EPR studies on H-abstraction from methylbenzenes by “magic blue” reagent

After mixing a methylbenzene 4 with “magic blue” solution in F113 (CClF₂CCl₂F) containing bis{perfluoro[1-(2-fluorosulfonyl)ethoxy]ethyl}nitroxide 2 and perfluoro-1-nitroso-1-[1-(2-fluorosulfonyl)ethoxy]ethane 3 at room temperature, benzylic H-atom of 4 could be selectively abstracted by 2, and benzyl radical 5 thus generated was immediately trapped by 3. Based on hyper-fine splitting constants (hfsc), the structure of the spin adducts perfluoro[1-(2-fluorosulfonyl)ethoxy]ethyl benzyl nitroxides 6 derived from seven methylbenzenes have been identified. The mechanism of the H-abstraction/spin trapping process is also discussed.     

Adsorption and reactions of ethanol on Mo2C/Mo(1 0 0)

The adsorption, desorption and dissociation of ethanol have been investigated by work function, thermal desorption (TPD) and high resolution electron energy loss (HREELS) spectroscopic measurements on Mo₂C/Mo(1 0 0). Adsorption of ethanol on this sample at 100 K led to a work function decrease suggesting that the adsorbed layer has a positive outward dipole moment By means of TPD we distinguished three adsorption states, condensed layer with a Tp = 162 K, chemisorbed ethanol with Tp = 346 K and irreversibly bonded species which decomposes to different compounds. These are hydrogen, acetaldehyde, methane, ethylene and CO. From the comparison of the Tp values with those obtained following their adsorption on Mo₂C it was inferred that the desorption of methane and ethylene is reaction limited, while that of hydrogen is desorption limited process. HREEL spectra obtained at 100 K indicated that at lower exposure ethanol undergoes dissociation to give ethoxy species, whereas at high exposure molecularly adsorbed ethanol also exists on the surface. Analysis of the spectral changes in HREELS observed for annealed surface assisted to ascertain the reaction pathways of the decomposition of adsorbed ethanol.     

2-(2-氯乙氧基)乙酸酯的合成及性质

在探索 2 氧代 1 ,4 二氧六环应用的实验中 ,我们发现利用 2 氧代 1 ,4 二氧六环与氯化亚砜及一些低碳醇反应 ,可以使 2 氧代 1 ,4 二氧六环发生开环反应 ,生成一类新的有机氯代醚酯类化合物——— 2 ( 2 氯乙氧基 )乙酸酯。其中 ,Ｒ分别为甲基、乙基、丙基、异丙基、丁基和仲丁基。该类化合物在酸性、碱性条件下水解 ,可以得到不同的产物。由于 2 氧代 1 ,4 二氧六环可由一缩二乙二醇经催化脱氢得到[1 ] ,而一缩二乙二醇又是工业上制备乙二醇的副产物。因而开展有关 2 ( 2 氯乙氧基 )乙酸酯的合成及性质方面的研究可为一缩二乙二…     

Ethoxy Groups on ZrO2, CuO,and CuO/ZrO2 Studied by IR Spectroscopy

The formation, properties, decomposition and reactions of ethoxy groups on ZrO₂, CuO, and CuO/ZrO₂ were followed by IR spectroscopy. The reaction of ethanol with terminal Zr-OH groups leads to the formation of monodendate ethoxy groups (type I), whereas the reaction of ethanol with tribridged Zr-OH grups results in the formation of bidendate ethoxyls (type II). In both cases, water is produced. Ethoxy groups of type II were also formed on CuO. The type of the surface species detected after interaction of ethanol with CuO/ZrO₂ was the same as detected for both oxides (i.e., ZrO₂ and CuO) separately. This suggests that no new phase was formed in the mixed oxide system. At higher temperatures, ethoxy groups were oxidized forming acetate ions. Gaseous ethanol present in the cell was oxidized to acetaldehyde without the intermediacy of ethoxy groups.     

