A mild, efficient and selective deprotection of t-butyldimethylsilyl-protected phenols using cesium carbonate

A mild and efficient method for the deprotection of aryl t-butyldimethysilyl (TBS) ethers is described. The protecting group TBS could be cleaved from aryl silyl ethers using cesium carbonate in DMF-H₂O at room temperature to give the corresponding phenols in excellent yields. The reaction conditions allowed selective deprotection of aryl TBS-protected phenols in the presence of TBS, phenyloxycarbonyl or tetrahydropyranyl-protected alcohols.     

Simultaneous determination of all-trans, 9-cis, 13-cis retinoic acid and retinol in rat prostate using liquid chromatography-mass spectrometry

Since retinoic acid (RA) and RA receptors are key developmental regulators during organogenesis, they might participate in the abnormal development of the prostate caused by early estrogen exposure. In order to test this assumption, a sensitive analytical method that can differentiate 9-cis, 13-cis, and all-trans RA in small tissue samples ( approximately 8 mg) is required. Since retinol is the metabolic precursor to RA, simultaneous quantification of retinol would also provide valuable information. Here, we report a liquid chromatography-mass spectrometry method for simultaneous determination of retinol and 9-cis, 13-cis, and all-trans RA in rat prostate. Mass spectrometric signal responses for RA were compared using positive ion atmospheric-pressure chemical ionization (APCI) and electrospray, as well as positive ion and negative ion APCI. Positive ion APCI was selected for all subsequent analysis for its better sensitivity, and to provide simultaneous determination of retinol and RA. Ventral prostate tissue samples were homogenized and extracted following simple protein precipitation without derivatization. Baseline separation of 9-cis, 13-cis, and all-trans RA standards was obtained by using a non-porous silica C18 column. Selected ion monitoring of the ions m/z 301 and m/z 269 was carried out for mass spectrometric quantitative analysis. The ion of m/z 301 corresponded to the protonated molecule of RA, whereas the ion of m/z 269 corresponded to loss of water or acetic acid from the protonated molecule of retinol or the internal standard retinyl acetate respectively. The method has a linear response over a concentration range of at least three orders of magnitude. The limit of quantitation was determined to be 702 fmol all-trans RA injected on-column. The method showed excellent intra- and inter-assay reproducibility and good recovery, and is suitable for analyzing RA and retinol in small tissue samples (approximately 8 mg).     

用θ-2θ型衍射仪测定溶液结构的新方法

叙述了用θ－２θ型Ｘ射线衍射仪精确测定电解质溶液结构的新实验技术。设计制作了具有恒温功能的超厚液体样品池，并建立了样品池窗口强度的校正方法。优化了液体Ｘ射线衍射数据和结构参数精细化的计算机程序，获得了非常令人满意的实验结果。由θ－２θ型Ｘ射线衍射仪精确测定的径向分布函数与θ－θ型衍射仪自由散射比较，表明ＤＲＦ分辨率有所提高。     

Anti-inflammatory activity of new guaiane type sesquiterpene from Wikstroemia indica

In our investigation of in vitro anti-allergic screening of medicinal herbal extracts, the ethyl acetate extract of the root of Wikstroemia indica was observed to inhibit nitric oxide (NO) production in a lipopolysaccharide (LPS) and recombinant mouse interferon-gamma (IFN-gamma) activated murine macrophage-like cell line, RAW 264.7. Fractionation of the active extract led to the isolation of one new guaiane type sesquiterpene, indicanone (1), and two known biflavonoids, sikokianin B (2) and sikokianin C (3). 1 inhibited NO production with IC50 values at 9.3 microM and also inhibit the inducible nitric oxide synhase (iNOS) gene expression. This is the first report of NO production inhibitory activity of Wikstroemia indica and supports the pharmacological use of it, which has been employed as an herbal medicine for the treatment of inflammation.     

