Friedel-Crafts Polymers. 6. Friedel-Crafts Polycondensation of p-Xylylerte Dibromide with Salicylic Acid and β-Resorcyiic Acid

Polymers were prepared by condensing p-xylylene dibromide separately with salicylic acid and β-resorcylic acid in the presence of anhydrous ferric chloride in dioxane. The polymer samples_were characterized by elemental analysis, by IR spectral study, by M determined by vapor pressure osmometry, by nonaqueous conducto-metric titration in pyridine, by TGA in air, and by viscosity measurements of polymer solutions in DMF. Polymeric metal chelates of Cu²⁺, Co²⁺, Zn²⁺, Ni²⁺, and Fe³⁺ with polymer samples were prepared and characterized by elemental analysis, by IR spectral study, and by TGA in air. The chelation ion-exchange properties of the polymer samples were studied by employing the batch equilibration method.     

湿化学法制备硅纳米线阵列及其光电化学产氢性能分析

为了探究不同方法条件下制备的硅纳米线阵列电极产氢性能异同,文中分别采用了两步金属辅助催化无电刻蚀法、一步金属辅助催化无电刻蚀法以及阳极氧化法来制备硅纳米线阵列用作为光电分解水电池光阴极材料。通过FESEM、XRD和UVVis-IR DRS等手段对实验样品的形貌、晶型、减反性表征,发现相比于其他2种方法所得硅纳米线样品,两步金属辅助催化无电刻蚀法制备的硅纳米线结构晶型保持更好,表面缺陷更少。光电化学测试表明两步金属辅助催化无电刻蚀法制备的硅纳米线光电化学性能表现最优,其光电流密度值是一步法的4倍,阳极氧化法的40倍;转移电荷电阻仅是一步法制备的硅纳米线阵列阻值的1/3,阳极氧化法制备的1/1 000。     

Akt is involved in the inhibition of cell proliferation by EGF

Axin is a negative regulator of the Wnt/beta-catenin pathway and is involved in the regulation of axis formation and proliferation. Involvement of Axin in the regulation of other signaling pathways is poorly understood. In this study, we investigated the involvement of Akt in growth regulation by Axin in L929 fibroblasts stimulated by EGF. Akt activity was increased by EGF treatment and Ras activation, respectively. Both the EGF- and Ras-induced Akt activations were abolished by Axin induction, as revealed by both Western blot and immunocytochemical analyses. The proliferation and Akt activation induced by EGF were decreased by Axin induction, and the effects of EGF were abolished by treatment of an Akt-specific inhibitor. Therefore, Axin inhibits EGF-induced proliferation of L929 fibroblasts by blocking Akt activation.     

铂修饰光阴极及其在纳晶太阳能电池中的应用

分别用真空镀膜法、热分解法和电化学法制备了铂金修饰导电玻璃,并以此作为光阴极组装了染料敏化纳晶TiO₂太阳能电池.用SEM观察了铂金修饰导电玻璃表面形貌,发现用真空镀膜法制备的铂金膜结构缺陷多、不均匀,存在较多的污点.用热分解法制备的铂金膜具有多孔状结构,但存在较多的有机物分解的残留物.用电镀法制备的铂金膜结构均匀、排列规则、缺陷少、污染少.测定了所制备铂金膜的电阻,结果表明由电镀法所制得的铂金膜电阻最小,用热解法和真空镀膜法制得的铂金膜电阻较大.测定了DSSC电池的光电性能,发现用电镀法制得的铂金膜的催化性能最好,大大提高了DSSC电池的性能;其次是热分解法,由真空镀膜法制备的铂金膜对电池的性能没有多大改善.     

Friedel-Crafts Polymers. 5. Friedel-Crafts Polycondensation of p-Xylylene Dichloride with Salicylaldehyde and o-Hydroxyacetophenone

Polymers were prepared by condensing p-xylylene dichloride (PXDC) separately with salicylaldehyde (SAL) and o-hydroxy-acetophenone (OHAC) in the presence of anhydrous ferric chloride in dioxane. The polymer samples were characterized by elemental analysis, measurement of their M by vapor pressure osmometry, by nonaqueous conductometric titration in pyridine, by IR spectral study, by TGA in air, and by viscometric study in DMF. The ion-exchange capacities of these polymeric ligands for selected metal ions were measured by the batch equilibration method and compared. Polymeric metal chelates of PXDC-SAL and PXDC-OHAC polymer samples with Cu^{2 +}, Ni²⁺, Co²⁺, Fe³ and Zn^{2 +} were prepared and characterized by elemental analyses, by IR spectral study, and by thermal analyses.     

