混合模式硅胶基质毛细管电色谱整体柱的制备及其电色谱性能研究

采用温和条件下的溶胶-凝胶技术，成功制备了阴离子交换-反相混合模式硅胶基质毛细管电色谱整体柱。通过调整反应液中不同前体的比例，优化了整体柱的制备条件。通过扫瞄电镜，对柱床进行了表征和分析。实验发现，所制备的整体柱电渗流的方向和大小可随流动相pH值的改变而改变，在酸性和中性条件下，具有从阴极流向阳极的电渗流；当流动相pH值升至约7．5时，电渗流方向发生了反转（由阳极流向阴极）。在优化的实验条件下，用所制备的整体柱对所考察的酸性（中性）化合物实现了快速分离，并获得了高达160，000N／m的柱效。     

Vacancy ion-exclusion chromatography of aromatic carboxylic acids on a weakly acidic cation-exchange resin

Determination of aromatic carboxylic acids by conventional ion-exclusion chromatography is relatively difficult and methods generally rely on hydrophobic interaction between the solute and the resin. To overcome the difficulties in determining aromatic carboxylic acids a new approach is presented, termed vacancy ion-exclusion chromatography, which is based on use of the sample as mobile phase and an injection of aqueous 10% methanol onto a weakly acidic cation-exchange column (TSKgel OApak-A). Highly sensitive conductivity detection occurred with sharp and well-shaped peaks, leading to very efficient separations. The effects of sulfuric acid concentration added to the mobile phase, flow-rate, and column temperature on the retention volume of tested aromatic carboxylic acids was investigated. Retention times were found to be affected by the concentration of the analytes in the mobile phase and to some extent also by the addition of an organic modifier such as methanol to the injected water sample. Separation of sulfuric acid (SA), naphthalenetetracarboxylic acid (NTCA), phthalic acid (PA) and benzoic acid (BA) was satisfactory using this new approach. Detection limits were 0.66, 0.67, 0.42 and 0.86 microM and detector responses were linear in the range 1-100, 1-80, 2.5-100 and 10-40 microM, for SA, NTCA, PA and BA, respectively. Precision for retention times was 0.36% and for peak areas was 1.5%.     

Quadrupole mass filters with octopole fields

The performance of quadrupole mass filters with added octopole fields in the range 2.0-4.0% has been investigated. The added fields are much greater than those normally added to conventional rod sets by mechanical tolerances or construction errors. Quadrupole rod sets with added octopole fields were constructed with round rods by making one pair of rods greater in diameter than the other pair. For positive ions, resolution at half height of only about 200 is possible if the negative direct current (dc) output of the quadrupole power supply is connected to the smaller rods. If the positive dc output of the quadrupole power supply is connected to the smaller rods, the resolution improves dramatically; a resolution at half height of 5800 has been observed with a rod set with 2.6% added octopole field. For negative ions the best resolution is obtained with the polarity of the dc reversed, i.e. with the negative dc applied to the smaller rods. These findings are unexpected in view of the literature that argues that to obtain high mass resolution with quadrupole mass filters, higher order multipoles must be kept as small as possible. Numerical simulations of peak shapes agree qualitatively with experiments. Simulation of the boundaries of the first stability region for positive ions shows that when the positive dc is applied to the smaller rods, the addition of a 2.0% octopole field causes the boundaries to shift slightly but the boundaries are well defined, and the tip of the stability region remains sharp. When the positive dc is applied to the larger rods, the boundaries of the stability region move out and become diffuse. For instruments that require a rod set that can be used both as a linear trap and a mass filter, these rod sets may offer improved trap performance while still being capable of providing conventional mass analysis.     

高效液相色谱检测反－2－苯基－邻－硝基肉桂酸

初探了反－２－苯基－邻－硝基肉桂酸（ＰＮＣＡ）的高效液相色谱分离，优选出了最佳分离条件。所建立的方法简单、快速，适用于工业生产中的控制及分析。     

Determination of chromium(III) in water by solid-phase microextraction with a polyimide-coated fiber and gas chromatography-flame photometric detection

A method for the determination of trace Cr(III) in aqueous solution by solid-phase microextraction (SPME) coupled with gas chromatography (GC)-flame photometric detection (FPD) was developed. Aqueous Cr(III) was first converted to the volatile chromium trifluoroacetylacetonate (Cr(tfa)3) by derivatization with 1,1,1-trifluoroacetylacetone (Htfa), followed by SPME extraction using a polyimide-coated silica fiber. The distribution constants (K) of derivatized cis- and trans-Cr(tfa)3 between the polyimide phase and aqueous phase were 2012 and 2214, respectively. The two Cr(tfa)3 isomers extracted can be efficiently separated by a DB-210 GC column within 9 min. Selective detection of Cr was performed by a FPD equipped with a 385-nm long-pass filter. Linearity (r> 0.99) over the concentration range 5-300 ng ml(-1) Cr was obtained and the limit of detection was 2 ng ml(-1) Cr. The relative standard deviation was 7% at 10 ng ml(-1) Cr (n = 5). Applicability of this method to water analysis was tested by analyzing the chromium content in a reference standard water sample and an industrial effluent.     

