砷、锑、铋类药物的应用历史和现状

近年来,由于对主族元素砷、锑、铋的生物功能研究的不断深入,人们已经从仅仅关注它们对人体的生物毒性到开始研究它们在化学药物领域的应用和潜力。本文简要的介绍了砷、锑、铋作为药物应用的历史,综述了近年来砷、锑、铋的化合物在抗癌、治疗白血病、抗寄生虫病和抗菌方面的一些应用,以及用于发现这些药物的靶分子和结合蛋白的现代生物技术。     

Chemometric approach to the optimisation of LC-FL and GC-MS methods for the determination of nitrite and nitrate in some biological,food and environmental samples

Gas chromatography–mass spectrometry (GC-MS) method and a liquid chromatography–fluorescence (LC-FL) detection method using experimental design and optimisation approach were improved for the quantitative determination of nitrite and nitrate in biological, food and environmental samples. The obtained recoveries of nitrite and nitrate ions from samples based on both GC-MS and LC-FL results ranged from 98.5% to 98.9% for nitrite and 97.9% to 98.4% for nitrate. The precision of these methods, as indicated by the relative standard deviations (RSDs), was within the range from 2.4% to 3.6% for nitrite and 2.5% to 3.8% for nitrate, respectively. The limits of detection of nitrite and nitrate ions from samples based on GC-MS and LC-FL results ranged from 0.01 to 0.14 ng L^?1 for nitrite and 0.02 to 0.71 ng L^?1 for nitrate, respectively. The optimised isolation procedure by central composite design was successfully applied to real samples. The results revealed that the proposed procedure combined with GC-MS and LC-FL techniques is more sensitive, reliable and selective compared to the other methods available for the precise determination of trace levels of nitrite and nitrate in biological, food and environmental samples.     

An organoantimony nitrate complex with azastibocine framework as water tolerant Lewis acid catalyst for the synthesis of 1,2-disubstitued benzimidazoles

A novel organoantimony complex of 6-cyclohexyl-6,7-dihydrodibenzo[c,f] [1,5]azastibocin-12(5H)-yl nitrate ( 2 ) was synthesized and systematically characterized by techniques such as NMR spectra, TG-DSC, and X-ray diffraction. It was found that the complex 2 exhibits relatively strong Lewis acidity (3.3 < Ho ≤ 4.8) and could be employed as a water tolerant Lewis acid catalyst for the synthesis of synthetically valuable benzimidazole derivatives starting from aldehydes and arylenediamines. This catalytic system shows excellent tolerance toward a wide variety of functional groups, such as methyl, methoxyl, fluoro, chloro, bromo, nitro, cyan, trifluoromethyl, 1-naphthaldehyde, furfural and n-butyl, together with facile reusability in 5 times scale enlarged synthesis.     

The Influence of Ammonium on Nitrate Uptake and Assimilation in 2-Year-Old Ash and Oak Trees - A Tracer-Study with 15N

Abstract

Interactions between ammonium and nitrate as competitive N sources depend on various biotic and abiotic factors. The preference for one of these N sources and the influence of ammonium on nitrate uptake and nitrate reductase activity was investigated in a ¹⁵N labelling experiment using 2-year-old potted plants of ash (Fraxinus excelsior L.) and oak (Quercus robur L.) under greenhouse conditions.

Seedlings of both tree species use ammonium and nitrate in equal amounts when both N forms are supplied in a 1:1 ratio (1.5 mM NH₄ ⁺ + 1.5 mM NO₃ ^?), although there is a slight tendency that ammonium is preferred. In both species total N uptake is higher if ammonium and nitrate are supplied simultaneously when compared with uptake of nitrate alone (3 mM nitrate). If nitrate is the sole N source N uptake is only half as high as if ammonium and nitrate are supplied in a ratio of 1:1.

The distribution of nitrate reductase between shoot and roots is not influenced by the N-form: nitrate reductase activity is always highest in the roots of both species under the conditions of this experiment.

Xylem sap analyses showed that both species transport higher concentrations of amino acids than of nitrate from the roots to the shoot. The amino acid composition is independent of the type of N source. Furthermore, ash trees contain more nitrate in the xylem sap than oak trees, reflecting the higher N uptake and the higher nitrate reductase activity in the leaves of this species.     

Reaction of Amino Acids,Di‐ and Tripeptides with the Environmental Oxidant NO3.: A Laser Flash Photolysis and Computational Study

Absolute rate coefficients for the reaction between the important environmental free radical oxidant NO₃^. and a series of N‐ and C‐protected amino acids, di‐ and tripeptides were determined using 355 nm laser flash photolysis of cerium(IV) ammonium nitrate in the presence of the respective substrates in acetonitrile at 298±1 K. Through combination with computational studies it was revealed that the reaction with acyclic aliphatic amino acids proceeds through hydrogen abstraction from the α‐carbon, which is associated with a rate coefficient of about 1.8×10⁶ m ^?1 s^?1 per abstractable hydrogen atom. The considerably faster reaction with phenylalanine [k=(1.1±0.1)×10⁷ m ^?1 s^?1] is indicative for a mechanism involving electron transfer. An unprecedented amplification of the rate coefficient by a factor of 7–20 was found with di‐ and tripeptides that contain more than one phenylalanine residue. This suggests a synergistic effect between two aromatic rings in close vicinity, which makes such peptide sequences highly vulnerable to oxidative damage by this major environmental pollutant.     

Determination of constant‐volume combustion energy for the complexes of zinc nitrate with three amino acids

Five solid complexes of zinc with L‐α‐methionine, L‐α‐phenylalanine and L‐α‐histidine were prepared. The constant‐volume combustion energies of the complexes, ΔE_c (coordination), were determined by a precise rotating bomb calorimeter at 298.15 K. They were ‐ 2969.03 ± 0.34, ‐2929.46 ± 1.59, ‐9597.13 ± 6.12, ‐4378.98 ± 3.27 and ‐14047 ± 6.75 kJ/mol, respectively. Their standard enthalpies of combustion, ΔH^θ_m,c(coordination, s, 298.15 K), and standard enthalpies of formation, ΔH^θ_m,f (coordination, s, 298.15 K), were calculated. They were ‐2959.73 ± 0.34, ‐2923.88 ± 1.59, ‐9649.18 ± 6.12, ‐4373.40 ± 3.27, ‐14048.53 ± 6.75 kj/mol and ‐1180.94 ± 0.92, ‐1401.26 ± 1.77, ‐2501.69 ± 6.50, ‐1381.47 ± 3.49, ‐1950.19 ± 7.65 kJ/mol, respectively.     

铋纳米管的快速合成与表征

以铁粉作还原剂在水溶液中通过置换反应在室温下成功地合成了铋纳米管,并采用透射电子显微镜、电子衍射、X射线粉末衍射仪和热重分析仪对样品进行了鉴定和表征．结果表明所合成的样品呈肩并肩式的管状结构,管径比较均一,并具有高的结晶性和相纯度．热重分析显示所制备的样品含有约3．2％的有机物,并具有良好的热稳定性能．