Determination of Mg, Ti and Cl in Ziegler-Natta catalysts by WDXRF

A method for determination of Mg, Ti and Cl in Ziegler-Natta (ZN) catalysts by wavelength dispersive X-ray fluorescence (WDXRF) spectrometry was developed. For comparative reasons, Ti was determined by spectrophotometry, Mg by complexometry and Cl by argentometric titration. Direct pressing was shown to be unsuitable for sample preparation due to catalyst decomposition. For Ti and Mg measurements, catalyst samples were calcinated at 1000 °C and pressed at 275 MPa. Their determination by the fundamental parameters based on the Ti Ka line measurement was shown to be equivalent to those results obtained by univariate calibration or by the classical methods. Cl was determined by aqueous extraction, followed by deposition on a support. Chloride loss was observed. Fixation of Cl as AgCl on polytetrafluoroethylene (FHLC) millipore membrane afforded the best results. Nevertheless, measurements by WDXRF were shown to be inferior to those obtained by argentometric titration.     

Synthesis, properties, and applications of urethane-modified acrylated poly(ester-amide)s

Epoxy resin-based unsaturated poly(ester-amide) resins (UPEAs) were treated with acryloyl chloride to afford acrylated UPEAs resins (AUPEAs). Urethane-based acrylated poly(ester-amide)s prepared by reaction with diisocyanate were characterized by elemental analysis, by molecular weight determination (by vapour pressure osmometry), by IR spectral study, and by thermogravimetry. The curing of interacting blends was monitored by differential scanning calorimetry (DSC). On the basis of DSC data in-situ glass-reinforced composites were prepared from the resulting materials and their mechanical, electrical, and chemical properties were characterized. Unreinforced blends were characterized by thermogravimetry.     

Optical resolution methods

Despite the large number of elaborate enantioselective syntheses for the preparation of a single enantiomer to achieve industrial and scientific goals, the separation and purification of enantiomers (components of racemic compounds) is also necessary. Hence, we present the most often used thought-provoking modern methods based on momentous recognitions (e.g. spontaneous resolution, induced crystallization, resolution by formation of diastereomers, resolution by formation of non-covalent diastereomers, resolution by diastereomeric salt formation, resolution by diastereomeric complex formation, "half equivalent" methods of resolution, separation by crystallization, separation by distillation, separation by supercritical fluid extraction, resolution with mixtures of resolving agents, resolution with a derivative of the target compound, enantioselective chromatography, resolution by formation of covalent diastereomers, resolution by substrate selective reaction, kinetic resolution without enzymes, kinetic resolution by enzyme catalysis, hydrolytic and redox enzymes, kinetic and thermodynamic control, resolutions combined with 2nd order asymmetric transformations, enrichment of partially resolved mixtures, role of the solvent and methods of optimization in the separation of diastereoisomers, non-linear effects and selected examples of resolution on an industrial scale).     

牛蒡寡糖的分离纯化及结构研究

以菊科植物牛蒡(ArctiumlappaL.)的等外根为材料,经热水浸提、木瓜蛋白酶-Sevag法脱蛋白、乙醇沉淀和SephadexG-50凝胶柱层析分离纯化,得到水溶性的牛蒡寡糖(BOS₂).采用化学分析方法研究了BOS₂的理化性质,并通过TLC,GC-MS,HP-GPC,UV,IR,¹HNMR及¹³CNMR等对BOS₂的纯度、结构和组成进行表征.结果表明,BOS₂由果糖和葡萄糖组成,摩尔比约为12∶1,纯度较高,为均一性组分;由12个呋喃型的果糖以β(2→1)糖苷键相连,1个吡喃型的葡萄糖以α(1→2)糖苷键连接在果糖末端的线性直链结构,是一种菊糖构型的低聚果糖.     

Novel Synthetic Approach to Thiophosphinates Incorporating Different N-Heterocycles

Eight new cycloiminylidenamidothiophosphinates incorporating pyridine, pyrimidine, thiazole, and benzothiazole heterocycles were synthesized by phosphorylation of the quaternary iminium salts of the heterocycles by diphenylchlorophosphine followed by in situ sulfurization by elemental sulfur. Crystalline solid products were well characterized by elemental analysis and NMR spectroscopy.     

