119mSn-Mössbauer-spektren von funktionell substituierten stannylenen und ihren stannio-komplexen mit chrom,molybdän- und wolfram-carbonyl-acceptoren

^119mSn Mössbauer data for a series of base-stabilized, intermolecularly associated tin(II) compounds ith O, Cl, P and As atoms bonded to tin are compared with isomer shifts (IS) and quadrupole splittings (QS) of their stannio complex derivatives with Cr, Mo and W carbonyls. Coordination at the tin lone-pair atom decreases IS to ca. 2.1 ± 0.2 mm s^?1 and increases the QS. QS values reflect the highly associated nature of the complexes (CO)₅MSn(Cl)E(t-Bu)₂ (M Cr, W; E  P, As) which are bridged through μ-E(t-Bu)₂ groups.     

Pulse radiolysis of one-electron oxidation of rare tricyclic nucleoside derivative

~~Pulse radiolysis of one-electron oxidation of rare tricyclic nucleoside derivative@赵红卫$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China @江致勤$Department of Chemistry, Tongji Unviersity!Shanghai 200092,China @窦大营$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China @吴铁一$Shanghai Institute of Nuclear Research, Chinese Academy of Sciences! Shanghai 201800,China @王文锋$Shanghai…     

Asymmetric Henry reaction catalyzed by C2-symmetric tridentate bis(oxazoline) and bis(thiazoline) complexes: metal-controlled reversal of enantioselectivity

[reaction: see text] C(2)-symmetric tridentate bis(oxazoline) and bis(thiazoline) ligands with a diphenylamine backbone have been investigated in the catalytic asymmetric Henry reaction of alpha-keto esters with different Lewis acids. Their Cu(OTf)(2) complexes furnished S enantiomers, while Et(2)Zn complexes afforded R enantiomers, both of them with higher enantioselectivities (up to 85% ee). Reversal of enantioselectivity in asymmetric Henry reactions was achieved with the same chiral ligand by changing the Lewis acid center from Cu(II) to Zn(II). The results show that the NH group in C(2)-symmetric tridentate chiral ligands plays a very important role in controlling both the yields and enantiofacial selectivity of the Henry products.     

A novel approach to carbon hollow spheres and vessels from CCl4 at low temperatures

Carbon hollow spheres (400-600 nm) and vessels (400 nm x 3000 nm) have been synthesized from sp3-CCl4 at 190 and 230 degrees C, respectively. The HRTEM images and Raman spectra reveal the sp2 nature of the as-obtained products, indicating that the transformation from carbon sp3 to sp2 occurs in the reactions. The possible mechanism has also been proposed.     

时间分辨激光荧光光谱分析方法研究——Ⅰ.铽、镝配合物共存时的分辨原理实验

本文对镝存在时铽的测定,进行了时间分辨激光荧光光谱分析方法的原理性实验。选择Tb、Dy-Sal乙醇溶液体系,测量了Tb~(3+)离子浓度范围为0.01～10μg/ml。Dy~(3+)离子浓度为0.1～100μg/ml范围内的荧光寿命。并得到了此范围内配合物离子浓度与荧光强度具有线性关系的结果。     

Degradation of 4-Chlorophenol using a Gas–Liquid Gliding Arc Discharge Plasma Reactor

The gas–liquid gliding arc discharge plasma is used directly to study degradation and dechlorination of 4-Chlorophenol (4-CP) in solution. The typical AC waveforms of discharge voltage and current revealed that the discharge behavior was not definitely periodic. The chemical oxygen demand (COD) abatement of 4-CP solution with stainless steel electrode is higher than that with aluminum or brass electrode; When air was used as carrier gas the COD abated from 1,679.2 to 190 mg/L (i.e., 88.68% abatement) after 76 min plasma treatment; Increasing gas–liquid mixing rate could also increase the degradation of 4-CP; adding appropriate amounts of Fe²⁺ or iron chips to the solution were found to be favorable for 4-CP degradation. The main intermediates of 4-CP degradation are p-benzoquinone, hydroquinone, 4-chlorocatechol, p-chloronitrobenzene, and ring cleavage products (acetic acid, glycol, propanone, and others). Furthermore, possible pathways of 4-CP degradation in solution are proposed.     

Preparation of Nano-Sized γ-Al2O3 Supported Iron Catalyst for Fischer-Tropsch Synthesis by Solvated Metal Atom Impregnation Methods

Two types of small iron clusters supported on γ-Al2O3-RT(dehydroxylated at room temperature) and γ-Al2O3-800 (dehydroxylated at 800 ℃) were prepared by solvated metal atom impregnation (SMAI) techniques. The iron atom precursor complex, bis(toluene)iron(0) formed in the metal atom reactor, was impregnated into γ-Al2O3 having different concentrations of surface hydroxyl groups to study the effect of surface hydroxylation on the crucial stage of iron cluster formation. Catalysts prepared in this way were characterized by TEM, M(o)ssbauer, and chemisorption measurements, and the results show that higher concentration of surface hydroxyl groups of γ-Al2O3-RT favors the formation of more positively charged supported iron cluster Fen/γ-Al2O3-RT, and the lower concentration of surface hydroxyl groups of γ-Al2O3-800 favors the formation of basically neutral supported iron cluster Fen/γ-Al2O3-800. The measured results also indicate that the higher concentration of surface hydroxyl groups causes the rapid decomposition of precursor complex, bis(toluene)iron(0), and favors the formation of relatively large iron cluster. Consequently, these two types of catalysts show different catalytic properties in Fischer-Tropsch reaction. The catalytic pattern of Fen/γ-Al2O3-RT in F-T reaction is similar to that of the unreduced α-Fe2O3 and that of Fen/γ-Al2O3-800 is similar to that of the reduced α-Fe2O3.     

氢化物发生—分光光度法测定染发剂中的微量铅

本文提出了用铁氰化钾将铅氧化至高价,再用氢化物发生-分光光度法测定铅的一种新方法。该法灵敏度高,简便快速,用于分析染发剂中的铅,取得了较好的效果。     

Stabilization and characterization of colloidal gas aphron dispersions

Colloidal gas aphrons (CGAs) are finding increasing application in water processing, bioseparation, bubble-entrained floc flotation, separation of oil from sand, etc. This article proposes an effective method of encapsulation to stabilize the CGA bubbles with silicic sol solution for their characterization. The stabilized CGA bubbles can keep shapes and sizes for at least 12 h; even the bubbles smaller than 25 mum can also be stabilized and exist for very long times. Effects of concentration and pH of silicic sol solution on CGA stabilization were studied. The optimal ranges of concentration and pH of silicic sol solution are 0.15-0.25 mol/dm(3) and 7-10, respectively. The bubble distortion behavior in disturbance and size distribution of CGAs were examined by using the stabilization method and photographic techniques.     

γ-氨丙基硅氧烷与八甲基环四硅氧烷乳液共聚合的研究

合成了γ-氨丙基七甲基环四硅型氧烷和γ-氨丙基甲基二乙氧基硅烷。研究了它们与八甲基环四硅氧烷在阳离子乳化剂及阴离子型乳化剂存在下的乳液共聚合反应。探讨了催化剂量、单体浓度、氨丙基含量及温度等对聚合的影响。