O,O,S-三甲基硫赶磷酸酯在甲胺磷中毒检验中的应用

利用气相色诤质谱(GC-MS)分析了甲胺磷中毒者的检材(血，胃内容物)，均检出了O，O，S-三甲基硫赶磷酸酯，确未检出过甲胺磷。研究了这一现象的原因和确定了O，O，S-三甲基硫赶磷酸酯(O，O，S-TMTP)可作为甲胺磷中毒的佐证物。     

Voltammetric determination of L-dopa using an electrode modified with trinuclear ruthenium ammine complex (Ru-red) supported on Y-type zeolite

The L-dopa is the immediate precursor of the neurotransmitter dopamine. Unlike dopamine, L-dopa easily enters the central nervous system and is used in the treatment of Parkinson’s disease. A sensitive and selective method is presented for the voltammetric determination of L-dopa in pharmaceutical formulations using a carbon paste electrode modified with trinuclear ruthenium ammine complex [(NH₃)₅Ru^IIIORu^IV(NH₃)₄ORu^III(NH₃)₅]⁶⁺ (Ru-red) incorporated in NaY zeolite. The parameters which influence on the electrode response (paste composition, potential scan rate, pH and interference) were also investigated. The optimum conditions were found to an electrode composition (m/m) of 25% zeolite containing 6.7% Ru, 50% graphite and 25% mineral oil in acetate buffer at pH 4.8. Voltammetric peak currents showed a linear response for L-dopa concentration in the range between 1.2×10⁻⁴ and 1.0×10⁻² mol l⁻¹ (r=0.9988) with a detection limit of 8.5×10⁻⁵ mol l⁻¹. The variation coefficient for a 1.0×10⁻³ mol l⁻¹ L-dopa (n=10) was 5.5%. The results obtained for L-dopa in pharmaceutical formulations (tablet) was in agreement with compared official method. In conclusion, this study has illustrated that the proposed electrode modified with Ru-red incorporated zeolite is suitable valuable for selective measurements of L-dopa.     

栝楼蛋白 2: 栝楼蛋白部分化学结构的初步测定

栝楼蛋白(Trichobitacin)是从栝楼(Trichosanthes kirilowiiMaxim, Cucurbitaceae)中新发现的核糖体失活蛋白, 分子量为27,228; pI为9.6。应用基质辅助的激光解析飞行时间质谱(MALDI-TOF-MS)和快原子轰击质谱法(FAB-MS)分别测定胰蛋白酶酶解栝楼蛋白和天花粉蛋白(Trichosanthin)的混合肽质谱, 通过比较发现了一些分子量相同的肽。由于这两种蛋白质都来源于栝楼块根, 同源性比较强, 所以这些肽序列在两种蛋白质中基本一样; 再结合蛋白N-端自动顺序仪测定栝楼蛋白N-端的结果, 确定了栝楼蛋白N-端38个氨基酸的顺序, 栝楼蛋白经胰蛋白酶酶解后所得肽段用HPLC分离纯化, 再用蛋白质自动顺序仪, DABITC/PITC双偶合手工法和质谱法共确定了栝楼蛋白N-端, C-端等100多个氨基酸残基的序列。     

Reactions of 2,3-Dioxopyrrolo[2,1-<Emphasis Type="Italic">a</Emphasis>]isoquinolines with Active N-Nucleophiles

It is shown that 2,3-dioxopyrrolo[2,1-a]isoquinolines react readily with aliphatic diamines and hydroxyamine with opening of the dioxopyrrole ring and formation of the corresponding bisenaminoketoamides and hydroxamic acids. Reaction with the thiosemicarbazide and hydrazides of aromatic acids proceeds without opening of the pyrrole ring at the ketone carbonyl. Derivatives of hexahydropyridazine are formed when compounds with carboxyethyl groups at position 1 react with hydrazine. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, 1383–1387, September, 2005.     

