2 adsorption-desorption isotherms results supported that the lowest pore diameters of Al2O3/SMFs close to the surface led to fast deactivation,compared with the other catalysts,especially at higher temperatures.     

Growth Orientation of the Mechanosynthesized Fluorapatite-Based Composite Nanopowders: Influence of Subsequent Thermal Treatment

Growth orientation of fluorapatite–zirconia nanopowders was investigated after mechanical activation and thermal annealing process in the range of 600–1,300 °C for 1 h. Results revealed that during heating of the composite nanopowders the transition of the monoclinic zirconia to tetragonal form and its stabilization by calcium fluoride originating from the decomposition of fluorapatite as well as the formation of a solid solution of calcium fluoride in zirconia occurred. The influence of annealing on the growth orientation of fluorapatite–zirconia composite nanopowders indicated that the crystal growth of fluorapatite was preferentially accentuated on the (002) face in the direction of the crystallographic c-axis after heat treatment. Based on FE–SEM observations, the experimental outcome was composed of both agglomerates and fine particles (~33 nm) after 600 °C, while annealing of the sample at 1,300 °C demonstrated the occurrence of abnormal grain growth.