Y2O3质点对β—NiAl涂层抗氧化性能的影响

本文用复合电沉积及粉末包装扩散渗铝技术获得了含Y_2O_3、质点的β-NiAl型新涂层,并研究了Y_2O_3、质点及其含量对涂层1100℃的氧化性能的影响。实验证明,Y_2O_3质点的加入有效地降低了涂层的氧化速率,提高了氧化膜的抗剥落能力。实验范围内的Y_2O_3含量对涂层氧化速率的影响并不明显,但通过改变涂层/氧化膜界面处氧化膜的形态可以对氧化膜的粘附性产生影响。向涂层内突出生长的针状氧化膜具有更显著的钉扎作用。复合电沉积层中弥散分布的Y_2O_3质点在渗铝过程中部分产生聚集,在制备出的复合铝化物涂层的基体/涂层界面附近形成了明显的Y_2O_3聚集层,在氧化过程中有效地抑制了涂层的退化。     

Determination of Benzo[a]pyrene in smoking-flavour agents (water-soluble liquid smoke) by second derivative constant-wavelength synchronous spectrofluorimetry

We have developed a simple, rapid, inexpensive method for the determination of benzo[a]pyrene (BP, a known carcinogen) in smoking-flavour agents (water-soluble liquid smoke; WSLS). After purification of the WSLS by a single passage through a Sep Pak C18 Plus cartridge, BP in the hexane eluate was determined by second derivative constant-wavelength synchronous spectrofluorimetry. Method precision (RSD < 6%) and recovery ( approximately 92%) were satisfactory, and the detection and quantification limits (1.05 and 2.28 mug kg(-1) respectively) indicated that the current maximum permissible concentration of BP in smoke flavourings (10 mug kg(-1)) can be monitored by this method.     

Coupled-column liquid chromatography method with photochemically induced derivatization for the direct determination of benzoylureas in vegetables

The coupled-column (LC-LC) system, consisting of a first column packed with internal surface reversed phase (ISRP) (50 x 4.6mm ID) and a Chrompack C18 (100 x 4.6 mm ID) as second column, allowed the simultaneous determination of five benzoylurea insecticides in dichloromethane (CH2Cl2) extracts of vegetable samples without any clean-up step. This system was combined with a photochemically induced fluorescence (PIF) post-column derivatization in order to provide strongly fluorescent photoproducts from the non-fluorescent benzoylureas. Limits of detection ranged from 0.21 to 0.98 microg L(-1) of pesticide (equivalent to 0.14-0.65 microg kg(-1) in vegetable samples) and limits of determination ranged from 4.0 to 10.0 microg L(-1) (equivalent to 2.7-6.7 microg kg(-1)). Linearity of the method was established between 2 and 1800 microg L(-1), depending upon the compound. Validation of the total method was performed by randomly analyzing recoveries of four vegetable samples (aubergine, cucumber, green bean, and tomato) spiked at two levels of concentration (10.0 and 33.3 microg kg(-1)). The combination of the LC-LC system with PIF detection provides a sensitive, selective, and rapid method for the determination of pesticides in vegetable samples at levels lower than the maximum residue levels (MRLs) established for these compounds by Spanish legislation.     

High-performance liquid chromatographic determination of tocopherols in infant formulas

A method for the simultaneous determination of alpha-tocopherol acetate and alpha-, delta-, and gamma-tocopherols by normal-phase high-performance liquid chromatography (HPLC) with a fluorescent detector in infant formula is proposed. The values obtained in the determination of the analytical parameters: linearity, precision, limit of detection and accuracy (analysis of a standard reference material, SRM 1846), confirm the quality of the method. The proposed method is useful for the determination of alpha-, delta-, and gamma-tocopherols and alpha-tocopherol acetate in infant formulas at a low cost and in a total time of 2 h.     

Use of highly efficient Draper-Lin small composite designs in the formal optimisation of both operational and chemical crucial variables affecting a FIA-chemiluminescence detection system

A new formal strategy in the multidimensional optimisation of the experimental variables affecting the chemiluminescence (CL) detection in flow injection analysis (FIA) is proposed here. The strategy implies several steps, being the most significant: selection of the variables to be studied and their experimental domain; use of a screening design to detect significant variables and interactions into the experimental region; study of the main effect of variables and second-order interactions; and finally application of a Draper-Lin small composite design (orthogonal) to obtain the optimum values of the significant variables. The methodology is applied to the determination of methylamine by FIA based on the use of the peroxyoxalate CL (PO-CL) reaction. Considering the high number of experiments required due to the different chemical and instrumental variables to be taken account and their adequate compatibility to obtain maximum sensitivity, the methodology offers a rigorous study of the main effects and interactions, achieving a reduction of experimental work.     

