Hexanes/acetonitrile: a binary solvent system for the efficient monosilylation of symmetric primary and secondary diols

Symmetric diols are useful compounds in the synthesis of natural products, their value often dependent on their successful monoprotection. A general and simple method for the monosilylation of symmetrical primary and secondary diols is reported. The method exploits the solubility differential of diols and their monosilylated counterparts in a binary hexanes/acetonitrile solvent system.     

An experimental study about the effect of arrangement on the fire behaviors of lithium-ion batteries

The gadolinium ferrochromite (GdFe_1?xCr_xO₃) was used as a case study of influence of chromium substitution on the perovskite structure in the entire composition range. By exploiting thermal analysis techniques (dilatometry, differential thermal analysis) the influence of chromium was investigated in the context of thermal stability of the canted antiferromagnetic ordering. It was found that the higher the chromium concentration was, the more the Néel temperature decreased, e.g., substitution of 26 % of iron atoms corresponded to a depression of about 60 K with respect to undoped gadolinium ferrite. For higher chromium concentrations the mixed gadolinium ferrochromite was paramagnetic at room temperature. Additional information on the crystal structure and, qualitatively, on the magnetic ordering as well was derived from the results of X-ray diffraction and Mössbauer spectroscopy measurements. For chromium content higher than 10 % the gadolinium ferrochromite may be regarded as a solid solution. For lower concentrations, however, a possible formation of clusters with different Fe/Cr ratio occurs as suggested by Mössbauer spectra.     

Cationic Lanthanide Luminescent Copolymer: Design,Synthesis and Interaction with DNA

Polymerizable rare earth complex Eu(AA)₃Phen was synthesized by complexion of europium ion, acrylic acid (AA), and 1,10-phenanthroline (Phen). The structure and fluorescence properties of the complex were studied by elemental analysis, ¹H-NMR spectroscopy, and fluorescence spectroscopy. Eu-containing copolymer poly(PEGMA-co-MMA-co-METAC-co-Eu(AA)₃Phen) (PPMMEu) was then synthesized by free radical copolymerization of Eu(AA)₃Phen and other functional monomers including poly(ethylene glycol) methyl ether methacrylate (PEGMA) and [2-(Methacryloyloxy) ethyl] trimethylammonium chloride (METAC). ¹H-NMR spectroscopy and fluorescence spectroscopy were used to characterize the copolymer and the interactions between the copolymer and DNA was investigated by TEM, fluorescence spectroscopy, and agarose gel electrophoresis. The desired luminescent cationic copolymer was successfully obtained. The copolymer can form micelles in water solution and can efficiently bind to DNA molecules through electrostatic interaction. The results suggest the potential use of PPMMEu in bioprobes and gene vectors.     

Cyano-Carbonates (II) -Eficient Iatent Acyl Carbanious in 1,4-Additions

Alkylations of cyano-carbonate anions with ethyl acrylate or methyl vinyl ketone followed by hydrolysis yield 1,4-addition products in excelleat yields.     

Unsaturated polyester resins modified with phosphorus-containing groups: Effects on thermal properties and flammability

A novel reactive phosphorus-containing monomer [1-oxo-2,6,7-trioxa-1- phosphabicyclo-[2.2.2]octane-methyl diallyl phosphate, PDAP] was synthesized, and various amounts of PDAP were combined with unsaturated polyester by radical bulk polymerization. The resulting flame-retardant unsaturated polyester resin (FR-UPR) samples were investigated by thermogravimetric analysis (TGA), microscale combustion calorimetry (MCC), and limiting oxygen index (LOI) tests. Due to the relatively high phosphorus content of PDAP (18.2 wt%), incorporation of this monomer into unsaturated polyester resin (UPR) led to a marked decrease in the heat release capacity (HRC), the total heat release (THR), an increase in the LOI and the char yield upon combustion. In order to elaborate the interactions between the UPR and PDAP in degradation, differences between the experimental and theoretical mass losses of a FR-UPR sample were evaluated. Furthermore, thermogravimetry-Fourier transform infrared (TG-FTIR) and real-time Fourier transform infrared (RTIR) spectroscopy were employed to investigate the degradation behavior of UPRs, providing insight into the degradation mechanism.     