ZnP2晶体合成机理研究

在抽空密封石英管内放置元素锌和磷合成ZnP_2过程中, 仔细考察了不同升温程序的实验结果, 发现磷蒸汽压条件对于形成磷化物的性质相当重要, 在大于4大气压时会生成近100％黑色ZnP_2。用缩短合成时间,考察合成过程的中间产物, 以及用称量法、化学分析法和扫描电镜法对中间产物的分析, 提出了ZnP_2合成过程的主要机理。     

Three new oleanene glycosides from Sophora flavescens.

Three new oleanene glycosides, sophoraflavosides II-IV (2-4) were isolated together with sophoraflavoside I (1) as the corresponding methyl ester forms from Sophorae Radix, the fresh roots of Sophora flavescens AITON (Leguminosae). Their structures have been elucidated as oxytrogenin 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-galactopyranosyl-(1-->2)-beta -D- glucuronopyranoside (2), 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-galactopyranosyl-(1-->2)-beta -D-glucuronopyranosyl oxytrogenin 22-O-alpha-L-arabinopyranoside (3) and 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-galactopyranosyl-(1-->2)-beta -D-glucuronopyranosyl oxytrogenin 22-O-beta-D-glucopyranosyl-(1-->2)-alpha-L-arabinopyranoside (4), along with unambiguous characterization as 3 beta,22 beta,24-trihydroxyolean-12-en-29-oic acid for their sapogenol, named oxytrogenin (5) on the bases of chemical reactions and spectral analyses.     

含金鸡纳碱的光活性聚合物──Ⅰ．金鸡纳碱／丙烯酰胺共聚物的合成与表征

研究了金鸡纳碱与丙烯酰胺的自由基共聚反应。发现在氯仿／乙醇混合溶剂中采用硫酸奎宁作为金鸡纳碱共聚单体可以合成收率和金鸡纳碱含量均较高的新型水溶性共聚物。对共聚物用元素分析、核磁共振、粘度和旋光度测定等方法进行表征，发现在假定丙烯酰胺链节为非光活性的条件下共聚物中金鸡纳碱链节的比旋光度随聚合配方中金鸡纳碱含量的增加而增加。     

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometric analysis of phospholipase A2 and fibrinolytic enzyme, two enzymes obtained from Chinese Agkistrodon blomhoffii Ussurensis venom

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used to analyze two enzymes, phospholipase A2 and fibrinolytic enzyme isolated from Chinese Agkistrodon blomhoffii Ussurensis venom. Using sinapinic acid as the matrix, positive ion mass spectra of the enzymes were obtained. In addition to the dominant protein [M + H]+ ions, multimeric and multiply charged ions were also observed in the mass spectra. The higher the concentration of the enzymes, the more multiply charged polymer and multimeric ions were detected. Our results indicate that MALDI-TOFMS can provide a rapid and accurate method for molecular weight determination of snake venom enzymes. Mass accuracies of 0.1 and 0.3% were achieved by analysis of highly dialyzed phospholipase A2 and fibrinolytic enzyme, and these results are much better than those obtained using sodium dodecyl sulfate-polyacrylamide gel electrophoresis. MALDI-TOFMS thus provides a reliable method to determine the purity and molecular weight of these enzymes, which are of potential use as therapeutants.     

Nuclear magnetic resonance spectroscopic study on ionic liquids of 1-alkyl-3-methylimidazolium salts

Chemical shifts of ¹H and ¹³C NMR of series of methylimidazolium salts (MIM⁺, X=Br⁻, BF₄⁻ and PF₆⁻) function on the length of alkyl groups on the ring, type of solvents and the concentration. The bromides series demonstrate more chemical shift variation on H2 upon the change of solvents and concentration. Unexpected H-D exchange reactions were also observed in the MIM⁺Br⁻ by using CD₃OD and D₂O. The exchange rates strongly depend on the length of the alkyl group, which could cause more steric factor to reduce the interaction between deuterium atom from solvent and C2 of the ring.