Lewis-Base Adducts of Group 11 Metal(I) Compounds. LXXVI Structural Studies in the Copper(I) Halide : Norbornadiene System

The structural characterizations of some copper(I) halide (CuX) adducts with norbornadiene (nbd) are recorded. CuCl : nbd (1:1)₄ (a redetermination), (2:1)_2(|), are systems both based around Cu₄Cl₄ cubane-type cluster arrays. CuBr : nbd (7:3)_(|)( 0.5 MeOH), a complex polymer with 3-symmetry, is believed to be the complex previously described as an adduct of 2:1 stoichiometry. Attempts to obtain an iodide counterpart have resulted in the definition of an ephemeral adduct CuI : MeCN (3:2)_(|). 0.5 C₇H₈ in which, remarkably, the nbd is uncoordinated; the complex is a polymer, related to the [AgX(quinoline)]_(|) (X = Cl, Br) saddle polymer.     

On-line determination of manganese in solid seafood samples by flame atomic absorption spectrometry

Manganese is extracted on-line from solid seafood samples by a simple continuous ultrasound-assisted extraction system (CUES). This system is connected to an on-line manifold, which permits the flow-injection flame atomic absorption spectrometric determination of manganese. Optimisation of the continuous leaching procedure is performed by an experimental design. The proposed method allows the determination of manganese with a relative standard deviation of 0.9% for a sample containing 23.4 μg g⁻¹ manganese (dry mass). The detection limit is 0.4 μg g⁻¹ (dry mass) for 30 mg of sample and the sample throughput is ca. 60 samples per hour. Accurate results are obtained by measuring TORT-1 certified reference material. The procedure is finally applied to mussel, tuna, sardine and clams samples.     

Complexometric determination of thallium(III) in pure solution,alloys, and complexes using semicarbazide hydrochloride as a releasing agent

A simple and accurate complexometric method is proposed for the determination of Tl(III) using semicarbazide hydrochloride as a releasing agent. In the presence of diverse metal ions, thallium is complexed first with a known excess of EDTA, and the surplus EDTA is then titrated with standard zinc sulfate at pH 5.0–6.0 (hexamine) using xylenol orange indicator. An excess of 5% aqueous neutral solution of semicarbazide hydrochloride is then added and the released EDTA is titrated against standard zinc sulfate solution. The method works well in the range 2–50 mg of Tl(III) with relative errors < 0.5%, standard deviations 0.05mg and coefficient of variation 0.4%. The method is applied for the determination of thallium content in complexes and alloy compositions     

新型Ni—Pd/碳化树脂催化剂的制备及在微量测定有机氧元素中的应用

本文报道一种新型Ni—Pd／碳化树脂催化剂的制备方法，用该法制备的催化剂具有高金属分散度和高机械强度，用于库仑法微量测定有机氧元素取得满意结果。文中对Ni和Pd颗粒在催化剂上表面形貌和分布、催化活性等作了初步探讨。     

Online preconcentration system for determining ultratrace amounts of Cd in vegetal samples using thermospray flame furnace atomic absorption spectrometry

A system has been developed for online preconcentration and determination of Cd using thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS). It is based on the solid-phase extraction of Cd in an Amberlite XAD-2 minicolumn loaded with 2-(2-thiazolylazo)-5-dimethylaminophenol (TAM), and the metal ion is eluted with 1 mol L⁻¹ hydrochloridric acid, followed by its determination. The online system allows determining Cd with a detection limit of 8.0 ng L⁻¹ and a quantification limit of 25.0 ng L⁻¹. The precision (repeatability), calculated as the relative standard deviation (% RSD) in sample solutions containing 0.5 and 3.0 μg L⁻¹ of Cd, was 6.1 and 4.5%, respectively. The preconcentration factor obtained was 24. The system’s accuracy was confirmed by analyzing the following certified reference materials (CRMs): Rice flour NIES 10b, Apple leaves NIST 1515 and Orchard leaves NBS 1571. This procedure was applied to the determination of Cd in cabbage and powdered guarana samples.