Formation and photoluminescence of silver nanoparticles stabilized by a two-armed polymer with a crown ether core

Silver nanoparticles were synthesized by the use of a two-armed polymer with a crown ether core [poly(styrene)]-dibenzo-18-crown-6-[poly(styrene)] based on the flexibility of the polymer chains and the complex effect of crown ether with Ag(+) and Ag. The size of silver nanoparticles could be tailored by controlling the initial concentrations of the polymer and Ag(+), and the molecular weight of the polymer. The emission of silver nanoparticles was blue-shifted, and the intensity of the photoluminescence of silver nanoparticles stabilized by the polymer was significantly increased due to the complex effect between the crown ether embedded in the polymer and the silver nanoparticles.     

Sorption behavior of 2,4-dichlorophenol on marine sediment

The sorption behavior of 2,4-dichlorophenol on marine sediments treated by different methods was investigated systematically. The sorption of 2,4-dichlorophenol on marine sediments was completed mainly via ion exchange and surface polar sorption. Both the Freundlich and Langmuir isotherms were fit for describing its sorption behavior. The sorption behavior of 2,4-dichlorophenol was affected by various factors including aqueous salinity and temperature. The sorption amount of 2,4-dichlorophenol on marine sediments increased with increasing ion strength, but decreased with increasing temperature.     

稀溶液中环型聚苯乙烯的激基缔合物荧光效应

采用乙酸乙酯为环型和线型聚苯乙烯的非良溶剂, 确定了Mark-Houwink方程分别为[η]_r=1.91×10~(-2)·M~(0.607)和[η]_l=4.06×10~(-2)·M~(0.572)。研究了环型和线型聚苯乙烯的激基缔合物的荧光效应。通过稀溶液中环型和线型高分子线团在柔顺性上存在着差异, 解释了二者之间在荧光效应方面的差异, 并根据实验结果,确定了(I_E/I_M)c→0～M关系式分别为(I_E/I_M)r,c→0=1.91+3.40×10~(-6)M和(I_E/I_M)l,c→0=2.15+3.05×10~(-6)M。     

Chemical Constituents from Cynoglossum gansuense

Two new alkaloids, i.e., (2,3‐dihydro‐1‐oxo‐1H‐pyrrolo[1,2‐a]pyrrol‐7‐yl)methyl (2S*,3S*)‐3‐[(β‐D ‐glucopyranosyl)oxy]‐2‐hydroxy‐2‐(1‐methylethyl)butanoate ( 1 ) and 1,2‐dihydro‐8‐methoxy‐2‐oxoquinoline‐4‐carboxylic acid ( 2 ), were isolated from the alcoholic extract of the whole plant of Cynoglossum gansuense, together with twelve known compounds Their structures were characterized by means of spectroscopic methods, especially by ¹H‐, ¹³C‐, and 2D‐NMR, as well as by HR‐MS experiments and comparison with literature data.     

Study the reactions of fluoroalkanesulfonyl azides with N-alkylindoles

The reactions of fluoroalkanesulfonyl azides R_fSO₂N₃1 with N-alkylindoles 2 have been studied in detail. It was found that both solvent and the amount of the azides seriously affected the product distribution. 1 reacted with equimolar of 2 in ether or 1,4-dioxane affording 2-(N-substituted-indolinylidene)fluoroalkane sulfonylimines 3 as major product; While, treatment of 2 with 2 equiv. of 1 in ethanol, an unexpected product N-substituted-2-fluoroalkanesulfonimino-3-diazo-indolines 4 were obtained in good yield. The reaction mechanism was discussed.     

