朱砂中汞的生物可接受性及其吸收与排泄

研究了朱砂中汞的生物可接受性及其在体内的吸收与排泄.采用体外消化透析法测定了朱砂中汞的生物可接受性;计算了大鼠灌胃给予临床剂量(50mg/kg)朱砂后汞的药动学参数;测定了给予临床剂量的朱砂后大鼠粪样中汞的排泄量.结果表明,朱砂中汞的溶出率为0.011%,生物可接受率为0.003 3%.大鼠灌胃给予临床剂量的朱砂后,汞的药动学参数为:最高血药浓度(ρmax)为(6.3±1.3)μg/L,达峰时间(tmax)为(1.3±0.4)h,半衰期(t1/2)为(4.2±0.5)h,血药浓度-时间曲线下面积(AUC)为(54.7±8.7)μg.h.L-1.给予朱砂12h后汞在粪便中排泄量最大,96h后在粪样中仍可检测到少量汞.朱砂中汞的生物可接受性较低,在体内吸收少,滞留时间较长,排泄缓慢,长期服用可在体内蓄积,产生毒性.     

柱前衍生化高效液相色谱法测定朱砂中可溶性汞的含量

采用二乙基二硫代氨基甲酸钠柱前衍生化高效液相色谱法测定了朱砂在人工胃液中的可溶性汞含量;本法简便,灵敏,精确,可用于朱砂及含朱砂的中成药中可溶性汞的含量测定及质量检验.     

大鼠服用朱砂后脑内氨基酸类递质含量的变化

研究了朱砂对大鼠脑组织中氨基酸类神经递质含量的影响.将32只Wistar大鼠随机分为低、中、高剂量组和对照组,朱砂灌胃给药14天后,采用高效液相色谱法测定大鼠脑组织中谷氨酸(Glu)、天门冬氨酸(Asp)、甘氨酸(Gly)、γ-氨基丁酸(GABA)和牛磺酸(Tau)的含量,并计算兴奋毒性指数(EI)的变化.与对照组相比较,脑组织中氨基酸类神经递质含量均呈下降趋势,其中Asp和Gly的中、高剂量组差异有统计学意义(P0.05),Tau和GABA的高剂量组有统计学差异(P0.05),Glu和EI所有剂量组均有统计学差异(P0.05).朱砂对氨基酸类神经递质具有一定的抑制作用.     

灌喂氯化汞大鼠组织中汞结合金属硫蛋白的色谱/质谱联用表征研究

通过测定大鼠脏器组织中汞的总量、金属硫蛋白(MTs)含量及利用尺寸排阻色谱(SEC)与电感耦合等离子体质谱(ICP-MS)联用技术,分析了灌喂HgCl2大鼠脏器组织中汞与MTs的积累量及金属与MTs的结合形态。结果表明,灌喂HgCl2大鼠各脏器中汞的积累量显著高于其相应的对照组,特别是在肾、肝和睾丸中汞的含量较高,表明此3个脏器受汞的危害最大。MTs的含量水平说明当大鼠脏器受汞污染时,肌体中的MTs将被大量诱导产生以对重金属进行解毒。通过SEC-ICP-MS联用技术获得了组织中的金属与MTs的结合形态,其     

冷原子荧光光谱法测定含朱砂中成药中痕量汞的样品消解溶剂选择

目的为了测定紫金锭、复方牛黄消炎胶囊等含朱砂中成药样品中痕量汞的含量,方法比较并确定了高压密封消解法适用的消解溶剂体系。结果以y（王水）＋V（H2O2）=5＋1为消解溶剂,高压密封消解-冷原子荧光法测得紫金锭和复方牛黄消炎胶囊样品的总汞含量分别为7．22％和2．66％,样品的加标回收率为96．2％-97．8％,RSD小于2％（n=3）;结论实验表明,y（王水）＋y（H2O2）=5＋1混合溶剂适用于紫金锭、复方牛黄消炎胶囊等含朱砂中成药样品的消化,获得的样品汞含量测定结果令人满意。     

增效荧光光谱法测定片剂药物中的甲睾酮

研究了甲睾酮与浓硫酸反应产物的荧光光谱性质,提出了利用表面活性剂增敏荧光光谱测量甲睾酮含量的新方法,初步探讨了表面活性剂十二烷基硫酸钠（SDS）的增敏作用机理,并证实溶液中溶解氧对本实验体系有明显的荧光猝灭作用。该法操作简便,检出限低,用于成品药物分析,结果令人满意。     

Gravimetric Determination of Mercury(II) and Vanadium(IV) with Benzoylacetanilide

Abstract

Gravimetric methods for the determinations of mercury(II) and vanadium(IV) with benzoylacetanilide have been described. These metals have been separated from commonly associated ions and a procedure for the determination of vanadium content of steel has been developed. By these methods, 14 to 50 mg. of mercury and 5 to 20 mg. of vanadium have been estimated with relative standard deviations of 0.18% and 0.10%, respectively.     

