Enantioselective Iodolactonizations of 4-Pentenoic Acid Derivatives Mediated by Chiral Salen-Co(II) Complex

This work presents the salen-Co(II) complex catalyzed enantioselective iodolactonizations of various 4-pentenoic acid derivatives with good enantioselectivities (up to 83% ee).

反式和顺式-1，2-二氰-（4-乙基苯）乙烯结构的谱学分析

合成了2种新型的可溶性四氮杂卟啉中间体：反式-1，2二氰-（4-乙基苯）乙烯和顺式-1，2-二氰（4-乙基苯）乙烯。通过UV-Vis，FFIR，GC／MS，^1H NMR等方法对这2种化合物的结构进行了表征，给出了它们完整的结构信息。分析比较了顺、反异构体结构上的差异，分析两者的紫外-可见光谱（UV-Vis）、红外光谱（FTIR）和核磁共振光谱（^1H NMR）谱图的差异及其产生原因。

Efficiency improvement of organic light-emitting diodes using 8-hydroxy-quinolinato lithium as an electron injection layer

Organic light-emitting diodes (OLEDs) using tris-(8-hydroxy-quinolinato) aluminum (Alq(3)) as an emitter, 8-hydroxy-quinolinato lithium (Liq) as an electron injection layer, were prepared. Experimental results show that the efficiency of device with Liq is three times higher than that without Liq. The device using Liq as an injection layer is less sensitive in efficiency to the Liq thickness than that using LiF. In addition to the Alq3 based devices, Liq is also very effective as an electron injection layer for 4,4'-bis(2,2-diphenylvinyl)-1,1'-biphenyl based blue OLED and poly (2-methoxy,5-(2-ethyl-hexyloxy)-1,4-phenylenevinylene) based orange polymer OLED. (c) 2004 Elsevier B.V. All rights reserved.

Anti-human Immunodeficiency Virus-1 Constituents of the Bark of Poncirus trifoliata

A total of 36 compounds (1-36) were obtained from the stem bark of Poncirus trifoliata including three new prenylated flavonoids, (-)-5,4'-dihydroxy-7,8-[(3 '',4 ''-cis-dihydroxy-3 '',4 ''-dihydro)-2 '',2 ''-dimethylpyrano]-flavone (1), (-)-5,4'-dihydroxy-7,8-[(3 ''-hydroxy-4 ''-one)-2 '',2 ''-dimethylpyrano]-flavone (2), and (-)-5,4'-dihydroxy-7,8-[(cis-3 ''-hydroxy-4 ''-ethoxy-3 '',4 ''-dihydro)-2 '',2 ''-dimethylpyrano]-flavone (3). The new structures were elucidated by means of spectroscopic methods. Compounds 1-20 were evaluated for their anti-human immunodeficiency virus-1 (HIV-1) activity, in which 2 showed significant anti-HIV-1 activity with high therapeutic index (T1) of 143.65.

Elevated levels of urinary 8-hydroxy-2'-deoxyguanosine in male electrical and electronic equipment dismantling workers exposed to high concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans, polybrominated diphenyl ethers, and polychlorinated biphenyls

To investigate the occupational exposure levels to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs), indoor dust (n = 3) in workshops and hair samples from male workers (n = 64) were collected at two electrical and electronic equipment waste (E-waste) dismantling factories located in the LQ area in east China in July 11-13, 2006. Pre- and postworkshift urines (64 of each) were also collected from the workers to study oxidative damage to DNA using 8-hydroxy-2'-deoxyguanosine (8-OHdG) as a biomarker. The concentrations of PCDD/Fs, PCDD/F-WHO-TEQs, PBDEs, PCBs and PCB-WHO-TEQs were (50.0 +/- 8.1) x 10(3), 724.1 +/- 249.6, (27.5 +/- 5.8) x 10(6), (1.6 +/- 0.4) x 10(9), (26.2 +/- 3.0) x 10(3) pg/g dry weight (dw) in dust, and (2.6 +/- 0.6) x 10(3), 42.4 +/- 9.3, (870.8 +/- 205.4) x 10(3), (1.6 +/- 0.2) x 10(6), 41.5 +/- 5.5 pg/g dw in hair, respectively. The homologue and congener profiles in the samples demonstrated that high concentrations of PCDD/Fs, PBDEs, and PCBs were originated from open burning of E-waste. The 8-OHdG levels were detected at 6.40 +/- 1.64 mu mol/mol creatinine in preworkshift urines. However, the levels significantly increased to 24.55 +/- 5.96 mu mol/mol creatinine in postworkshift urines (p < 0.05). Then, it is concluded that there is a high cancer risk originated from oxidative stress indicated by the elevated 8-OHdG levels in the E-waste dismantling workers exposed to high concentrations of PCDD/Fs, PBDEs, and PCBs.

Light alkenes preparation by the gas phase oxidative cracking or catalytic oxidative cracking of high hydrocarbons

The preparation of light alkenes by the gas phase oxidative cracking (GOC) or catalytic oxidative cracking (COC) of model high hydrocarbons ( hexane, cyclohexane, isooctane and decane in the GOC process and hexane in the COC process) was investigated in this paper. The selection for the feed in the GOC process was flexible. Excellent conversion of hydrocarbons ( over 85%) and high yield of light alkenes ( about 50%) were obtained in the GOC of various hydrocarbons including cyclohexane at 750 degreesC. In the GOC process, the utilization ratio of the carbon resources was high; CO dominated the produced COX (the selectivity to CO2 was always below 1%); and the total selectivity to light alkenes and CO was near or over 70%. In the COC of hexane over three typical catalysts (HZSM-5, 10% La2O3/HZSM-5 and 0.25% Li/MgO), the selectivity to COX was hard to decrease and the conversion of hexane and yield of light alkenes could not compete with those in the GOC process. With the addition of H-2 in the feed, the selectivity to COX was reduced below 5% over 0.1% Pt/HZSM-5 or 0.1% Pt/MgAl2O4 catalyst. The latter catalyst was superior to the former catalyst due to its perfect performance at high temperature, and with the latter, excellent selectivity to light alkenes ( 70%) and the conversion of hexane (92%) were achieved at 850 degreesC ( a yield of light alkenes of 64%, correspondingly).