一种用于测定D-氨基酸的羊肾组织膜电极

将羊肾切片组织配合氨气敏电极可制成对D-氨基酸具有高选择性的羊肾组织膜电极。该电极在D-丙氨酸浓度3.0×10~(-5)-1.0×10~(-3)M范围内呈良好线性关系,其检测极限达2.0×l0~(-5)M。在最佳操作条件下,电极的活性至少保持12天不变。本文对电极的特性及实际样品中的分析功能进行了考察。     

Binuclear Cu2+ complex mediated discrimination between L-glutamate and L-aspartate in water

L-glutamate and L-aspartate selectivity is achieved by the action of two Cu2+ metal ions rightly disposed in a cyclophane-type macrocyclic framework; electrochemical sensing of glutamate has been achieved by adsorption of the copper complexes on graphite electrodes.     

新型[(吡嗪-3-基)甲氧基]芳酸衍生物的合成及其抗血小板聚集活性

以具有活血化瘀作用的中药有效成分阿魏酸为先导物，利用基于受体结构的理性药物设计方法，设计并合成了6个新化合物[(吡嗪-3-基)甲氧基]芳酸衍生物（6a~6f）。以2-甲基吡嗪和不同取代的芳香酸甲酯为起始原料，经自由基卤代反应、醚化反应和水解反应合成6a~6f，其结构经¹H NMR， ¹³C NMR， IR和MS表征。体外药效筛选结果显示：6a~6f具有明显的抗血小板聚集活性，其中(E)-3-甲氧基-4-(吡嗪-2-甲氧基) 苯丙烯酸(6a)和3-(2-吡嗪甲氧基)-4-甲氧基-苯甲酸(6e)的活性优于奥扎格雷和阿魏酸。(E)-3-甲氧基-4-(吡嗪-2-甲氧基)-苯丙烯酸(6a)的抗血小板聚集活性，优于化合物(E)-3-(4-(吡啶-3-基)甲氧基)-3-甲氧基苯基)丙烯酸。     

三元体系C_sCl-SbCl_3-HOAc(25℃)的研究

本文测定了三元体系CsCl-SbCl_3-HOAc在25℃时的稳定平衡态的溶度及饱和溶液折光指数,绘制了相应的溶度图。稳定平衡态时体系中有五种固相:CsCl,SbCl_3两种原始盐;3CsCl·SbCl_3,3CsCl·2SbCl_3两种二元复盐和CsCl·5SbCl_3·4HOAc三元复盐。3CsCl·2SbCl_3相区极大,该复盐是固液同组成的。3CsCl·SbCl_3与CsCl·5SbCl3·4HOAc是固液异组成的。三元复盐在以往的文献中未见报道。3CsCl·SbCl_3,3CsCl·2SbCl_3在空气中稳定,不吸潮水解。三元复盐仅能在溶液中稳定存在,移出母液后易转变为3CsCl·2SbCl_3。测定了该体系25℃时一根甚长的介稳溶度曲线及饱和溶液折光指数。介稳溶度曲线所对应的固相为5CsCl·2SbCl_3。向该体系中的饱和溶液加入晶种,长时间搅拌,5CsCl·2SbCl_3转变为稳定态的3CsCl·2SbCl_3,溶液的组成亦降到3CsCl·2SbCl_3的溶度曲线上。在本实验条件下没有发现7CsCl·5SbCI_3复盐形成。除了文献报道过的从液态SO_2中制取3CsCl·8bCl_3的方法之外,本文提供了又一种制取该复盐的方法。本文为从铯榴石中提取CsCl的工艺及铯的定量分析,提供了相图上的根据.     

Development and validation of a capillary electrophoresis method for the determination of phenothiazines in human urine in the low nanogram per milliliter concentration range using field-amplified sample injection

A capillary zone electrophoresis (CZE) method with ultraviolet-visible detection has been established and validated for the determination of five phenothiazines: thiazinamium methylsulfate, promazine hydrochloride, chlorpromazine hydrochloride, thioridazine hydrochloride, and promethazine hydrochloride in human urine. Optimum separation was obtained on a 64.5 cm x 75 microm bubble cell capillary using a buffer containing 150 mM tris(hydroxymethyl)aminomethane and 25% acetonitrile at pH 8.2, with temperature and voltage of 25 degrees C and 20 kV, respectively. Naphazoline hydrochloride was used as an internal standard. Field-amplified sample injection (FASI) has been applied to improve the sensitivity of the detection. Considering the influence of parameters affecting the on-line preconcentration (nature of preinjection plug, sample solvent composition, injection times, and injection voltage) and due to the significant interactions among them, in this paper we propose for the first time the application of a multivariate approach to carry out the study. The optimized conditions were as follows: preinjection plug of water for 7 s at 50 mbar, electrokinetic injection for 40 s at 6.2 kV, and 32 microm of H3PO4 in the sample solvent. Also, a solid-phase extraction (SPE) procedure is developed to obtain low detection limits and an adequate selectivity for urine samples. The combination of SPE and FASI-CZE-UV allows adequate linearities and recoveries, low detection limits (from 2 to 5 ng/mL), and satisfactory precisions (3.0-7.2% for an intermediate RSD %).