Development of aryl-containing dipyrrolyldiketone difluoroboron complexes (BONEPYs): Tune the hydrogen bond o–CH···F for fluoride recognition

Dipyrrolyldiketone difluoroboron complexes (BONEPYs) were synthesized by condensation of the corresponding pyrroles and malonyl chloride followed by treatment with BF₃·OEt₂. The aryl-substituted pyrrole is introduced to form a cyclic system in order to investigate anion binding studies. In BONEPYs 1–3 the o-H of the aryl group forms hydrogen bonding with F⁻ to give a more table complex. In contrast, the intramolecular hydrogen-bonded BONEPY endo-4 is more stable than its exo isomer. While adding F⁻, the hydrogen bonds must be broken first to give 4·(3)F⁻. Owing to the electron-rich group (-OMe), the o-H of the phenyl group can hardly interact with F⁻ via hydrogen bonding to give the less stable complex 4·(5)F⁻. The energy differences between the different conformations were calculated using DFT methods, which is consistent to the experimental observations.     

Molybdenum complexes of bioinorganic interest. New dioxomolybdenum(VI) complexes of schiff bases derived from salicylaldehydes and salicylhydrazide

Summary New dioxomolybdenum(VI) complexes MoO₂L · H₂O (LH₂=Schiff base) derived from Salicylhydrazide and salicylaldehyde, 5-chloro-, 5-bromo-, 5-nitro-, 3-methoxy, 3-ethoxy-, 3,5-dichlorosalicylaldehyde and 2-hydroxy-1-naphthaldehyde have been synthesized and characterized, together with the MoO₂L · THF adducts. The complexes are monomers, nonelectrolytes and diamagnetic, and contain acis O=Mo=O     

Novel strategy for constant-distance imaging using alternating current scanning electrochemical microscopy

Scanning electrochemical microscopy (SECM) still lacks reliable means for performing constant-distance imaging experiments. We demonstrate, for the first time, that the same negative alternating current (AC) feedback can be observed on approach to an insulator and an unbiased conductor at optimal experimental conditions. This leads to a novel constant-distance imaging mode. To perform AC-SECM imaging, only minor modifications of the existing SECM set-up were necessary. The new constant-distance AC-SECM imaging was conducted to provide topographical information not affected by variations in sample conductivity and reactivity. Furthermore, simultaneous AC and DC SECM measurements were carried out to demonstrate that both topographical and chemical information could be revealed.     

Asymmetric Negishi reaction for sterically hindered couplings: synthesis of chiral binaphthalenes

A new synthetic approach affording, for the first time chiral binaphthalene derivatives via an asymmetric Negishi reaction, in good yields (55–95%) and good enantioselectivities (49–85% ee), is reported.     

马钱子中两种微量生物碱异构体的电喷雾多级串联质谱分析

采用电喷雾多级串联质谱方法, 通过分子量和多级串联质谱的信息对马钱子总生物碱提取物中微量生物碱异构体伪士的宁、士的宁氮氧化物进行了分析研究; 并研究了异构体质谱碎裂规律与结构之间的关系. 建立了马钱子中生物碱同分异构体区分的简便、快速、灵敏的新方法.     

Preparation and characterization of self-assembled nanoparticles based on glycol chitosan bearing adriamycin

An anthracycline drug, adriamycin, was chemically conjugated onto the backbone of glycol chitosan via an acid-labile cis-aconityl linkage. The physicochemical characteristics of the glycol chitosan–adriamycin (GC–ADR) conjugates were investigated by dynamic light scattering, atomic force microscopy, and fluorescence spectroscopy. The GC–ADR conjugates were capable of forming nano-sized self-aggregates in an aqueous medium, when the adriamycin content in the conjugate was in the range of 2.0–5.0 wt.%. The self-aggregates were spherical in shape, and had mean diameters of 238–304 nm, depending on the adriamycin content. The critical aggregation concentrations of the conjugates, estimated by the fluorescence quenching method, were as low as 1.0–2.5×10⁻² mg/ml. The size of self-aggregates was not affected by the polymer concentration in the range from 50 to 2,000 μg/ml, and was maintained up to 8 days in phosphate-buffered saline (pH 7.4), indicating high colloidal stability. The release of adriamycin from self-aggregates was significantly dependent on the pH of the medium due to the cis-aconityl linkage; e.g., the amount of adriamycin released for 4 days was 7.3±0.3% at pH 7, whereas it was 29.3±1.9% at pH 4. The cell viability results demonstrated that free adriamycin shows more potent cytotoxicity than the conjugates, primarily attributed to the sustained release of adriamycin from self-aggregates. In conclusion, the self-aggregates, formed by GC–ADR conjugates, might be useful for the site-specific delivery of adriamycin in a sustained manner.     

