三梅片成份分析研究

医药品冰片有天然品与合成品之分,天然品有:由龙脑香科(Dipterocarpaceae)植物龙脑香(Dryobalanops aromatica G aertn,f.)制得的结晶,称龙脑香冰片;白菊科(Compositae)植物艾纳香(Blumea balsamifera DC.)所得的结晶,名艾片。艾片因其晶形似梅花片,又有梅片之称,根据梅花片状又分为大梅片,二梅片,三梅片,天然品化学成分为龙脑(Borneol,Ⅰ),合成冰片(又名合成龙脑),除含龙脑外尚含较大量的异龙脑(ISO-borneol,Ⅱ)     

The effect of capillary column diameter on the performance of thermal conductivity detectors

The concentration sensitivity of a thermal conductivity detector (TCD) depends, among other factors, on the amount of sample mixture in the detector's sensing cell. Since the cell volume has to be appropriately matched with column diameter, it makes the concentration sensitivity of a TCD dependent on column diameter and, therefore, on the speed of gas chromatography. Through reduction of column diameter, higher speed tends to lead to a reduction in the concentration sensitivity of the cell. The factor which the most directly affects the concentration sensitivity of a TCD cell is the heat power conducted through the cell. The higher the power, the greater the sensitivity. The limit of detection of a TCD depends on the concentration-sensitivity of its cell and on the level of statistical errors in the measurement. The errors increase with increasing analysis speed. As the column diameter is reduced, the errors cause additional worsening (on top of the decrease in concentration sensitivity) of the detection limit, dynamic range, and other performance characteristics of the TCD.     

神经网络法用于多元混酸同时测定

利用多层神经网络误差反向传播算法处理酸碱电位滴定数据，求得出多元混合酸各组分的浓度，优化了神经网络的结构和参数，测定了三组分有机酸混合样品，结果良好，平均相对偏差ＲＳＤ≤４％。     

电解沉积压电频移分析的理论与验证

提出了控制电位电解和恒电流电解两类电解沉积的压电频移分析法测定的理论公式,用实验结果验证了它的正确性.     

Darstellung,Kristallstruktur und Normalkoordinatenanalyse der bindungsisomeren Pentachlororhodanoosmate(IV)

Preparation, Crystal Structure and Normal Coordinate Analysis of Linkage Isomeric Pentachlororhodanoosmates(IV) By treatment of [OsCl₅I]^2? with (SCN)₂ in dichloromethane the linkage isomers [OsCl₅(NCS)]^2? and [OsCl₅(SCN)]^2? are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on single crystals of (Ph₄As)₂[OsCl₅(NCS)] (monoclinic, space group P2₁/a, a = 18.872(2), b = 11.6024(2), c = 22.786(1), β = 109.057(1)°, Z = 4) and (Ph₄As)₂[OsCl₅(SCN)] (monoclinic, space group P2₁/a, a = 19.057(2), b = 11.306(2), c = 22.612(1), β = 106.64(2)°, Z = 4) reveals the complete ordering of the complex anions. The thiocyanate group is located above one of the Cl ligands of the equatorial plane with the Os? N? C angle of 166.1° for N bonding and the Os? S? C angle of 109.9° for S bonding. The IR and Raman spectra of both linkage isomers known from literature are assigned by normal coordinate analysis based on the general valence force field using the molecular parameters of the X-ray determination. The valence force constants are f_d(OsN) = 1,81 and f_d(OsS) = 1,32 mdyn/Å. Taking into account increments of the trans influence a good adjustment between observed and calculated frequencies is achieved.     

Aspects of investigating scrambling in the synthesis of porphyrins: different analytical methods

Herein, we discuss the analyses and quantification of the different components in porphyrin mixtures, prepared from p-anisaldehyde, p-tolualdehyde, and 5-(4-bromophenyl)-dipyrromethane with acid catalysis, using NMR and HPLC. The advantages and disadvantages of these analytical methods are emphasized. Due to the similar size of a bromine atom and a methyl group it was possible to grow crystals suitable for X-ray crystallographic studies from a mixture of porphyrins, where the 4-position of the meso-phenyl rings was either substituted with methyl groups or bromine atoms. We also show that X-ray studies are inferior to NMR analysis for determining the components in a porphyrin mixture.     