Strong Morphological Effect of Mn3O4 Nanocrystallites on the Catalytic Activity of Mn3O4 and Au/Mn3O4 in Benzene Combustion

Gold nanoparticles (3–4 nm) were deposited on Mn₃O₄ nanocrystallites with three distinct morphologies (cubic, hexagonal, and octahedral). The resulting structures were characterized, and their activities for benzene combustion were evaluated. The dominant exposed facets for the three kinds of Mn₃O₄ polyhedrons show the activity order: (103)≈(200)>(101). A similar activity order was derived for the interfaces between the Au and the Mn₃O₄ facet: Au/(200)≈Au/(103)>Au/(101). The metal–support interactions between the Au nanoclusters and specific facets of the Mn₃O₄ polyhedrons lead to a unique interfacial synergism in which the electronic modification of the Au nanoparticles and the morphology of the Mn₃O₄ substrate have a joint effect that is responsible for a significant enhancement in the catalytic activity of the Au/Mn₃O₄ system.     

Phosphorescent Cyclometalated Iridium(III) Complexes That Contain Substituted 2‐Acetylbenzo[b]thiophen‐3‐olate Ligand for Red Organic Light‐Emitting Devices

We report the synthesis of a new class of thermally stable and strongly luminescent cyclometalated iridium(III) complexes 1 – 6 , which contain the 2‐acetylbenzo[b]thiophene‐3‐olate (bt) ligand, and their application in organic light‐emitting diodes (OLEDs). These heteroleptic iridium(III) complexes with bt as the ancillary ligand have a decomposition temperature that is 10–20 % higher and lower emission self‐quenching constants than those of their corresponding complexes with acetylacetonate (acac). The luminescent color of these iridium(III) complexes could be fine‐tuned from orange (e.g., 2‐phenyl‐6‐(trifluoromethyl)benzo[d]thiazole (cf₃bta) for 4 ) to pure red (e.g., lpt (Hlpt=4‐methyl‐2‐(thiophen‐2‐yl)quinolone) for 6 ) by varying the cyclometalating ligands (C‐deprotonated C^N). In particular, highly efficient OLEDs based on 6 as dopant (emitter) and 1,3‐bis(carbazol‐9‐yl)benzene (mCP) as host that exhibit stable red emission over a wide range of brightness with CIE chromaticity coordinates of (0.67, 0.33) well matched to the National Television System Committee (NTSC) standard have been fabricated along with an external quantum efficiency (EQE) and current efficiency of 9 % and 10 cd A^?1, respectively. A further 50 % increase in EQE (>13 %) by replacing mCP with bis[4‐(6H‐indolo[2,3‐b]quinoxalin‐6‐yl)phenyl]diphenylsilane (BIQS) as host for 6 in the red OLED is demonstrated. The performance of OLEDs fabricated with 6 (i.e., [(lpt)₂Ir(bt)]) was comparable to that of the analogous iridium(III) complex that bore acac (i.e., [(lpt)₂Ir(acac)]; 6 a in this work) [Adv. Mater.­ 2011 , 23, 2981] fabricated under similar conditions. By using ntt (Hnnt=3‐hydroxynaphtho[2,3‐b]thiophen‐2‐yl)(thiophen‐2‐yl)methanone) ligand, a substituted derivative of bt, the [(cf₃bta)₂Ir(ntt)] was prepared and found to display deep red emission at around 700 nm with a quantum yield of 12 % in mCP thin film.     

有序排列PMMA 模板法合成三维有序纳米孔道MgO

"利用由无乳化剂的乳液聚合法和水浮法联用技术合成得到的有序排列的聚甲基丙烯酸甲酯(PMMA)微球为硬模板,以硝酸镁为镁源,并采用硝酸镁-柠檬酸-乙醇混合溶液浸渍PMMA微球后经干燥以及先后在300 ℃恒温灼烧3 h和500 ℃恒温灼烧5 h,制备出具有有序纳米孔道结构的MgO粒子．应用X射线衍射、高分辨扫描电子显微镜、透射电子显微镜/选区电子衍射以及N2吸附-脱附法等技术表征了PMMA和MgO样品的物理化学性质．结果表明,所得PMMA微球颗粒较为均匀,粒径约为284 nm,且排列规整有序．由PMMA硬模板     

Halogen-Bonding Strapped Porphyrin BODIPY Rotaxanes for Dual Optical and Electrochemical Anion Sensing

Anion receptors employing two distinct sensory mechanisms are rare. Herein, we report the first examples of halogen-bonding porphyrin BODIPY [2]rotaxanes capable of both fluorescent and redox electrochemical sensing of anions. ¹H NMR, UV/visible and electrochemical studies revealed rotaxane axle triazole group coordination to the zinc(II) metalloporphyrin-containing macrocycle component, serves to preorganise the rotaxane binding cavity and dramatically enhances anion binding affinities. Mechanically bonded, integrated-axle BODIPY and macrocycle strapped metalloporphyrin motifs enable the anion recognition event to be sensed by the significant quenching of the BODIPY fluorophore and cathodic perturbations of the metalloporphyrin P/P^+. redox couple.