聚[(甲氧基乙氧基乙氧基)1.0(乙氧基吡咯烷酮)1.0]膦腈的合成及性能研究

用三氯化铝催化六氯三聚膦腈开环聚合制得线性聚二氯膦腈(PDCP), 通过PDCP磷原子上的亲核取代反应, 合成了新的水溶性高分子聚[(甲氧基乙氧基乙氧基)_1.0(乙氧基吡咯烷酮)_1.0]膦腈(P3), 用³¹P NMR, ¹H NMR, ¹³C NMR和IR对其结构进行了确证, 用DSC测定了其玻璃化转变温度T_g和熔融温度T_m, 用蒸汽压渗透法(VPO)测定了其数均分子量. 改进了聚二(乙氧基吡咯烷酮)膦腈(P2)的合成方法. 体外降解实验表明, P3具有和P2类似的pH响应性降解行为, 降解速率在pH=5.0时最快, 而在pH=7.4和8.0时较慢. P3在所测试的3个pH缓冲溶液中均比P2降解慢. 用³¹P NMR、薄层色谱(TLC)和滴定法对降解产物进行了检测, 初步推断了P3在不同pH介质中的水解机理, 其在pH=5.0的缓冲溶液中的降解, 除侧链断裂外, 聚膦腈的骨架也裂解; 而在pH=7.4和8.0时的降解仅为侧链的断裂. 用噻唑蓝(MTT)比色法进行的体外细胞毒性评价实验表明, P3及其在pH=5.0的缓冲溶液中降解49 d后的产物均对细胞表现出了很好的生物相容性, 而且其降解产物在浓度为800 μg/mL时还表现出一定的促进细胞增殖作用.     

Unusual open chain quinolinyl peroxol and its alcohol counterpart obtained through a modified Skraup–Doebner–Von Miller quinoline synthesis: theoretical studies and complete 1H‐ and 13C‐NMR assignments

Because of their extreme instability, it is generally difficult to synthesize and fully characterize open chain peroxides, also known as peroxols. In our attempt to investigate the mechanism of the Skraup–Doebner–Von Miller quinoline synthesis, we were able to obtain an unusual open chain peroxy‐quinoline, namely, 4‐(8‐ethoxy‐2,3‐dihydro‐1H‐cyclopenta[c]quinolin‐4‐yl)butane‐1‐peroxol (1), and its alcohol counterpart, namely 4‐(8‐ethoxy‐2,3‐dihydro‐1H‐cyclopenta[c]quinolin‐4‐yl)butan‐1‐ol (2) obtained as a side product during the same reaction. Although structurally similar, these two compounds appeared to display some very distinct physical and spectroscopic characteristics. This work reports detailed NMR studies and full ¹H and ¹³ C NMR assignments for these two compounds. These assignments are based upon the analysis of the NMR spectra of these compounds including ¹H, ¹³ C, COSY, gHSQC and gHMBC. The effect of the peroxide functional group on the chemical shift of neighboring carbons and protons was also investigated by comparing the NMR data of these two compounds. Furthermore, the effects of potential hydrogen bondings in 1, 2, and possible 1–1 dimer, 2–2 dimer and in prototypical model systems, as well as the stability of these compounds, were investigated computationally. The computed dissociation energies and NMR data support the interpretation of the experimental data. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis of novel biodegradable poly(ethylene glycol) analogue:Water-soluble aliphatic polyester with pendant oligo(ethylene glycol) chains

A novel poly(ethylene glycol)(PEG) analogue composed of aliphatic polyester backbone and pendant oligo(ethylene glycol) short chains is reported.The PEG analogue is a copolymer synthesized by ring-opening alternating copolymerization of succinic anhydride with 2-((2-(2-metho xyethoxy)ethoxy)methyl)oxirane.The structure of the copolymer was confirmed by ~1H NMR spectrum.The effects of the monomer feed ratio on the copolymerization were studied and the polymerization mechanism was given.The PEG analogue di...     

正相高效液相色谱法分离检测壬基酚和短链壬基酚聚氧乙烯醚

建立了一种以正相高效液相色谱等强度洗脱分离检测壬基酚和短链壬基酚聚氧乙烯醚的新方法。采用Cosmosil5SL-Ⅱ(250mm×4.6mmi.d,5μm)色谱柱,以乙酸乙酯-乙醇为流动相,流速1.0mL/min,281nmUV检测,在10min内可分离检测p-壬基酚以及短链壬基酚聚氧乙烯醚混合物的3种主要组分。运用本方法对NP,NPnEO(n=1~3)进行测定的相对标准偏差分别为1.4%、1.6%、2.5%和1.4%;检出限分别为0.1mg/L(NP)和0.5mg/L(NPnEO),重复性好且灵敏度高。