Determination of urinary oxidative DNA damage marker 8-hydroxy-2 '-deoxyguanosine and the association with cigarette smoking

8-hydroxy-2'-deoxyguanosine (8OHdG) has been widely used as a biomarker of oxidative DNA damage in both animal models and human studies. To evaluate the effect of cigarette smoking on oxidative stress, we studied the levels of urinary 8OHdG from smokers and non-smokers and investigated the association with cigarette smoking. The urinary 8OHdG concentrations were determinated by capillary electrophoresis with end-column amprometric detection (CE-AD) after a single-step solid phase extraction (SPE), and then quantitatively expressed as a function of creatinine excretion. To increase the concentration sensitivity, a dynamic pH junction was used and the focusing effect was obvious when using 30 mM phosphate (pH 6.50) as sample matrix. The limit of detection is 4.3 nM (signal-to-noise ratio S/N = 3). The relative standard deviation (R.S.D.) was 1.1% for peak current, and 2.3% for migration time. Based on the selected CE-AD method, it was found that the mean value of urinary 8OHdG levels in the smokers significantly higher than that in non-smokers (31.4 +/- 18.9 nM versus 14.4 +/- 7.6 nM, P = 0.0004; 23.5 +/- 21.3 mug g(-1) creatinine versus 12.6 +/- 13.2 mug g(-1) creatinine, P = 0.028). (C) 2004 Elsevier B.V. All rights reserved.

Microwave-assisted hydrothermal synthesis of hydroxy-sodalite zeolite membrane

A high quality pure hydroxy-sodalite zeolite membrane was successfully synthesized on an alpha-Al2O3 support by a novel microwave-assisted hydrothermal synthesis (MARS) method. Influence of synthesis conditions, such as synthesis time, synthesis procedure, etc., on the formation of hydroxy-sodalite zeolite membrane by MAHS method was studied by X-ray diffraction (XRD), scanning electron microscopy (SEM) and gas permeation measurements. The synthesis of hydroxy-sodalite zeolite membrane by MAHS method only needed 45 min and synthesis was more than 8 times faster than by the conventional hydrothermal synthesis (CHS) method. A pure hydroxy-sodalite zeolite membrane was easily synthesized by MAHS method, while a zeolite membrane, which consisted of NaX zeolite, NaA zeolite and hydroxy-sodalite zeolite, was usually synthesized by CHS method. The effect of preparation procedures had a dramatic impact on the formation of hydroxy-sodalite zeolite membrane and a single-stage synthesis procedure produced a pure hydroxy-sodalite zeolite membrane. The pure hydroxy-sodalite zeolite membrane synthesized by MARS method was found to be well inter-grown and the thickness of the membrane was 6-7 mum. Gas permeation results showed that the hydrogen/n-butane permselectivity of the hydroxy-sodalite zeolite membrane was larger than 1000. (C) 2004 Elsevier Inc. All rights reserved.

A comparative study of non-oxidative pyrolysis and oxidative cracking of cyclohexane to light alkenes

Naphthene is generally considered difficult to convert in traditional pyrolysis, but the ring rupture becomes fairly easy with the presence of oxygen in the gas phase oxidative cracking of the model compound, cyclohexane. About 86.8% conversion of cyclohexane, 43.7% yield of light alkenes, 6.6% yield of benzene and 14.3% yield of CO could be obtained at 750 degreesC, at which temperature the pyrolysis of cyclohexane was negligible, while at 850 degreesC, the total yield of alkenes, benzene and CO was as high as 80% (50%, 12% and 18%, respectively) with 98% conversion of cyclohexane. The gas phase oxidative cracking process could be run in an autothermal way (cyclohexane/O-2 mole ratio of 0.69-0.8 in theory), which would minimize energy consumption and capital costs of the whole process. CO prevailed in the produced CO, and the yield Of CO2 was always below 1%, which means about 90% Of CO2 emission by fuel burning in pyrolysis would be saved. The gas phase oxidative cracking process appears to be an environmentally benign and efficient route for light alkene production with naphthene rich feedstocks. (C) 2004 Published by Elsevier B.V.

Highly cis-1,4 selective polymerization of dienes with homogeneous Ziegler-Natta catalysts based on NCN-pincer rare earth metal dichioride precursors

The first aryldiimine NCN-pincer ligated rare earth metal dichlorides (2,6-(2,6-C6H3R2N=CH)(2)C6H3)LnCl(2)(THF)(2) (Ln = Y, R = Me (1), Et (2), Pr (3); R = Et, Ln = La (4), Nd (5), Gd (6), Sm (7), Eu (8), Tb (9), Dy (10), Ho (11), Yb (12), Lu (13)) were successfully synthesized via transmetalation between 2,6-(2,6-C2H3-R2N=CH)(2)-C6H3Li and LnCl(3)(THF)(1 similar to 3.5). These complexes are isostructural monomers with two coordinating THF molecules, where the pincer ligand coordinates to the central metal ion in a kappa C:kappa N: kappa N' tridentate mode, adopting a meridional geometry.