二苯基型及ω－唑基季磷盐的合成与生物活性

合成了具有不同阴离子的二苯基型季磷盐４ａ～ｈ和ω－唑基季磷盐６ａ～ｄ，并对它们的抑菌、除草及植物生长调节活性进行了研究。结果表明：部分季磷盐具有一定的生物活性。

The Effect of Titania Structure on Ni/TiO_2 Catalysts for p-Nitrophenol Hydrogenation

The catalytic hydrogenation of p-nitrophenol to p-aminophenol was investigated over Ni/TiO2 catalysts prepared by a liquid-phase chemical reduction method. The catalysts were characterized by inductively coupled plasma (ICP), X-ray powder diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectra (XPS) and temperature-programmed reduction (TPR). Results show that the titania structure has favorable influence on physio-chemical and catalytic properties of Ni/TiO2 catalysts. Compared to commercial Raney nickel, the catalytic activity of Ni/TiO2 catalyst is much superior, irrespective of the titania structure. The catalytic activity of anatase titania supported nickel catalyst Ni/TiO2(A) is higher than that of rutile titania supported nickel catalyst Ni/TiO2(R), possibly because the reduction of nickel oxide to metallic nickel for Ni/TiO2(A) is easier than that for Ni/TiO2(R) at similar reaction conditions.

Indomethacin but not a selective cyclooxygenase-2 inhibitor inhibits esophageal adenocarcinogenesis in rats

AIM： To evaluate the effects of indomethacin [dual cyclooxygenase （COX）-I/COX-2 inhibitor] and 3-（3,4-difluorophenyl）-4-（4-（methylsulfonyl） phenyl）- 2-（5H）-furanone （MF-tricyclic） （COX-2 selective inhibi- tor） in a rat experimental model of Barrett＇s esophagus and esophageal adenocarcinoma.METHODS： A total of 112 surviving post-surgery rats were randomly divided into three groups： the control group （n = 48）, which did not receive any treatment; the indomethacin group （n = 32）, which were given 2 mg/kg per day of the COX-I/COX-2 inhibitor; and the MF-tricyclic group （n = 32）, which received 10 mg/kg per day of the selective COX-2 inhibitor. Randomly se- lected rats were killed either 8 wk or 16 wk after sur- gery. The timing of the deaths was in accordance with a previous study performed in our group. Only rats that were killed at the times designated by the protocol were included in the study. We then assessed the histology and prostaglandin E2 （PGE2） expression levels in the rat esophagi. An additional group of eight animals that did not undergo esophagojejunostomy were included in order to obtain normal esophageal tissue as a control. RESULTS： Compared to a control group with no treat- ment （vehicle-treated rats）, indomethacin treatment was associated with decreases in ulcerated esophageal mucosa （16% vs 35% and 14% vs 17%, 2 mo and 4 mo after surgery, respectively; P = 0.021）, length of intestinal metaplasia in continuity with anastomosis （2 4- 1.17 mm vs 2.29 ＋ 0.75 mm and 1.25 4- 0.42 mm vs 3.5 4- 1.54 mm, 2 mo and 4 mo after surgery, respec- tively; P = 0.007）, presence of intestinal metaplasia beyond anastomosis （20% vs 71.4% and 0% vs 60%, 2 mo and 4 mo after surgery, respectively; P = 0.009）, severity of dysplasia （0% vs 71.4% and 20% vs 85.7% high-grade dysplasia, 2 mo and 4 mo after surgery, re- spectively; P = 0.002）, and adenocarcinoma incidence （0% vs 57.1% and 0% vs 60%, 2 mo and 4 mo after surgery, respectively; P 〈 0.0001）. Treatment with the selective COX-2 inhibitor, MF-tricyclic, did not prevent development of intestinal metaplasia or adenocarci- noma. In parallel, we observed a significant decrease in PGE2 levels in indomethacin-treated rats, but not in those treated with MF-tricyclic, at both 2 mo and 4 mo. Compared to control rats that did not undergo surgery （68 ＋ 8 ng/g, P = 0.0022 Kruskal-Wallis test） there was a significant increase in PGE2 levels in the esophageal tissue of the rats that underwent surgery either 2 mo （1332 ＋ 656 ng/g） or 4 mo （1121 ＋ 1015 ng/g） after esophagojejunostomy. However, no differences were found when esophageal PGE2 levels were compared 2 mo vs 4 mo post-esophagojejunostomy. At both the 2- and 4-mo timepoints, we observed a significant decrease in PGE2 levels in indomethacin-treated rat esophagi compared to those in either the control or MF-tricyclic groups （P = 0.049 and P = 0.017, respec- tively）. No differences in PGE2 levels were found when we compared levels in rats treated with MF-tricyclic to not-treated rats. CONCLUSION： In this rat model of gastrointestinal reflux, indomethacin was associated with a decrease in the severity of esophagitis and reduced development of esophageal intestinal metaplasia and adenocarcinoma.

A Structure-properties Study of MDI-based Hydrophilic Polyether-polyester Polyurethane

A series of segmented polyether-polyester polyurethane with amorphous hydrophilic soft segment domains were prepared from 4,4'- diphenylmethane diisocyanate (MDI), polybutylene adipate (Glycol) 2000 (PBA2000), and polyethylene glycol 1000 (PEG1000), with 1,4-butanediol (BDO) as the chain extender. Furthermore, several representative properties of the polyurethanes, such as moisture permeability, water resistance, hydrophilic property, and phase inversion temperature, were investigated. The studies show that the structure and concentration of soft segment have a remarkable effect on the main application properties of polyurethane. On the contrary, the functional properties of the polyurethane are almost not affected by its hard segment.

