Tb(III) Speciation in Human Blood Plasma by Computer Simulation

With the wide application of rare earth fertilizer and medicines1, more and more rare earths enter into environment, and also into human body via food chain. Now it is very urgent to study the biological effect of rare earths on human health and environment. After entering into human body by whatever route, lanthanide ions are transported to secondary deposition sites mainly via the plasma in the blood stream. So it is very important to study lanthanides speciation in human blood plasma. Becau…     

Organometallics in the nearshore marine environment of Australia

This review draws together published information on the occurrence and biogeochemical cycling of selenium, arsenic and tin in the nearshore marine environment of Australia. The selenium content of marine organisms is well documented but little information is available on the selenium content of waters and sediments. The speciation of selenium in organisms, water and sediments is unknown although it appears that selenium is associated with proteins. The occurrence and speciation of arsenic in marine organisms has been extensively studied, with arsonobetaine being isolated as the probable end-product of arsenic metabolism in marine food chains. However, organisms can produce other organoarsenic compounds, e.g. trimethylarsine oxide, which may be metabolized to toxic end-products. Little is known about the occurrence and speciation of arsenic in waters and sediments. Arsenic(V) is dominant in oxygenated waters, with appreciable quantities of arsenic(III) in some deoxygenated waters. There are few data for tin in water, sediments or organisms and no data on naturally occurring tin species. Tributyltin has been measured in water, sediment and organisms from areas affected by boating activity.     

The use of fast protein liquid chromatography with ICP-OES and ES-MS-MS detection for the determination of various forms of aluminium in the roots of Chinese cabbage

The distribution of aluminium (Al) species was investigated in the roots of Al-tolerant Chinese cabbage (Brassica rapa L. ssp. pekinensis) by employing fast protein liquid chromatography (FPLC) with inductively coupled plasma optical emission spectrometry (ICP-OES) and electrospray tandem mass spectrometry (ES-MS-MS) detection. The cabbage was exposed to a nutrient solution that contained 10 μg cm⁻³ of Al³⁺. The results demonstrated that after 24 h of exposure, Al was quantitatively taken up by the cabbage and was distributed in different parts of the plant. 36 ± 6% of total Al was located in the roots, while the remaining 64 ± 10% was transferred to the leaves. It was found that in the roots Al was partially present in the root sap (15.5%), while the majority (84.5%) was accumulated in its apoplasmic compartments. It was further demonstrated that the proportion of Al that entered the symplasm formed a complex with organic acid. Speciation analysis by FPLC with ICP-OES detection and ES-MS-MS identification of the binding ligand indicated that Al-citrate complex was the prevailing species in the root sap.The results of the present study showed that both immobilization of Al in the apoplasmic compartments of the roots and transformation of Al³⁺ to Al-citrate are most likely responsible for the tolerance of Chinese cabbage (B. rapa L. ssp. pekinensis) to the toxic effects of Al³⁺.     

Tandem Chemoselective Suzuki–Miyaura Cross‐Coupling Enabled by Nucleophile Speciation Control

Control of boronic acid speciation is presented as a strategy to achieve nucleophile chemoselectivity in the Suzuki–Miyaura reaction. Combined with simultaneous control of oxidative addition and transmetalation, this enables chemoselective formation of two C? C bonds in a single operation, providing a method for the rapid preparation of highly functionalized carbogenic frameworks.     

原子吸收光谱法测定烟叶中的重金属总量及形态分析

采用火焰原子吸收光谱法测定烟叶中Mn,Cu,Zn元素,石墨炉原子吸收光谱法测定Cd,Cr,Pb元素,以HNO3-H2O2微波消解法获取烟叶中的重金属总量,以超声水提取法获取水溶态重金属进行初级形态分析,以Tessier逐级提取法获取5种形态的重金属进行次级形态分析。实验结果表明,原子吸收光谱法检测6种重金属线性良好,相关系数(r2)不低于0.998 8,检出限为0.16~3.1μg·L-1。烟叶样品中Mn,Cu,Zn,Cd元素主要以可交换态和碳酸盐结合态的形式存在;Cr主要以残渣态的形式存在;而Pb主要以碳酸盐结合态和残渣态的形式存在。     

Stabilities and Biological Activities of Vanadium Drugs: What is the Nature of the Active Species?