Synthesis and Characterization of [Hg(sulfamethoxazolato)2]·2DMSO and[Cu2(μ‐CH3CO2)4(sulfamethoxazole)2]

[Hg(sulfamethoxazolato)₂]·2DMSO ( 1 ) and [Cu₂(CH₃COO)₄(sulfa‐methoxazole)₂] ( 2 ) can be obtained by the reaction of sulfamethoxazole with mercury acetate or copper acetate in methanol. The structures of the two complexes were characterized by single crystal X—ray diffractometry. Compound 1 consists of sulfamethoxazolato ligands bridging the metal ions building an unidimensional chain. Two solvent dimethylsulfoxide molecules are involved via N‐H···O hydrogen bridges. The mercury atom shows a linear primary coordination arrangement formed by two trans deprotonated sulfonamidic nitrogen atoms. The overall coordination around the metal atom may be regarded as a strongly distorted octahedron when the interactions of mercury with four sulfonamidic oxygen atoms [bond distances of 2.761(4) Å—2.971(4) Å] are also considered to build an equatorial plane and the N1 and N1′ atoms [bond distance of 2.037(5) Å] occupy the apical positions. Compound 2 is a dinuclear complex in which the copper ions are bridged by four syn‐syn acetate ligands which are related by a symmetry centre located in the centre of the complex. Each copper atom presents a nearly octahedral coordination where the equatorial plane is formed by four oxygen atoms and an isoxazolic nitrogen atom and the second copper atom occupy the apical positions.     

Synthesis and Conformational Analysis of 1′‐ and 3′‐Substituted 2‐Deoxy‐2‐fluoro‐D‐ribofuranosyl Nucleosides

Convergent syntheses of the 9‐(3‐X‐2,3‐dideoxy‐2‐fluoro‐β‐D ‐ribofuranosyl)adenines 5 (X=N₃) and 7 (X=NH₂), as well as of their respective α‐anomers 6 and 8 , are described, using methyl 2‐azido‐5‐O‐benzoyl‐2,3‐dideoxy‐2‐fluoro‐β‐D ‐ribofuranoside ( 4 ) as glycosylating agent. Methyl 5‐O‐benzoyl‐2,3‐dideoxy‐2,3‐difluoro‐β‐D ‐ribofuranoside ( 12 ) was prepared starting from two precursors, and coupled with silylated N⁶‐benzoyladenine to afford, after deprotection, 2′,3′‐dideoxy‐2′,3′‐difluoroadenosine ( 13 ). Condensation of 1‐O‐acetyl‐3,5‐di‐O‐benzoyl‐2‐deoxy‐2‐fluoro‐β‐D ‐ribofuranose ( 14 ) with silylated N²‐palmitoylguanine gave, after chromatographic separation and deacylation, the N⁷‐β‐anomer 17 as the main product, along with 2′‐deoxy‐2′‐fluoroguanosine ( 15 ) and its N⁹‐α‐anomer 16 in a ratio of ca. 42 : 24 : 10. An in‐depth conformational analysis of a number of 2,3‐dideoxy‐2‐fluoro‐3‐X‐D ‐ribofuranosides (X=F, N₃, NH₂, H) as well as of purine and pyrimidine 2‐deoxy‐2‐fluoro‐D ‐ribofuranosyl nucleosides was performed using the PSEUROT (version 6.3) software in combination with NMR studies.     

Analysis of selected ionic liquid cations by ion exchange chromatography and reversed-phase high performance liquid chromatography

The chromatographic behavior of 8 ionic liquids - 7 homologues of 1-alkyl-3-methylimidazolium and 4-methyl-N-butylpyridinium - has been investigated with a strong cation exchange adsorbent. In particular, the dependence of the retention properties of these solutes on mobile phase composition, pH, and buffer concentration was evaluated with the aim of optimizing and improving the selectivity and retention of solute separation. While using the SCX stationary phase, several interactions occurred with varying strengths, depending on the mobile phase composition. Cation exchange, nonspecific hydrophobic interactions, and adsorption chromatography behavior were observed. Reversed phase chromatography occurred at low concentrations of acetonitrile, electrostatic and adsorption interactions at higher organic modifier concentrations. Elevated buffer concentrations lowered the retention factors without affecting the selectivity of ionic liquids. Obtained results were further compared to the chromatographic behaviour of ionic liquids in the reversed phase system. All analyzed ionic liquids follow reversed-phase behavior while being separated. Much lower selectivity in the range of highly hydrophilic compounds is obtained. This suggests preferred use of ion chromatography for separation and analysis of compounds below 4 carbon atoms in the alkyl side chain.