Further monoterpene chromane esters from Peperomia obtusifolia: VCD determination of the absolute configuration of a new diastereomeric mixture

A reinvestigation of the monoterpene chromane ester enriched fraction from Peperomia obtusifolia using chiral chromatography led to the identification of a minor peak, which was elucidated by NMR and HRMS as fenchyl-3,4-dihydro-5-hydroxy-2,7-dimethyl-8-(3″-methyl-2″-butenyl)-2-(4′-methyl-1′,3′-pentadienyl)-2H-1-benzopyran-6-carboxylate, the same structure assigned to two other fenchyl esters described previously, pointing out a stereoisomeric relationship among them. Further NMR analysis revealed that it was actually a mixture of two compounds, whose absolute configurations were determined by VCD measurements. Although, almost no vibrational transitions could be assigned to the chiral chromane, the experimental VCD spectrum was largely opposite to that obtained for the average experimental VCD [(2S,1?R,2?R,4?S + 2R,1?R,2?R,4?S)/2] for fenchol derivatives. These results allowed us to assign the putative compounds as a racemic mixture of the chiral chromane esterified with the monoterpene (1S,2S,4R)-fenchol, which had not been identified in our early work.     

A concise total synthesis of (+)-deoxocassine and (−)-deoxoprosophylline from d-xylose

A concise total synthesis of (+)-deoxocassine (1) and (−)-deoxoprosophylline (2) has been achieved for the first time from d-xylose. The key steps involved in these synthesis are alkyl Grignard reaction, S_N2 substitution of mesylate by azide, Wittig reaction, and reductive amination.     

Ionic Liquids for and by Analytical Spectroscopy

Abstract

In this mini‐review we highlight two aspects of ionic liquids that to date have either no or limited studies. They are (1) exploitation of unique features of ionic liquids to develop novel spectroscopic methods and (2) development of novel spectroscopic methods, for the sensitive and accurate determination of thermal physical properties of ionic liquids. In the first category, we will describe several novel methods which were developed utilizing unique properties of ionic liquids for measurements which are not possible otherwise. They include the sensitive and accurate method to determine enantiomeric compositions of a variety of pharmaceutical products with different size, shape, and functional groups. This method is based on the use of a chiral IL which serves both as a solvent and also as a chiral selector. Ionic liquids have also been successfully used to substantially enhance the sensitivity of thermal lens measurements. In the second category, we will describe recent development in which transient grating technique and thermal lens technique have been successfully used for the sensitive, accurate, nondestructive determination of thermal physical properties of ILs.     

Application of Flow Injection Method for the Determination of Thioridazine

Abstract

A simple flow-injection spectrophotometric method for the determination of thioridazine is described. The method is based on the oxidation of thioridazine with phosphotungstic acid in hydrochloric acidic media. Concentrations of thioridazine in the range 10 – 60 ppm are determined with a relative standard deviation of 1.1%. The method was applied to the determination of thioridazine in pharmaceutical formulations.     

Enantioselective syntheses of bioactive epoxyquinone natural products (+)-harveynone and (−)-asperpentyn

Stereo- and enantioselective syntheses of (+)-harveynone and (−)-asperpentyn are reported.     

Voltammetric Detection of a Specific DNA Sequence of Avian Influenza Virus H5N1 Using HS‐ssDNA Probe Deposited onto Gold Electrode

The working principle of a genosensor is based on the mechanism of ion‐channel mimetic sensors. The analytical signals generated upon hybridization processes were recorded by a redox active marker [Fe(CN)₆]^3?/4? present in the sample solution using voltammetric techniques. The developed genosensor was suitable for determination of 20‐mer complementary oligonucleotide sequence, and also of the PCR products containing the complementary 20‐mer sequence in various positions, with detection limits in the 10 pM range. The noncomplementary 20‐mer oligonucleotide sequence as well as the PCR product without complementary region generated very weak response. The good discrimination of the position of the complementary part in the PCR products was observed.     