Methyl-substituted trans-1,2-cyclohexanediamines as new ligands for oxaliplatin-type complexes

Three different pathways for the synthesis of substituted trans-(±)-1,2-cyclohexanediamines as new ligands for oxaliplatin-type compounds are presented. The different synthetic routes lead (i) by the synthesis of the compound via ortho-bromination of a substituted cyclohexanone followed by reaction with hydroxylamine and reduction by hydrogen, (ii) by addition of azide to cyclohexene mediated by manganese(III) acetate and reduction by hydrogen, or (iii) by trans-dihydroxylation of cyclohexene, and subsequent conversion into the respective mesylate or tosylate, followed by substitution by azide, and reduction in the case of 4-methyl-trans-(±)-1,2-cyclohexanediamine to a preferentially equatorially, mainly axially, or exclusively equatorially or axially oriented 4-methyl group, respectively.     

湿化学法制备硅纳米线阵列及其光电化学产氢性能分析

为了探究不同方法条件下制备的硅纳米线阵列电极产氢性能异同,文中分别采用了两步金属辅助催化无电刻蚀法、一步金属辅助催化无电刻蚀法以及阳极氧化法来制备硅纳米线阵列用作为光电分解水电池光阴极材料.通过FESEM、XRD和UV-Vis-IRDRS等手段对实验样品的形貌、晶型、减反性表征,发现相比于其他2种方法所得硅纳米线样品,两步金属辅助催化无电刻蚀法制备的硅纳米线结构晶型保持更好,表面缺陷更少.光电化学测试表明两步金属辅助催化无电刻蚀法制备的硅纳米线光电化学性能表现最优,其光电流密度值是一步法的4倍,阳极氧化法的40倍;转移电荷电阻仅是一步法制备的硅纳米线阵列阻值的1/3,阳极氧化法制备的1/1000.     

Effect of sample handling on alkaloid and mineral content of aqueous extracts of greater celandine (Chelidonium majus L.)

The authors examined the extraction of alkaloids from the greater celandine (Chelidonium majus L.) by different methods (traditional pressing and tea making, microwave and supercritical fluid extraction). The extractants were water and propylene glycol. For comparison of the extraction methods, the yield was evaluated according to total alkaloid content measured by spectroscopy. The highest alkaloid yield was obtained by microwave extraction and by making tea. Distribution of the components was studied by thin-layer chromatography and densitometry. The concentration and the ratio of alkaloid components in extracts are significantly different depending on the extraction method. The solution obtained by supercritical fluid extraction contains coptisine and chelidonine, while berberine could be obtained by microwave extraction only. Extracts with high coptisine content were obtained by supercritical fluid extraction, followed by pressing and microwave extraction. Mineral element content of the drug and extracts was also determined by inductively coupled plasma atomic emission spectrometry. Element content (Na, Ca, Fe) was found to be highest in microwave extracts.     

New designer drug 2,5-dimethoxy-4-ethylthio-beta-phenethylamine (2C-T-2): studies on its metabolism and toxicological detection in rat urine using gas chromatography/mass spectrometry

Studies are described on the metabolism and the toxicological analysis of the phenethylamine-derived designer drug 2,5-dimethoxy-4-ethylthio-beta-phenethylamine (2C-T-2) in rat urine using gas chromatography/mass spectrometry (GC/MS) after enzymatic cleavage of conjugates, liquid-liquid extraction and derivatization. The structures of 14 metabolites were assigned tentatively by detailed interpretation of their mass spectra. Identification of these metabolites indicated that 2C-T-2 was metabolized by sulfoxidation followed by N-acetylation and either hydroxylation of the S-ethyl side chain or demethylation of one methoxy group, O-demethylation of the parent compound followed by N-acetylation and sulfoxidation, deamination followed by reduction to the corresponding alcohol followed by partial glucuronidation and/or sulfation or by oxidation to the corresponding acid followed either by partial glucuronidation or by degradation to the corresponding benzoic acid derivative followed by partial glucuronidation. Furthermore, 2C-T-2 was metabolized by N-acetylation of the parent compound followed either by O-demethylation and sulfoxidation or by S-dealkylation, S-methylation and sulfoxidation. The authors' systematic toxicological analysis (STA) procedure using full-scan GC/MS after acid hydrolysis, liquid-liquid extraction microwave-assisted acetylation allowed the detection of an intake of a dose of 2C-T-2 in rat urine, which corresponds to a common drug users' dose. Assuming similar metabolism, the described STA procedure should be suitable for proof of an intake of 2C-T-2 in human urine.     

