Copper(I)-Catalyzed Cycloaddition of Methyl O-Propargylpodocarpate and Azides at Room Temperature

Copper iodide was employed as an efficient catalyst for the synthesis of 1,2,3-triazole derivatives of podocarpic acid at room temperature through “click” chemistry cycloaddition reactions of methyl O-propargylpodocarpate and propargyl O-propargylpodocarpate with azides.

Determination of mono-ortho substituted chlorobiphenyls by multidimensional gas chromatography and their contribution to TCDD equivalents

The mono-ortho chlorobiphenyls (CBs) 60, 74, 114, 123, 157, 167 and 189 were determined in Aroclor mixtures and aquatic organisms by multidimensional gas chromatography with electron capture detection (MDGC/ECD), using a combination of an Ultra 2 and an FFAP column. MDGC/ECD is recommended as the most suitable technique for direct determination of these CBs, without a liquid chromatographic (LC) pre-separation of mono-ortho CBs from the other CBs. Dependent, to some extent, on the stationary phase used, single-column determinations of these CBs easily yield too high results due to the presence of interferences. The contribution of the mono-ortho CBs studied to the total 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) equivalents (TEQs) from CBs in fish is highly dependent on the toxic equivalency factors (TEFs) used and varies between 0.02 and 22%. This contribution is mainly due to CBs 74, 114, 157 and 167 which may easily be determined by taking three heart-cuts and combining them into one MDGC/ECD run. The analytical error is negligible compared with the huge uncertainty of the TEFs. A need for more precise TEFs is emphasized.     

毛细管电泳法测定人发中铝

用毛细管离子分析 (CIA)法 ,采用 10mmol·L- 1咪唑为背景电解质 ,4 0 %甲醇为选择性改性剂 ,在 pH 2 .5、分离电压为 2 5kV、柱温为 2 2℃的电泳条件下 ,采用间接紫外检测 (2 14nm ) ,在5min内测定了人发中铝 ,方法简便、快速、灵敏度高、重现性好、测定成本低     

Synthesis, structures and membrane properties of siloxane-imide co-polymers produced by aqueous polymerization

We report for the first time, the synthesis of siloxane-imide co-polymers by the reaction of mixtures of 1,4-bis(aminobutyl)tetramethyldisiloxane (ABTMDS) and 1,3-bis(4-aminophenoxy)benzene (TPE-R) with bisphenol A diphthalic anhydride (BPADA) using water as the polymerization solvent. A series of co-polymers were prepared incorporating 10, 20, 40 and 100 mol% of ABTMDS with the aromatic diamine TPE-R as the co-monomer. The synthesized co-polymers showed number average molecular weights in the range of 25,000–60,000. As expected the glass transition temperatures (T_gs) and moduli of the polymers were found to decrease with increasing amounts of the siloxane monomer and the homo-polymer containing only the siloxane diamine showing the lowest T_g (60 °C). The resulting polymers could be solution cast into strong and flexible membranes which showed significant decreases in water absorption and moisture permeability compared to the control polymer without siloxane groups. The polymers were characterized by FTIR, ¹³C and ¹H NMR, GPC, DSC and mechanical properties and structural comparisons were made with similar polymers made by standard solvent synthesis methods. Also cross-linked polymers were prepared by the reaction of ABTMDS with the aromatic homo-polymer control and their membrane properties were compared to those of the water synthesized siloxane co-polymers with a similar siloxane content.     

Untersuchungen zum System SmOCl/SeO2

Investigations on the System SmOCl/SeO₂ The existence of three ternary phases SmSeO₃Cl, SmSe₂₋O₅Cl, and SmSe₃O₇Cl is shown on the quasibinary line SmOClSeO₂. The phase barogram and the phase diagram are determined by total pressure measurements and DTA, respectively. SmSe₃O₇Cl melts peritectical at 340 ± 10 °C, SmSe₂O₅Cl melts peritectical at 560 ± 10 °C while SmSeO₃Cl shows no thermal effects up to 900 °C The data of enthalpies and entropies of the phases are evaluated from the total pressure measurements (Data see „Inhaltsübersicht”︁)     

电化学溶解金属铜制备纳米CuO

有机电解合成;铜电极;水解;电化学溶解金属铜制备纳米CuO     

Dimeric hexakis(4‐methyl­benzoato)­bis(1,10‐phenanthroline)didyspros­ium(III)

The title compound, [Dy₂(C₈H₇O₂)₆(C₁₂H₈N₂)₂], forms binuclear complexes, viz. di‐μ‐4‐methyl­benzoato‐κ⁴O:O′‐bis[bis(4‐methyl­benzoato‐κ²O,O′)(1,10‐phenanthroline‐κ²N,N′)dyspros­ium(III)] tetra‐μ‐4‐methyl­benzoato‐κ⁸O:O′‐bis[(4‐methyl­benzoato‐κ²O,O′)(1,10‐phenanthroline‐κ²N,N′)dyspros­ium(III)]. There are two independent binuclear com­plexes in the asymmetric unit, both of which are centrosymmetric. In one, the Dy^III ions are linked by two bridging 4‐­methyl­benzoate groups, while in the other, the Dy^III ions are linked by four bridging 4‐methyl­benzoate groups. The remaining 4‐methyl­benzoate groups and 1,10‐phenanthroline units coordinate to just one metal ion in bidentate modes.     

Reactions of [60]Fullerene with Di(azidomethyl) benzenes

Alargenumberofadditionsto[6O]fullerenehavebeeninvestigated.However,mostoftheworkhaveconcentratedontheformationofthemono-additionproductS0f[60]fullerene'-Thedevelopment0fselechveroutestomultipleadductShascurrentlybecomethefrontierinthechendstryof[60]fuIlerene'~'.FollowingtheaPplicahonoftether-directedremotefunctionalizati0ntotheregi0specificformati0nofthedi-andtriadductSof[60]fullerene,F.Diederichetal6alsodescribed'awayforthedirectdifunctionalizationof[60]fullerenebasedonacyclizationreachono…     

Novel Copolymers of Styrene. 12. Halogen Ring-Substituted Methyl 2-Cyano-3-Phenyl-2-Propenoates

Electrophilic trisubstituted ethylenes, halogen ring-substituted methyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO₂CH₃ (where R is 3-Br-4-CH₃O, 5-Br-2-CH₃O, 2-F-5-CH₃, 2-F-6-CH₃, 4-F-3-CH₃, 4-F-3-PhO, 2-F-5-I, 2-F-6-I, 2-F₃C, 4-F₃C) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and methyl cyanoacetate, and characterized by CHN analysis, IR, ¹H and ¹³C-NMR. All the ethylenes were copolymerized with styrene (M₁) in solution with radical initiation (ABCN) at 70°C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, ¹H and ¹³C-NMR. The order of relative reactivity (1/r ₁) for the monomers is 2-F-5-CH₃ (6.4) > 4-F-3-PhO (5.6) > 4-F₃C (4.8) > 3-Br-4-CH₃O (3.7) > 2-F-5-I (3.6) > 2-F₃C (2.2) > 2-F-6-I (2.1) > 5-Br-2-CH₃O (1.9) > 4-F-3-CH₃ (1.8) > 2-F-6-CH₃ (1.2). Relatively high T _g of the copolymers in comparison with that of polystyrene indicates a decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200-500°C range with residue (2–21% wt), which then decomposed in the 500–800°C range.