Arsenic speciation based on ion exchange high-performance liquid chromatography hyphenated with hydride generation atomic fluorescence and on-line UV photo oxidation

An on-line method capable of the separation of arsenic species was developed for the speciation of arsenite As(III), arsenate As(V), monomethylarsenic (MMA) and dimethylarsenic acid (DMA) in biological samples. The method is based on the combination of high-performance liquid chromatograph (HPLC) for separation, UV photo oxidation for sample digestion and hydride generation atomic fluorescence spectrometry (HGAFS) for sensitive detection. The best separation results were obtained with an anion-exchange AS11 column protected by an AG11 guard column, and gradient elution with NaH2PO4 and water as mobile phase. The on-line UV photo oxidation with 1.5% K2S2O8 in 0.2 mol L(-1) NaOH in an 8 m PTFE coil for 40 s ensures the digestion of organoarsenic compounds. Detection limits for the four species were in the range of 0.11-0.15 ng (20 microL injected). Procedures were validated by analysis of the certified reference materials GBW09103 freeze-dried human urine and the results were in good agreement with the certified values of total arsenic concentration. The method has been successfully applied to speciation studies of blood arsenic species with no need of sample pretreatment. Speciation of arsenic in blood samples collected from two patients after the ingestion of realgar-containing drug reveals slight increase of arsenite and DMA, resulting from the digestion of realgar.     

Norvancomycin-capped silver nanoparticles: Synthesis and antibacterial activities against E. coli

The synthesis of norvancomycin (NVan)-capped silver nanoparticles (Ag@NVan) and their notable in vitro antibacterial activities against E. coli, a Gram-negative bacterial strain (GNB), are reported here. Mercaptoacetic acid-stabilized spherical silver nanoparticles with a diameter of 16±4 nm are prepared by a simple chemical reaction. The formation process of the silver nanoparticles is investigated by UV-visible (UV-vis) spectroscopy and transmission electron microscopy (TEM). NVan is then grafted to the terminal carboxyl of the mercaptoacetic acid in the presence of N-(3-Dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride (EDAC). The TEM images of single bacteria treated with Ag@NVan show that plenty of Ag@NVan aggregate in the cell wall of E. coli. A possible antibacterial mechanism is proposed that silver nanoparticles may help destroy the stability of the outer membrane of E. coli, which makes NVan easier to bind to the nether part of the peptidoglycan structure. The antibacterial activities of silver nanoparticles on their own, together with the rigid polyvalent interaction between Ag@NVan and cell wall, enables Ag@NVan to be an effective inhibitor of GNB. This kind of bionanocomposites might be used as novel bactericidal materials and we also provide an effective synthesis method for preparing functional bioconjugated nanoparticles here. Supported by the National Natural Science Foundation of China (Grant No. 50373036) and Fok Ying Tung Education Foundation (Grant No. J20040212)     

Estrogen receptor ligands. 12. Synthesis of the major metabolites of an ERalpha-selective, dihydrobenzoxathiin antagonist for osteoporosis

[reaction: see text] During the course of drug metabolism studies, a major metabolite of compound 1 was detected in rhesus monkeys and assigned structure 4. The intriguing biotransformation of 1 leading to 4 was confirmed by a 19-step total synthesis starting from resorcinol (11), the key feature of which was the construction of the oxygen bridge utilizing a phenolic oxidation and trapping sequence. In addition, the synthesis of a related metabolite (5) is described.     

Effect of La_2O_3/γAl_2O_3 Catalyst on the Activation of CH_4 and CO_2 to C_02 Hydrocarbons under Non-equilibrium Plasma

The oxidative coupling of methane (OCM) to C2 hydrocarbons using carbon dioxide as oxidant is an attractive process from environmental point of view. Only a few research papers reported for it1-3. In general, the yield of C2 hydrocarbons was about 6%. This indicated that the method of catalytic activation was unfavorable to the reaction. It is necessary for us to find a new method in order to activate reaction and improve C2 hydrocarbon yield. Non-equilibrium plasma is a cold plasma in…     

嘧啶基苯硫甲基磺酰脲化合物的合成及除草活性

４，６－二氯－２－嘧啶基苯硫甲基磺酰脲与甲醇钠反应，合成了１５个 见文献报道的标题化合物。它们的结构经ＩＲ，＾１ＨＮＭＲ，ＭＳ，元素分析证实。其中一类化合物具有较强除草活性。     

聚苯醚砜在二甲基甲酰胺中稀溶液性质的研究(Ⅱ)

本文用广角及准弹性光散射法测定了聚苯醚砜各级分在DMF中和在θ溶剂中25℃时的均才半径R_G,第二维利系数A_2,流体力学半经R_H,扩散系数D_O,扩散系数的浓度依赖性k_F以及这些参数与分子量M的关系。它们的结果如下R_G=0.031MO~(0.55) D_O(θ)=0.906×10~(-4)M~(0.5) D_0=1.445×10~(-4)M~(0.55)A_2=0.033M~(-0.35) k_D(θ)=0.5M~(0.34) k_D=2.3×10~(-6)M~(1.36)α_H=R_H/R_H(θ)=0.63M~(0.05)R_H(θ)=0.0299M~(0.5)R_H=0.0188M~(0.55) 作者讨论了静态与动态两种高分子尺寸之间的关系;三种溶胀因子α_η和、α_H、α_G之间的关系;以及摩擦系数的浓度系数k_F与流体力学体积V_H之间的关系。它们的结果满足下面各关系式: R_H/R_G=[π(v+1)(2v+1)/3]~(1/2)(2-v)(1-v)/2, α_η~3=α_(G)~2α_H, k_F=1.2A_2M+N_AV_H/M,K_F(θ)=N_AV_H/M     

Dioxygen Affinities and Catalytic Oxidation Performance of Cobalt (II)Complexes with N-Aryl Hydroxamic Acid

It is well known that the study on biomimetic oxygen carriers not only has important theoretic significance to discover the mechanism of reversible bonding, activating oxygen as well as the oxidation reaction in organism, but also has potential application in separating oxygen from air and realizing the high efficiency and selectivity of catalytic oxidation reaction under a mild condition1. Metal- porphyrin and metal- phthalol- gaunine have been extensively used as biomimetic oxygen carriers u…     

Total synthesis of methyl protodioscin: a potent agent with antitumor activity

Methyl protodioscin (1), otherwise known as 3-O-[alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-rhamnopyranosyl-(1-->4)]-beta-d-glucopyranosyl]-26-O-[beta-D-glucopyranosyl]-22-methoxy-25(R)-furost-5-ene-3 beta,26-diol, has been synthesized for the first time from diosgenin through nine steps in an overall yield of 7.8%.     

Direct Synthesis of Oxygenates from Water and Methane via Dielectric-barrier Discharge

In this investigation, a clean, atomic economic and direct synthesis of oxygenates (methanol, ethanol) form water and methane via dielectric-barrier discharge was developed at room temperature and under atmospheric pressure. The effect of discharge voltage on this process was studied. The results showed that the conversion of water can be as high as 7%, the selectivity of methanol and ethanol can be as high as 100%.     

Linear response time-dependent density functional theory for van der Waals coefficients

A linear response time-dependent density functional theory is described and used to calculate the dynamic polarizabilities and van der Waals C(6) coefficients of complex atom pairs. We present values of C(6) for dimers of main group atoms and the first row of transition metal atoms.