Stability analysis for double-stranded DNA oligomers and their noncovalent complexes with drugs by laser spray

Laser spray, which is a newly developed ionization technique, can characterize the stability of noncovalent complexes in the solution phase. By using this advantage, laser spray has been applied to probe the intrinsic stability of double-stranded DNA (dsDNA) sequences and their binding affinities with various drugs in the solution phase. Systematic experiments were carried out using six 16-mer and three 22-mer dsDNA oligomers, together with the complexes of the 16-mer dsDNA with minor groove binders: berenil, Hoechst 33342, DAPI, and netropsin. Dissociation curves for each dsDNA or each complex were plotted as a function of laser power. The laser power (E50%), where 50% of each dsDNA or each complex was dissociated, was compared with its melting temperature (Tm) determined by UV spectroscopy. Linear correlations between E50% and Tm were obtained not only for the dsDNA oligomers (correlation factor r = 0.9835) but also for the 16-mer dsDNA complexes with minor groove binders (r = 0.9966). In addition, laser spray has successfully clarified the binding affinities of a 16-mer dsDNA with two intercalators: daunomycin and nogalamycin. In the case of the dsDNA-daunomycin complex, by changing the molar ratio of dsDNA : drug from 1 : 1 to 1 : 5, the concentration-dependent stability of the complex was confirmed by laser spray. The present results demonstrate that laser spray mass spectrometry can be a powerful and convenient method to investigate the relative binding affinities of dsDNA-ligand complexes in the solution phase, which could be applied to the early stage of high-throughput screening of drugs targeting for dsDNA.     

Validation study on 660 pesticide residues in animal tissues by gel permeation chromatography cleanup/gas chromatography-mass spectrometry and liquid chromatography-tandem mass spectrometry

A new method using gel permeation chromatography (GPC) cleanup followed by gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-tandem mass spectrometry (LC-MS-MS) has been established for quantitative determination of 437 pesticide residues in animal tissues such as beef, mutton, pork, chicken, and rabbit. Based on an appraisal of the characteristics of both GC-MS and LC-MS-MS, validation experiments were conducted for 660 pesticides. In the method, 10 g animal samples were mixed with 20 g sodium sulfate and extracted with 35 mL of cyclohexane+ethyl acetate (1+1) twice by blender homogenization, centrifugation, and filtration. Evaporation was conducted and an equivalent of 5 g sample was injected into a 400 mm x 25 mm S-X3 GPC column, with cyclohexane+ethyl acetate (1+1) as the mobile phase at a flow rate of 5 mL/min. The 22-40 min fraction was collected for subsequent analysis. For the 368 pesticides determined by GC-MS, the portions collected from GPC were concentrated to 0.5 mL and exchanged with 5 mL hexane twice. For the 69 pesticides by LC-MS-MS, the portions collected from GPC were dissolved with acetonitrile+water (60+40) after taking the extract to dryness with nitrogen gas. In the linear range of each pesticide, the correlation coefficient was r > or = 0.98, exceptions being dinobuton, linuron, and fenamiphos sulfoxide. At the low, medium and high three fortification levels of 0.2-4800 microg/kg, recoveries fell within 40-120%, among which 417 pesticides recoveries between 60% and 120%, accounting for 95%, 20 analytes between 40% and 60%, accounting for 5%. The relative standard deviation was below 28% for all 437 pesticides. The limits of detection for the method were 0.2-600 microg/kg, depending on each pesticide.     

Novel Water‐Soluble Shape‐Regulatable Luminescent Nanoparticles by Non‐Covalently Bonded Self‐Assembly

Summary: Novel non‐covalently connected water‐soluble nanoparticles that contain poly(fluorene‐co‐phenylene) with hydroxy‐capped alkoxy side chains (PF3BOH) and poly(acrylic acid) (PAA) have been obtained and characterized. With different proportions of PF3BOH and PAA, the shape and size of the nanoparticles can be regulated. The nanoparticles are quite stable in water with no precipitate being observed after weeks. Transmission electron microscopy and dynamic laser light scattering are used to confirm the morphology of the PF3BOH/PAA nanoparticles. Their optical properties have been investigated and show similar optoelectronic properties to a PF3BOH solid film although they do not undergo aggregation.

TEM images of the nanoparticles obtained upon varying the PAA/PF3BOH content.     

纳米富勒烯(nC60)的生态毒性效应

随着纳米技术的飞速发展,纳米材料的应用日趋广泛.同时,纳米材料的大规模生产和应用对人体健康与生态环境可能产生的安全风险也引起了人们的普遍关注.富勒烯是应用最广泛的纳米材料之一,在水中能形成稳定的水溶性纳米颗粒,进而增大其在环境中的迁移性与生物暴露几率.然而目前对纳米富勒烯(nC60)的环境和毒性效应还知之甚少.本文综合评述了水溶性nC60纳米颗粒的制备、稳定机制、在环境中的迁移特性及其与环境中污染物的相互作用,并着重阐述了nC60可能产生的生物毒性效应.分析表明,nC60的生物毒性效应主要与nC60的表面化学特性和颗粒大小有关,同时环境介质也影响nC60的毒性.最后讨论了nC60生态环境效应研究中应加强的若干方面.     