Formation and characterization of quasi-free clusters

The Si clusters are prepared by inert gas condensation method and then softly land on the mother skeleton of the porous silicon (PS), and thus quasi-free clusters are formed. Several new Raman peaks are observed and identified as surface modes of Si clusters and their combination with TA modes for the first time. Good agreement is achieved between the experimental observations and the calculated results.     

Interaction of tetrandrine with human serum albumin: a fluorescence quenching study.

The interaction of tetrandrine with human serum albumin (HSA) was studied by measuring fluorescence quenching spectra, synchronous fluorescence spectra and ultra-violet spectra. The fluorescence quenching spectra of HSA in the presence of tetrandrine showed that tetrandrine quenched the fluorescence of HSA. The quenching constants of tetrandrine on HSA were determined using the Stern-Volmer equation. Static quenching and non-radiation energy transfer were the two main reasons leading to the fluorescence quenching of HSA by tetrandrine. According to the F?rster theory of non-radiation energy transfer, the binding distances (r) and the binding constants (K(A)) were obtained. The thermodynamic parameters obtained in this study revealed that the interaction between tetrandrine and HSA was mainly driven by a hydrophobic force. The conformational changes of HSA were investigated by synchronous spectrum studies.     

Ion mobility spectrometry as flow-injection detector and continuous flow monitor for aniline in hexane and water

Ion mobility spectrometry (IMS) was used as a flow-injection detector to quantitatively examine the ionization chemistry of aniline in hexane. A 5-microl sample was vaporized at 15-90-sec intervals in a flowing air stream and analyzed with an IMS equipped with acetone reactant ion chemistry, ambient temperature drift tube and membrane-based inlet. Precision was 3-11% relative standard deviation for 1-100 ppm aniline in hexane with 90-sec injection intervals and detection limits were ca. 0.5 ppm with 5-microl injections. Matrix effects with amine and organic solvent mixtures were observed and corrected for low and medium proton affinity interferences with standard addition methods. Pronounced fouling of the IMS occurred when a continuous water flow was introduced for aqueous flow injection-IMS. Continuous water monitoring without degraded IMS performance was possible by sampling air flow through a Silastic tube immersed in an aqueous sample.     

Adsorption of NH3 onto activated carbon prepared from palm shells impregnated with H2SO4

Adsorption of ammonia (NH3) onto activated carbons prepared from palm shells impregnated with sulfuric acid (H2SO4) was investigated. The effects of activation temperature and acid concentration on pore surface area development were studied. The relatively large micropore surface areas of the palm-shell activated carbons prepared by H2SO4 activation suggest their potential applications in gas adsorption. Adsorption experiments at a fixed temperature showed that the amounts of NH3 adsorbed onto the chemically activated carbons, unlike those prepared by CO2 thermal activation, were not solely dependent on the specific pore surface areas of the adsorbents. Further adsorption tests for a wide range of temperatures suggested combined physisorption and chemisorption of NH3. Desorption tests at the same temperature as adsorption and at an elevated temperature were carried out to confirm the occurrence of chemisorption due to the interaction between NH3 and some oxygen functional groups via hydrogen bonding. The surface functional groups on the adsorbent surface were detected by Fourier transform infrared spectroscopy. The amounts of NH3 adsorbed by chemisorption were correlated with the contents of elemental oxygen present in the adsorbents. Mechanisms for chemical activation and adsorption processes are proposed based on the observed phenomena.     

Addition of grignard reagents to aryl acid chlorides: an efficient synthesis of aryl ketones

[chemical reaction: see text]. Direct addition of Grignard reagents to acid chlorides in the presence of bis[2-(N,N-dimethylamino)ethyl] ether proceeds selectively to provide aryl ketones in high yields. A possible tridentate interaction between Grignard reagents and bis[2-(N,N-dimethylamino)ethyl] ether moderates the reactivity of Grignard reagents, preventing the newly formed ketones from nucleophilic addition by Grignard reagents.