Luminescent,optical, magnetic and metamaterial behavior of cerium complexes

The complexes of cerium with nitrogen, oxygen and sulfur donor ligands were prepared by conventional method. These newly synthesized complexes were characterized by FTIR, UV–Vis, DART Mass, TGA, PXRD, SEM and TEM techniques. The magnetic studies were carried out by the vibrating sample magnetometer. The optical constants were measured by absorption and reflection spectra as a function of wavelength. The concentration dependence of refractive index and absorption was observed by the experimental method, which reveals that these parameters are affected by change in concentration. The optical band gap obtained from Tauc-plot indicates its probability to be a good semiconductor. The luminescence behavior of these cerium complexes was observed by the absorption and emission spectra and the emission life time was calculated by their life time spectra.     

Phosphaquinomethane and phosphathienoquinomethanes, and their anion radicals

Phosphaquinomethane and phosphathienoquinomethanes sterically protected by Mes* (Mes* = 2,4,6-tri-tert-butylphenyl) were synthesized by 1,6-dehydration of the corresponding 4-phosphinoaryl carbinols. Structural similarities to the conventional quinoid compounds were revealed by 1H, 13C, and 31P NMR study and further confirmed by X-ray crystallography of the phosphathienoquinomethane. The corresponding anion radicals were generated by reduction with sodium, and considerable delocalization of an unpaired electron was demonstrated by EPR.     

Method extension study to validate applicability of AOAC Official Method 996.14 Assurance polyclonal enzyme immunoassay for detection of Listeria monocytogenes and related Listeria spp. from environmental surfaces: collaborative study

Test portions from 3 environmental surface types, representative of typical surfaces found in a food production facility, were analyzed by the Assurance Listeria Polyclonal Enzyme Immunoassay (EIA) and the U.S. Department of Agriculture/Food Safety and Inspection Service (USDA/FSIS) culture method for Listeria monocytogenes and related Listeria species. In all cases, naturally contaminated environmental test samples were collected from an actual food production facility by sponge or swab. Test samples from concrete surfaces were collected by both swab and sponge; sponge test samples were collected from rubber surfaces, and swabs were used to sample steel surfaces. Test portions from each surface type were simultaneously analyzed by both methods. A total of 23 collaborators, representing government agencies, as well as private industry in both the United States and Canada, participated in the study. During this study, a total of 550 test portions and controls was analyzed and confirmed, of which 207 were positive and 336 were negative by both methods. Six test portions were positive by culture, but negative by the EIA. Three test portions were negative by culture, but positive by the EIA. Two test portions were negative by EIA and by culture, but confirmed positive when EIA enrichment broths were subcultured to selective agars. The data reported here indicate that the Assurance Listeria EIA method and the USDA/FSIS culture method are statistically equivalent for detection of L. monocytogenes and related Listeria species from environmental surfaces taken by sponges or swabs.     

Determination of ni,zn and al in bronzes and brasses after determining cu-pb-sn-sb by controlled-potential electrolysis

A method is given, which allows nickel, zinc and aluminium to be determined in the solution remaining after the determination of copper, lead, tin and antimony by controlled-potential electrolysis. Nickel is precipitated by dimethylglyoxime, zinc is deposited by controlled-potential electrolysis and aluminium is precipitated first by oxine and then by ammonium benzoate.     

Method extension study to validate applicability of AOAC Official Method 997.03 visual immunoprecipitate assay (VIP) for Listeria monocytogenes and related Listeria spp. from environmental surfaces: collaborative study

Test portions from 3 environmental surface types, representative of typical surfaces found in a food production facility, were analyzed by the Visual Immunoprecipitate assay (VIP) and the U.S. Department of Agriculture/Food Safety and Inspection Service (USDA/FSIS) culture method for Listeria monocytogenes and related Listeria species. In all cases, naturally contaminated environmental test samples were collected from an actual food production facility by sponge or swab. Test samples from concrete surfaces were collected by both swab and sponge; sponge test samples were collected from rubber surfaces, and swabs were used to sample steel surfaces. Test portions from each surface type were simultaneously analyzed by both methods. A total of 27 laboratories, representing government agencies as well as private industry in both the United States and Canada, participated in the study. During this study, a total of 615 test portions and controls was analyzed and confirmed, of which 227 were positive and 378 were negative by both methods. Nine test portions were positive by culture, but negative by the VIP. Five test portions were negative by culture, but positive by the VIP. Four test portions were negative by VIP and by culture, but confirmed positive when VIP enrichment broths were subcultured to selective agars. The data reported here indicate that the VIP method and the USDA/FSIS culture method are statistically equivalent for detection of L. monocytogenes and related Listeria species from environmental surfaces taken by sponges or swabs.