Identification of clusters from reactions of ruthenium arene anticancer complex with glutathione using nanoscale liquid chromatography fourier transform ion cyclotron mass spectrometry combined with <Superscript>18</Superscript>O-labeling

Reactions of the anticancer complex [(eta(6)-bip)Ru(en)Cl](+) (where bip is biphenyl and en is ethylenediamine) with the tripeptide glutathione (gamma-L-Glu-L-Cys-Gly; GSH), the abundant intracellular thiol, in aqueous solution give rise to two ruthenium cluster complexes, which could not be identified by electrospray mass spectrometry (ESI-MS) using a quadrupole mass analyzer. Here we use Fourier transform ion cyclotron mass spectrometry (nanoLC-FT-ICR MS) to identify the clusters separated by nanoscale liquid chromatography as the tetranuclear complex [{(eta(6)-bip)Ru(GSO(2))}(4)](2-) (2) and dinuclear complex [{(eta(6)-bip)Ru(GSO(2))(2)}(2)](8-) (3) containing glutathione sulfinate (GSO(2)) ligands. Use of (18)OH(2) showed that oxygen from water can readily be incorporated into the oxidized glutathione ligands. These data illustrate the power of high-resolution MS for identifying highly charged multinuclear complexes and elucidating novel reaction pathways for metallodrugs, including ligand-based redox reactions.     

Magnetic microsphere-based methods to study the interaction of teicoplanin with peptides and bacteria

Teicoplanin (teic) from Actinoplanes teichomyceticus is a glycopeptide antibiotic used to treat many Gram-positive bacterial infections. Glycopeptide antibiotics inhibit bacterial growth by binding to carboxy-terminal d-Ala-d-Ala intermediates in the peptidoglycan of the cell wall of Gram-positive bacteria. In this paper we report the derivatization of magnetic microspheres with teic (teic-microspheres). Fluorescence-based techniques have been developed to analyze the binding properties of the microspheres to two d-Ala-d-Ala terminus peptides. The dissociation constant for the binding of carboxyfluorescein-labeled d-Ala-d-Ala-d-Ala to teic on microspheres was established via fluorimetry and flow cytometry and was determined to be 0.5 × 10⁻⁶ and 3.0 × 10⁻⁶ mol L⁻¹, respectively. The feasibility of utilizing microparticles with fluorescence methods to detect low levels (the limit of bacterial detection was determined to be 30 colon-forming units; cfu) of Gram-positive bacteria has been demonstrated. A simple microfluidic experiment is reported to demonstrate the possibility of developing microsphere-based affinity assays to study peptide–antibiotic interaction.     

In situ chemical fabrication of polyaniline/multi-walled carbon nanotubes composites as supports of Pt for methanol electrooxidation

Science China Chemistry - In this study, platinum (Pt)-polyaniline(PANI)/MWNTs catalysts were synthesized by two sequential reactions. First, core-shell structural PANI/MWNTs composites were...     

HPLC-MS/MS enantioseparation of triazole fungicides using polysaccharide-based stationary phases

The enantiomeric separation of 21 triazole fungicides was carried out on four polysaccharide-derived chiral stationary phases in the reversed phase separation mode using high performance liquid chromatography coupled with tandem mass spectrometry. All fungicides were detected in electrospray ionization (ESI) positive mode with selected reaction monitoring (SRM). Complete enantioseparation was achieved for 21 fungicides except for difenoconazole based on cellulose tris (3,5-dimethylphenylcarbamate) and cellulose tris (3-chloro-4-methylphenyl carbamate) columns by optimizing experimental conditions including mobile phase and column temperature. Mobile phase was 0.1% formic acid aqueous solution mixed with methanol or acetonitrile in different proportions. Among all the fungicides, 15 with two enantiomers and three with four stereoisomers (bitertanol, bromuconazole, and cyproconazole) were successfully separated at 25°C. Enantioseparation for the other three fungicides (propiconazole, triadimenol, and difenoconazole) with four stereoisomers could be achieved by changing the column temperature from 10 to 40°C. Propiconazole and triadimenol were enantioseparated on baseline at 40 and at 35°C, respectively, and difenoconazole was enantioseparated partially with the R(s) > 1.1 at 25°C. Moreover, linearities and limits of detection (LODs) of 21 fungicides except for difenoconazole were studied, showing coefficients of determination (R(2)) higher than 0.99 and LODs lower than 2.5 μg/L.     