Diverse biological activities of vanadium(V) drugs mainly arise from their abilities to inhibit phosphatase enzymes and to alter cell signaling. Initial interest focused on anti‐diabetic activities but has shifted to anti‐cancer and anti‐parasitic drugs. V‐based anti‐diabetics are pro‐drugs that release active components (e.g., H₂VO₄⁻) in biological media. By contrast, V anti‐cancer drugs are generally assumed to enter cells intact; however, speciation studies indicate that nearly all drugs are likely to react in cell culture media during in vitro assays and the same would apply in vivo. The biological activities are due to V^V and/or V^IV reaction products with cell culture media, or the release of ligands (e.g., aromatic diimines, 8‐hydroxyquinolines or thiosemicarbazones) that bind to essential metal ions in the media. Careful consideration of the stability and speciation of V complexes in cell culture media and in biological fluids is essential to design targeted V‐based anti‐cancer therapies.     

The use of 1-phenyl-3-methyl-4-benzoyl-5-pyrazone as chemical modifier for low-temperature electrothermal vaporization for separation and determination of Cr(III) and Cr(VI) by ICP-MS

Based on thermal stability and volatility of 1-phenyl-3-methyl-4-benzoyl-5-pyrazone (PMBP) chelate, a novel method was described for the determination of Cr(III) and Cr(VI) by low-temperature electrothermal vaporization (LETV) combined with inductively coupled plasma mass spectrometry (ICP-MS). It was found that Cr(III) could be rapidly formed in a graphite furnace, and quantitatively vaporized into ICP at a relatively low temperature of 1000 °C with the use of PMBP as a chemical modifier, while Cr(VI) was retained in the graphite tube. Thus, the separation of Cr(III) and Cr(VI) could be realized. The main factors affecting the formation and vaporization of Cr(III)-PMBP chelate were investigated in detail. Under the optimized conditions, the detection limit of Cr(III) for this method was 0.031 ng mL⁻¹ and the relative standard deviation (RSD) for 1.0 ng mL⁻¹ Cr(III) was 5.3% (n = 9, v = 10 μL). The linear range of calibration curve spanned three orders of magnitude. The proposed method was applied to the determination of Cr(III) and Cr(VI) in water samples with satisfactory results.     

Electrochemical speciation of dissolved Cu, Pb and Zn in an estuarine ecosystem (Ria de Vigo, NW Spain): comparison between data treatment methods

The total concentration and chemical speciation of Cu, Pb and Zn were determined by square wave anodic stripping voltammetry (SWASV) in the Ría de Vigo, an estuarine area located in NW Spain. Surface and bottom waters from 6 locations were collected in two seasons during 3 years. The total Pb was below 1 nM, and Cu and Zn concentrations, ranged from 3 to 44 nM and from 9 to 300 nM respectively. A gradient from sampling points located in the port of Vigo to external areas was observed. The speciation of the metals (ligand concentration and apparent complex formation constant K′) was calculated using several methods: The Langmuir and Scatchard linear fits for one and two ligands, the Lorenzo non-linear fit for one ligand and Langmuir non-linear fit for two ligands. The capability of the different methods to achieve reliable results have been discussed and Langmuir linear fit as well as Lorenzo non-linear fit are the most suitable. Cu presented the highest ligand concentrations, followed by Zn and Pb, while mean log K′ values fell in the range 5-9 (±0.6) for all metals and samples. The adjustment of the data treatment methods used to calculate the speciation parameters was found to vary depending on the extent of complexation and on whether one or two ligands needed to be considered.     

反相离子对色谱-电感耦合等离子体质谱法测定化妆品中不同形态的铬

建立了反相离子对色谱(RP-IPC)与电感耦合等离子体质谱(ICP-MS)联用技术快速分离测定化妆品中Cr(III)和Cr(VI)的方法。样品经乙二胺四乙酸钠盐(EDTA)50 ℃水浴中提取后,采用XDB-C18色谱柱分离,以5%(v/v)甲醇-2.0 mmol/L四正丁基铵盐(TBA)水溶液(pH 6.0)作为流动相,流速为1.0 mL/min,进样量为100 μL。采用碰撞池技术消除ICP-MS测定时40Ar12C+、35Cl16O1H+对52Cr+的光谱学干扰。Cr(III)和Cr(VI)的分离过程在5 min内完成。样品中加标量为0.01～0.50 μg时,其回收率为82.7%～107.2%,相对标准偏差(RSD)小于5.62%。该方法操作简便、灵敏度高、重现性好,适合于化妆品中Cr(III)和Cr(VI)的同时分析。