Application of two-stage biofilter system for the removal of odorous compounds

Biofiltration is a biological process which is considered to be one of the more successful examples of biotechnological applications to environmental engineering, and is most commonly used in the removal of odoriferous compounds. In this study, we have attempted to assess the efficiency with which both single and complex odoriferous compounds could be removed, using one- or two-stage biofiltration systems. The tested single odor gases, limonene, α-pinene, and iso-butyl alcohol, were separately evaluated in the biofilters. Both limonene and α-pinene were removed by 90% or more EC (elimination capacity), 364 g/m³/h and 321 g/m³/h, respectively, at an input concentration of 50 ppm and a retention time of 30 s. The iso-butyl alcohol was maintained with an effective removal yield of more than 90% (EC 375 g/m³/h) at an input concentration of 100 ppm. The complex gas removal scheme was applied with a 200 ppm inlet concentration of ethanol, 70 ppm of acetaldehyde, and 70 ppm of toluene with residence time of 45 s in a one- or two-stage biofiltration system. The removal yield of toluene was determined to be lower than that of the other gases in the one-stage biofilter. Otherwise, the complex gases were sufficiently eliminated by the two-stage biofiltration system.     

Ce(III)在辣根体中的迁移

应用放射性同位素示踪法, 即结合放射自显影和液体闪烁器检测及电镜放射自显影技术, 首次定性、定量地研究Ce(III)离子在辣根植物中的迁移. 结果表明: (1) Ce(III)离子能被辣根植物吸收并随时间发生迁移; (2)电镜放射自显影结果显示, Ce(III)离子迁移是通过质外体至共质体进入细胞的. Ce(III)离子在辣根植物体中的行为, 为稀土离子植物环境效应机理及辣根植物安全防护提供借鉴.     

Determination of Hg(II) in waters by on-line preconcentration using Cyanex 923 as a sorbent — Cold vapor atomic absorption spectrometry

Using a solid phase extraction mini-column home-made from a neutral extractant Cyanex 923, inorganic Hg could be on-line preconcentrated and simultaneously separated from methyl mercury. The preconcentrated Hg (II) was then eluted with 10% HNO₃ and subsequently reduced by NaBH₄ to form Hg vapor before determination by cold vapor atomic absorption spectrometry (CVAAS). Optimal conditions for and interferences on the Hg preconcentration and measurement were at 1% HCl, for a 25 mL sample uptake volume and a 10 mL min^− 1 sample loading rate. The detection limit was 0.2 ng L^− 1 and much lower than that of conventional method (around 15.8 ng L^− 1). The relative standard deviation (RSD) is 1.8% for measurements of 40 ng L^− 1 of Hg and the linear working curve is from 20 to 2000 ng L^− 1 (with a correlation coefficient of 0.9996). The method was applied in determination of inorganic Hg in city lake and deep well water (from Changchun, Jilin, China), and recovery test results for both samples were satisfactory.     

Zirconium–BINOLate-catalyzed,enantioselective aldol-Tishchenko reactions of aromatic ketone aldols

3,3′-Substituted BINOL’s have been identified as suitable chiral ligands for the zirconium-catalyzed aldol-Tishchenko reaction of aromatic ketone aldols with aliphatic aldehydes. 1,3-anti-Diol monoesters were obtained in excellent yields, complete anti-diastereocontrol, and enantioselectivities of up to 60% ee.