高碘酸氧化法快速测定进口粗甘油中甘油含量

建立了高碘酸氧化法快速测定进口粗甘油中甘油含量的分析方法。对高碘酸钠加入量、溶液pH值和放置时间等主要影响因素进行了考察。经试验确定了最佳实验条件:质量浓度为60 g/L的高碘酸钠溶液加入量35mL,pH值在0.4～1.6之间,放置时间40 min。在选定实验条件下,该方法测定结果的相对标准偏差为1.26%(n=7),加标回收率为97.2%～104.1%。     

Cu-DNAzyme facilitates highly sensitive immunoassay

A simple Cu-DNAzyme system is used for signal transduction of a CuO nanoparticle-labeled immunoassay, which makes the immunoassay fast, simple, cost-effective, and sensitive, thus promising for biomedical applications and point-of-care testing.     

不锈钢1Cr18Ni9Ti中铬含量测量不确定度的评定

采用国际通用的方法研究了过硫酸铵氧化容量法测定铬含量的不确定度,分析了容量法中摩尔质量、样品质量、溶液的体积、温度等因素对测量不确定度的影响,评估了各参数的标准不确定度、合成标准不确定度和扩展不确定度。找出了影响容量法测定铬含量准确度的主要原因。     

Recent advances in molecular imprinting technology: current status, challenges and highlighted applications

Molecular imprinting technology (MIT) concerns formation of selective sites in a polymer matrix with the memory of a template. Recently, molecularly imprinted polymers (MIPs) have aroused extensive attention and been widely applied in many fields, such as solid-phase extraction, chemical sensors and artificial antibodies owing to their desired selectivity, physical robustness, thermal stability, as well as low cost and easy preparation. With the rapid development of MIT as a research hotspot, it faces a number of challenges, involving biological macromolecule imprinting, heterogeneous binding sites, template leakage, incompatibility with aqueous media, low binding capacity and slow mass transfer, which restricts its applications in various aspects. This critical review briefly reviews the current status of MIT, particular emphasis on significant progresses of novel imprinting methods, some challenges and effective strategies for MIT, and highlighted applications of MIPs. Finally, some significant attempts in further developing MIT are also proposed (236 references).     

Structure of aqueous sodium metaborate solutions: X-ray diffraction study

A structural analysis of aqueous sodium metaborate solutions (NaBo₂ · nH₂O, n = 10, 15, 20) at 298 ± 0.5 K by a rapid liquid ??-?? X-ray diffractometry with a highly effective X??celerator detector is reported in present paper. The radial distribution functions (RDF) and theoretical partial radial distribution functions for B-O, O-O, Na-O, Na-B, and Na-Na atom pairs were obtained from precisely diffraction data processing. Structure of aqueous sodium metaborate solutions was given through model calculation and described in three different items: hydrated sodium ion, hydrated metaborate ion and ion association. Effects of concentration on the structure of the solutions were discussed in detail. The mechanisms of ion aggregation and the formation of crystal nuclei in the solution are proposed. The results show that a clear picture of the structure of aqueous sodium metaborate solution has been acquired.     

Highly oxidized graphene with enhanced fluorescence and its direct fluorescence visualization

We prepared hyper-oxidized graphene (HOG) as a form of graphene derivative by additional oxidation of graphene oxide (GO) sheets. HOG, which formed more functional groups and isolated conjugated clusters on the sheets, accordingly showed high solubility in water and alcohols, high transmittance and film transparence, longer fluorescence decay constant time, and enhanced fluorescence in states of solution and solid. By contrast, GO has much weaker fluorescence in solution and its fluorescence is totally quenched in solid. The influences of concentration, metallic ions, and pH on HOG fluorescence in aqueous solution were also investigated in detail. Due to HOG’s strong fluorescence, direct visualization was realized on substrates and in solution. In addition, direct 3D fluorescence visualizations of HOG phase in polymer composites were achieved. These results show the great potential of HOG in a broad range of applications, from biological labeling, probes, and drug carriers to high-performance composites and nanomanipulation.