纳米ZnO/聚醋酸乙烯酯复合薄膜的光催化性能研究

采用溶胶-凝胶和浸渍-提拉而后煅烧的方法得到了在可见光作用下具有光催化性能的纳米ZnO/聚醋酸乙烯酯(PVAc)复合薄膜.通过正交设计实验,研究了PVAc的浓度、煅烧温度、煅烧时间、复合薄膜层数和附加ZnO膜层数等工艺因素对光催化性能的影响,并通过SEM,XRD和FT-IR对其进行了分析与表征.在室内普通照明用白炽灯作用下,以甲基橙溶液为催化对象,PVAc含量10%的、在250℃煅烧30min所得到的纳米ZnO/PVAe复合薄膜的光催化性能的实验结果表明,复合薄膜对甲基橙降解率达60%,而使用250℃煅烧30min所得到的纳米ZnO 4层薄膜或PVAc 4层薄膜催化的甲基橙溶液的浓度变化很小.     

加速溶剂萃取-高效液相色谱法测定土壤中的亚当氏剂

加速溶剂萃取仪(ASE)提取土壤中亚当氏剂残留的最佳条件为:甲醇作提取剂,萃取温度90℃,压力为10689.7kPa(1550psi),样品经提取、浓缩后,以高效液相色谱测定含量.方法简便、快速,对土壤中亚当氏剂的回收率为81.2%～102.5%,相对偏差为5.4%,检出限为0.091mg/L.     

Gold nanoparticles enhance the anti-leukemia action of a 6-mercaptopurine chemotherapeutic agent

6-mercaptopurine and its riboside derivatives are some of the most widely utilized anti-leukemic and anti-inflammatory drugs. Their short biological half-life and severe side effects limit their use. A new delivery method for these drugs based on 4-5 nm gold nanoparticles can potentially resolve these issues. We have found substantial enhancement of the antiproliferative effect against K-562 leukemia cells of Au nanoparticles bearing 6-mercaptopurine-9-beta-d-ribofuranoside compared to the same drug in typically administered free form. The improvement was attributed to enhanced intracellular transport followed by the subsequent release in lysosomes. Enhanced activity and nanoparticle carriers will make possible the reduction of the overall concentration of the drug, renal clearance, and, thus, side effects. The nanoparticles with mercaptopurine also showed excellent stability over 1 year without loss of inhibitory activity.     

黄烷类衍生物的合成及其生物活性研究

An efficient and feasible synthetic approach was developed for the synthesis of an array of new flavane derivafives from the substituted benzaldehyde with the reduction of chalcones and subsequent cyclization as the key steps. The purity and structure of the products were confirmed by the elemental analysis and a combination of its IR, ^1H and ^13C NMR, and mass spectra. These synthetic compounds were tested for xanthine oxidase （XO） inhibitions and antifungal actions against Candida albicans, Cryptococcus neoformans, Aspergillus sp. and Trichophyton rubrum. 7-Hydrazinocarbonylmethoxy-4＇-methoxyflavane （9） was found to be the most XO inhibitory with IC50=76.4 μmol/L, and the most potent antifungal compound was 4＇-hydrazinocarbonylmethoxyflavane （12） with minimal inhibition concentration MIC=8 μg/mL against Trichophyton rubrum.     

Unsymmetric-1,3-disubstituted imidazolium salt for palladium-catalyzed Suzuki–Miyaura cross-coupling reactions of aryl bromides

A series of 1-(ferrocenylethyl)-3-substituted-imidazolium salts [3-substitute = 2,6-di(iso-propyl)phenyl (1a), 2,4,6-trimethylphenyl (1b), tert-butyl (1c), 1-Ad (1d), cyclohexyl (1e)] have been synthesized from a racemic ferrocenylethyl acetate and the corresponding N-substituted imidazole in high yields (70–94%). A combination of Pd(OAc)₂ and 1a–d was found to form an excellent catalyst system for the Suzuki–Miyaura cross-coupling reactions of aryl bromides with phenylboronic acid in the presence of Cs₂CO₃.     

Radiation effects in the transient hot-wire technique

The transient hot-wire technique is widely used for absolute measurements of the thermal conductivity and thermal diffusivity of fluids. It is well established that fluid radiation effects significantly influence these measurements, especially those for the thermal diffusivity. Corrections for radiation effects are based on the models developed and deviations of the measured data from the ideal line source model. In this paper, the effect of fluid radiation on the measurements of the thermal conductivity of n-pentane is presented. For comparison, the influence of thermal radiation effect on measurement of transparent fluids, such as argon is also shown. The difference between the influence of natural convection and thermal radiation is also demonstrated.