Mixed micellar medium for the spectrophotometric determination of molybdenum in molybdenum/tungsten mixtures

Effects of cetyltrimethylammonium bromide (CTAB) and/or nonylphenoxypolyethoxyethanol (OP) on the absorption spectra of the complexes of molybdenum and tungsten with bromopyrogallol red (BPR) were studied. Based on these effects, a mixture of CTAB and OP was thus selected as a medium for the selective and sensitive determination of Mo in Mo/W binary mixtures. Under the optimum conditions, Beer's law was obeyed over the range 0.06-0.8 mug ml(-1) Mo with molar absorptivity being 1.3x10(5) l mol(-1) cm(-1) and detection limit 0.025 mug ml(-1). For 1.0 mug Mo, at least 20 mug W did not interfere in the determination of Mo with average recovery and relative standard deviation being 99.5% and <2%, respectively. The method developed maintained the features of simplicity and rapidity and, moreover, its selectivity and sensitivity enhanced greatly due to the use of CTAB/OP mixed micellar medium. When coupled with a compatible concentration method, the proposed method could be used for the determination of trace Mo in natural waters.     

对称三唑Schif碱和氯化铜配合物的研究

本文介绍水杨配合与４－氨基－３，５－二乙基－１，２，４－三唑缩合而成对称三唑Ｓｃｈｉｆ碱（ＳＡＥＴＺ）与氯化铜（ＣｕＣｌ２）形成一种新的配合物Ｃｕ（ＳＡＥＴＺ）２（ＳＡＥＴＺ＝４－（邻羟苯基亚甲基）－亚胺－３，５－二乙基－１，２，４－三唑）。配合物的晶体结构表明，分子中两个偶氮甲碱的Ｎ原子及两个酚氧原子与中心Ｃｕ原子形成规则的平面配位结构。晶体属单斜晶系，空间群Ｐ２１／ｎ，ａ＝８．６８８（２），ｂ＝９．３１４（１），ｃ＝１６．５１５（４），β＝９４．３４（２）。，Ｖ＝１３３２．５（７）３，Ｚ＝２。     

微交联聚合物降滤失剂的合成与性能

针对深井、超深井钻井液体系中的降滤失剂受长时间高温、高矿化度作用易降解的问题，以氮丙啶与3-氯丙烯反应制得-N-烯丙基氮丙啶（ALAI）； ALAI与乙二胺反应制得四烯基交联剂单体（EAAD）； EAAD与丙烯酰胺（AM）和2 丙烯酰胺基-2-甲基丙磺酸（AMPS）发生水溶液自由基共聚反应，合成了微交联共聚物降滤失剂(PAAT)，其结构和性能经¹H NMR, IR和TG-DTG表征。结果表明：PAAT可抗220 ℃高温，在高温、高矿化度条件下可维持钻井液的滤失量与流变性能，API滤失量均低于4.0 mL，高温高压滤失量均小于13.0 mL。     

Dissolution nature of the lithium hydroxide by water molecules

The structures, stabilities, thermodynamic quantities, dissociation energies, infrared spectra, and electronic properties of LiOH hydrated by up to seven water molecules are investigated by using the density-functional theory and the M?ller-Plesset second-order perturbation theory (MP2). Further accurate analysis based on the coupled-cluster theory with singles, doubles, and perturbative triples excitations agrees with the MP2 results. The Li-OH stretch mode significantly shifts with the increase of water molecules, and it eventually disappears upon dissociation. It is revealed that seven water molecules are needed for the stable dissociation of LiOH (as a completely dissociated conformation), in contrast to the cases of RbOH and CsOH which require four and three water molecules, respectively.     

含环氧端基酚酞聚芳醚酮E-PEK的合成及表征

由酚酞和4,4′-二氯二苯酮经亲核缩聚制得了一系列不同分子量的含—OK端基的聚醚酮低聚物,将其与环氧氯丙烷反应得到了分子量为1000～8000的含环氧端基聚芳醚酮(E-PEK)。用IR和~1H NMR表征了E-PEK的分子链结构,测定了T_g、溶解性和熔融粘度。研究了E-PEK/DDE体系的固化,固化后树脂的T_(g∞)=183～215℃,与低聚物的初始分子量有关。