基于毛细管电泳的苦参碱转运过程中的血清白蛋白行为成像

利用毛细管电泳(CE)技术在体外条件下建立了苦参碱(MT)与血清白蛋白(SA)相互作用的分析方法。生理条件下通过淌度移动法和前沿分析法(FA)研究苦参碱与血清白蛋白的结合状况,构建配体(MT)-受体(SA)相互作用模型。其中,淌度移动法采用非线性拟合方法获得苦参碱与人血清白蛋白(HSA)结合参数;FA运用非线性回归方程、Scatchard方程、Klotz方程3种方程获得苦参碱与人血清白蛋白结合参数,分析其相互作用状况进而分析模型适用度。利用淌度移动法可知,人血清白蛋白与苦参碱表观结合常数KB为8.072×103 mol/L;利用FA法可知,采用非线性回归方程、Scatchard方程、Klotz方程3种方程获得苦参碱与人血清白蛋白表观结合常数KB分别为1.434×103、1.781×103和2.133×103 mol/L,且二者结合位点数在1.0左右,说明苦参碱与人血清白蛋白作用只有单一类型的结合位点。通过计算分析得到3个方程的相关系数(r),关系为rKlotz>r非线性>rScatchard。结果表明:淌度移动法和FA法均适用于分析MT-HSA体系的结合状况;由于FA法可以计算出表观结合常数的同时又能计算出结合位点数,因而更适合MT-HSA体系的分析研究;分析比较得出3种方程之中Klotz方程为最适理论模型。结合参数表明,MT-HSA相互作用体系之间发生的结合反应为单一类型的结合位点且结合稳定。相关工作阐明了典型生物碱与血清白蛋白的相互作用机制,可为生物碱的血液输运机制的深入研究提供有益参考。     

Synthesis and Multinuclear NMR Study of Benzoyl Methylene Triparatolylphosphorane Ylide and the Reaction of this Ylide with Mercury(II) Halides

The reaction of the title ylide {PhCOCHP(p-tolyl)₃} with Pd(II), Pt(II). Hg(II), and Ag(I) in equimolar ratios using CH₃CN, CH₃OH, and CH₂Cl₂ as solvents have yielded [{(p-tolyl)₃PCHCOC₆H₅} PdCl₂]₂ (I), [{(p-tolyl)₃ PCHCOC₆H₅} PtCl₂]₂(2), [Hg(NO₃)₂ {(p-tolyl)₃ PCHCOC₆H₅}](3), and [Ag{(p-tolyl)₃ PCHCOC₆H₅ < eqid1 > ₂]⁺ (4). The IR, ¹H ¹³C, and ³¹P NMR together with micro analysis data of the products were obtained.     

Cyclic Voltammetric Behavior of Uranyl ion in Sulfuric Acid Solutions. Application to Some Nuclear Materials Characterization

Abstract

The U(VI) reduction at mercury electrode in sulfuric acid solutions was examined by cyclic voltammetry (C. V.). A diffusion coefficient, D, was (5.30 ± 0.08) × 10^?6 cm²/sec was obtained for the depolarizer at 25.0±0.2°C in 1 N K₂SO₄ (pH = 2). In 1 N K₂SO₄/1 N H₂,SO₄ systems the disproportionation of U(V) was found to occur with the constant rate of K_d/[H⁺] = 6.500 ± 1.000 M^?2 sec^?1.

In 1 M H₂SO₄ supporting electrolyte pure kinetic control was achieved over the range of scan rates and uranyl concentration (C) investigated, hence linear correlation between cathodic peak current and C (above 5x10^?6 M) was obtained. Strong complexing oxyanions, such as phosphate and pyrosulphate, do not interfere with the cathodic peak current. Rapid determination of O/U ratios in uranium oxides and of U in mixed U-Th materials were performed respectively in 1 M H₂SO₄/1.5 M H₃PO₄ and 1 M H₂SO₄/0.2 M K₂S₂0₄ supporting media, with a reproducibility of ± 1.3% standard deviation.     