氮杂Brazilin/二芳基茚杂合物的合成研究

天然产物在药物化学中具有非常重要的地位,天然产物杂合物的设计合成,可以为药物筛选提供数目更多、结构更多样化的生物活性分子,是发现更多的新药先导化合物的一条非常重要的途径.以邻苯二甲醚为原料,经傅克酰基化、酮酯缩合、Knoevenagel缩合、Nazarov环化、酮酸酯的胺解、1,3-二羰基化合物的α-羟基化、酮羰基和酰胺的还原及分子内的傅克环化共9步反应,合成了氮杂brazilin(Aza-brazilin)与1,3-二芳基茚类化合物的一个杂合物.     

快速高效液相色谱-串联质谱法同时测定水产品中5类33种药物残留

建立了快速高效液相色谱-串联质谱法(RRLC-MS/MS)同时测定水产品中四环素类、喹诺酮类、磺胺类、磺胺增效剂和三苯甲烷类共5大类33种药物残留的方法。样品用Na2EDTA-Mcllvaine缓冲溶液及乙腈提取,正己烷脱脂后,用RRLC进行分离。在电喷雾正离子模式下,以动态多反应监测(Dynamic MRM)方式采集数据进行定性与定量分析。33种药物在相应的浓度范围内线性良好,相关系数均大于0.99;在3个不同浓度添加水平下,平均回收率为63.6%～115.2%;相对标准偏差(RSD)为4.6%～14.6%;检出限(LOD,S/N=3)和定量限(LOQ,S/N=10)分别为0.1～2.0μg/kg和0.5～5.0μg/kg。本方法简便快速、灵敏可靠,适用于水产品中药物多残留的同时快速定性与定量测定。     

Analysis of Corrosion Products Formed on Cu-Ni Alloys Immersed in Sea Water

Abstract

A method was developed for separation and analysis of corrosion products formed on the surface of Cu-Ni alloys immersed in sea water polluted by sulphide ions. This method is based on the selective dissolution of oxidation compounds by suitable solvents dissolving the metal matrix only to a negligeable extent.

The following solvents were used: 1) methanol to dissolve Na⁺, Cu²⁺, Ni²⁺ chlorides and sulphates; 2) glycine to dissolve bivalent metal compounds - Cu²⁺, Ni²⁺ oxides, sulphides, oxysulphates, oxychlorides and oxycarbonates; 3) ammonia solution to dissolve Cu⁺ compounds (i.e. Cu₂O and CuCl); 4) potassium cyanide to dissolve CU⁺ sulphides.

Reasonable agreement between chemical and X-Ray analysis results was observed only for copper compounds, since nickel and iron compounds could not tie observed by X-Ray diffraction. The results of Auger and chemical analyses better agree with each other, yet no Fe compounds could be detected. This is to be attributed to the non-homogeneous corrosion layer which notably contains Fe compounds in the innermost region at a depth where Auger spectroscopy is unable to detect them, whereas their detection is possible by chemical analysis, since it is a bulk analysis.     

Determination of Riboflavin Using the Polarographic Reduction Wave of Its Photochemical Reaction Products

Abstract

A new, simple, and sensitive method for the determination of riboflavin based on the single-sweep polarographic reduction wave of the photolysis products of riboflavin has been developed. Under the irradiation of an iodine-tungsten lamp, the photolysis reaction of riboflavin in pH 9.3 NH₃-NH₄Cl buffer solution can be complete in about 20 min. The reaction products yield a single adsorptive reduction wave at ?0.63 V (vs. SCE) negative to the reduction wave of riboflavin by 0.18 V. The derivative wave height is linearly proportional to the concentration of riboflavin in the range of 0.01–17.5 µg/mL (correlation coefficient 0.996). The detection limit is 0.00 5µg/mL. The proposed method has been applied to the determination of multivitamin tablets with satisfactory results. In comparison with the methods directly using the reduction wave of riboflavin for the determination, this method eliminates the effect of the degradation of riboflavin on the determination accuracy and is much more sensitive. The new method could be useful in many fields.