Enhanced Desorption of PAHs from Manufactured Gas Plant Soils Using Different Types of Surfactants

Surfactant enhanced remediation is thought to be an effective method for the remediation of soils polluted with hydrophoblc organic compounds. Desorption of polycyclic aromatic hydrocarbons （PAHs） from an abandoned manufactured gas plant （MGP） soil was evaluated using four eluting agents including Triton X-100 （TX100）, sodium dodecylbenzene sulfonate （SDBS）, rhamnolipid water solution （RWS） and rhamnolipid fermentation broth （RFB）. The weight solubilization ratios for acenaphthene and fluorene were in the order of TX100 〉 SDBS 〉 RWS 〉 RFB. The Sm value, which indicates the maximum amounts of surfactants adsorbed in the soil, was in the order of RWS 〉 RFB 〉 SDBS 〉 TX100. By using 8 g L-1 of TX100, SDBS and RWS and 100% of RFB, the T-PAHs removal for the MGP soil contaminated with 207.86 mg T-PAHs kg-1 dry soil was 48.0%, 45.7%, 1.9%, and 8.6%, respectively, while that decreased to 41.6%, 37%, 0.38%, and 1.3% for the soil contaminated with 3494.78 mg T-PAHs kg-1 dry soil. Only 8 g L-1 TX100 could remove all types of the 16 PAHs partly in the MGP soil, and the removal efficiencies of different PAHs ranged from 13% to 77.8%. The results of this study herein provide valuable information for the selection of TX100 surfactant for remediating PAH-contaminated soils in MGP.

Influences of fluorination on homoleptic iridium complexes with C^N=N type ligand to material properties, ligand orientation and OLED performances

Two new iridium complexes with C^N=N type ligand （i.e., Ir（BFPPya）3{tris[3,6-bis（4-fluorophenyl）pyridazine]iridium（III）} and Ir（BDFPPya）3{tris[3,6-bis（2,4-di-fluorophenyl）pyridazine]iridium（III）}） attaching with fluorine atoms, were synthesized and the effects of fluorination on the material properties and device performance were investigated. Compared with our previously reported fluorine-free analogue material, that is Ir（BPPya）3{tris[3,6-bis（phenyl）pyridazine]iridium（III）}, blue shifts in the emission spectra as well as in the long wavelength region of the absorptions were observed. The photoluminescence quantum yield （PLQY） （0.44 and 0.84 vs. 0.29）, phosphoresces lifetime （0.88 and 1.31 vs. 0.66 gs）, and oxidation potential （1.10 and 1.37 vs. 0.95 V） increased obviously after fluorinating the ligand. In contrast, the thermal stability of the iridium complexes decreased slightly （Td： 435 and 402 vs. 440 ℃）. In the density functional theory （DFT） calculations, by comparing the steric shape of the three ligands within one optimized molecule, orientational differences among the complexes were observed. In OLED device studies, bluish green electroluminescence with peak emission of 500 nm, using the electron-transporting host of TPBI [2,2＇,2＂-（1,3,5-benzenetriyl）tris（1-phenyl-lH-benzimidazole）] and the most fluorinated dopant of Ir（BDFPPya）3, was achieved with maximum efficiency of 20.3 cd/A. On one hand this efficiency is not satisfactory considering a high PLQY of 0.84. On the other hand with the similar device structure, that the （HOMO-LUMO）s of all the dopants are wrapped within that of the host TPBI, and all the triplet energies of the dopants are smaller than that of the host TPBI, it is abnormal that the ordering of device efficiencies is contradictory to that of PLQY. Assisting with the phosphorescent spectrum of TPBI and the absorption spectra of the dopant, the contradiction was interpreted reasonably.

Tetrahydroxy stilbene glucoside improved the behavioral disorders of APP695V717l transgenic mice by inhibiting the expression of Beclin-1 and LC3-Ⅱ

OBJECTIVE:To observe the effect of tetrahydroxy stilbene glucoside(TSG) on the behavior of APP695V717 I transgenic mouse models and the expression of autophagy-associated proteins Beclin-1and LC3-Ⅱ.METHODS:Forty 3-month-old APP695V717 I transgenic mice were randomized equally into either a TSG group(n = 20) or a model group(n = 20).A normal control group consisted of C57BL/6J mice of the same age and background(n = 20).The TSG group received TSG intragastric administration for1 month.Behavior was measured using the Morris water maze and the Y-maze tests.Changes in protein expression and mRNA of autophagy-associated Beclin-1 and LC3-Ⅱ in mice hippocampus were detected by western blot and Reverse Transcription-Polymerase Chain Reaction(RT-PCR) analyses.RESULTS:The number of electric-stimulus escapes significantly increased and the Morris water maze test showed prolonged escape latency,greater swimming distance,less time taken to cross the exact former platform location in the model group,and increased mRNA and protein expressions of Beclin-1 and LC3-Ⅱ compared with the control group(P < 0.05).The TSG group showed a decrease in the number of electric-stimulus escapes,shorter escape latency and swimming distance,greater time taken to cross the exact former platform location,and decreased mRNA and protein expressions of Beclin-1 and LC3-Ⅱ compared with the model group(P< 0.05).CONCLUSION:These results indicate that tetrahydroxy stilbene glucoside can decrease expressions of Beclin-1 and LC3-Ⅱ in the autophagy pathway.It can attenuate injury to endoplasmic reticulum functions caused by Ab neurotoxicity,improving learning,memorizing,and spatial orientation behavior in mice.