基于Schiff base结构化合物载体的汞离子选择性电极的制备与表征

高产率合成了一种新的Schiffbase结构化合物,并将其表征为高选择性聚合物膜汞离子选择性电极载体。考察了不同增塑剂及离子交换剂对膜电极响应性能的影响,在最佳膜组分条件下测得该电极对汞离子的线性响应范围为10×10-6~30×10-4mol/L,响应斜率为(293±03)mV/dec,检出限为26×10-7mol/L;该电极响应速率快（小于12s）,可在较宽的pH范围内（pH28~56）使用,且其它常见碱金属、碱土金属以及过渡金属离子对该测试电极的干扰小;可准确检测自来水中汞离子的浓度。     

Direct Detection of Mercury-Bound Metalloproteins (metallothionein and Cu,Zn-Superoxide Dismutase) Using a Combination of Gel Electrophoresis and One Dimensional Synchrotron Radiation X-Ray Fluorescence Analysis

Abstract

Metallothionein-II (MT-II) and Cu, Zn-superoxide dismutase (Cu, Zn-SOD) interacted with mercury were detected by a new method utilizing isoelectric focusing-agarose or -polyacrylamide gel electrophoresis (IEF-AGE or IEF-PAGE) and nondestructive one-dimensional synchrotron radiation X-ray fluorescence (SR-XRF) analysis. When MT-II reacted with mercuric chloride, an obvious change of isoelectric point (pI = 3.7 - 4.7) for the intact form to alkaline pI (9.4) was observed. This marked migration of MT-II by the metal was blocked by addition of glutathione, suggesting that sulfhydryl functions participate in the pI variation. In contrast, interaction of Cu, Zn-SOD with mercury did not cause any changes of its pI although the metal bound tightly to Cu, Zn-SOD after electrophoresis; however, the enzyme activity was drastically suppressed. These observations indicate that combination of electrophoresis with SR-XRF analysis is an useful technique for detecting structural or functional alteration of protein attributable to the binding of the mercury.     

对羟基苯甲醛缩邻氨基苯甲酸与汞的荧光猝灭反应及其应用

合成了一种新的席夫碱荧光试剂--对羟基苯甲醛缩邻氨基苯甲酸(HBAA).研究了HBAA与汞离子的络合反应及其反应条件,HBAA在390.0 nm处有一强荧光峰,汞离子存在时,可与其形成稳定的络合物并使HBAA的荧光猝灭.利用该反应建立了荧光测定痕量汞的新方法,方法的线性范围为0 ～90.0 μg/L,检出限为0.61 μg/L.考察了40种常见共存离子的干扰影响,结果表明合成的HBAA试剂具有很高的选择性.该方法简便、快速,可用于矿泉水、自来水、河水中痕量汞的测定.     

Recent progress of calixarene-based fluorescent chemosensors towards mercury ions

In recent years, calixarene-based fluorescent chemosensors for mercury(II) are mushroom growth because of its intrinsic sensitivity. The design of the highly selective calixarene-based chemosensors towards mercury(II) is still a challenging task. In this paper, the progress of highly selective fluorescent sensor for mercury(II) based on calixarene derivatives is reviewed according to a mono-fluorophore chemosensor and a bi-fluorophore chemosensor. Some new developments such as calixarene-modified nanoparticles are also covered.     

2-羟基-4-磺酰氨基苯重氮氨基偶氮苯的合成及环境污水中微量汞的测定

研究了 2 羟基 4 磺酰氨基苯重氮氨基偶氮苯 (HSDAA)与汞的显色反应。在TritonX -1 0 0表面活性剂存在下 ,pH 9 5～ 1 1 5的Na2 B4 O7-NaOH缓冲溶液中 ,该试剂与汞 (Ⅱ )生成配合比为 3∶1的深红色配合物。配合物的最大吸收峰位于λ=5 2 0nm处 ,表观摩尔吸光系数 1 47× 1 0 5L·mol- 1·cm- 1。Hg2 + 的质量浓度在 0～ 480 μg/L范围内符合比耳定律。用拟定方法测定环境污水中的微量汞 ,结果满意。     

The Potential Response Of Copper(Ii) Sulfide Ion Selective Electrode To Hg(Ii) Ions In Aqueous Solution

Abstract

The application of a cupric ion-selective electrode with a membrane of mixed Ag₂S-CuS to measure the activity of Hg(II) is presented. The linear electrode response curve which covers near three decades, from 10^?5 to 10^?2 mol dm^?3, of mercuric concentration range was obtained, under background of acetate buffer.     

The association mode of arsenic accumulated in the freshwater alga Chlorella vulgaris

Arsenic accumulated in living Chlorella vulgaris cells was solvent-fractionated with chloroform/methanol (2:1), and the fractions were analyzed for arsenic. A large part of the accumulated arsenic was localized in the extract residues. The extract residue from the same extraction of C. vulgaris, which had been, however, cultured in any arsenic-free Detmer medium (MD), adsorbed arsenic physico-chemically at a concentration of 1.1 mg As g^?1 dry weight. Arsenic was found to be combined with protein with molecular weight around 3000 in the arsenicaccumulated living cells. The arsenic-bound protein was analyzed for amino acids. The experimental results showed that no metallothionein-like protein was inductively biosynthesized in C. vulgaris on the exposure to arsenic.