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.     

Study on the Anion Recognition Properties of Synthesized Receptors （Ⅲ）： Convenient Synthesis and Anion Recognition Property of Bisthiosemicarbazone Derivative

A new series of bisthiosemicarbazone derivative receptors(1,2 and 3)have been synthesized by simple steps ingood yields.Their anion recognition properties were studied by UV-Vis and ~1H NMR spectroscopy.The resultshowed that the receptors 1,2 and 3 all had a better selectivity to F~-,CH_3COO~- and H_2PO_4~-,but no evidentbinding with Cl~-,Br~-,I~-,NO_3~- and HSO_4~-.Upon addition of the three anions to the receptors in DMSO,thesolution acquired a color change from colorless to dark yellow that can be observed by the naked-eyes,thus the re-ceptors can act as fluoride ion sensors even in the presence of other halide ions.The data showed that it was regularthat the three receptors had different binding ability with the three anions.For the same anion,the association con-stants followed the trend:receptor 1>3>2.The UV-Vis data indicates that a 1:1 stoichiometry complex isformed through hydrogen bonding interactions between compound 1,2 or 3 and anions.     

Immunoassay of P-glycoprotein on single cell by capillary electrophoresis with laser induced fluorescence detection

The cellular mechanism based on P-glycoprotein (PGP) for its drug pump function has become very important in multidrug resistance (MDR) research. A method has been established to characterize PGP on single K562 cell by coupling capillary electrophoresis with laser induced fluorescence detection. A permeable intact cell after the immunoassay binding with fluorescence labeling antibody was injected into the capillary and directly separated without lysis. It was found that once 5-10 optional cells were detected in batch, the PGP amount on this cell line could be outlined and calculated clearly. The PGP amount on K562 MDR cell line is 3.88 times higher than that on K562 sensitive cell line. These two cell lines with immunoassay binding were also analyzed by injection of multi-cells in order to improve the throughput. A resistance factor so called multidrug resistance multiple (MRM) was introduced to evaluate the MDR difference between cell lines. The MRM values of the cell line K562 measured by single cell analysis are well correlated with those by flow cytometry, which also prove the validity of our method in single cell analysis for the possibility of cancer diagnosis, pharmacokinetics and drug screening in future.     

Supercritical fluid chromatography of petroleum products using flameless sulfur chemiluminescence detection

Supercritical fluid chromatography using flameless sulfur chemiluminescence detection has been investigated for the analysis of sulfur compounds in petroleum products. The chromatography and detection system was easy to implement and exhibited good precision, linearity, selectivity, and sensitivity. A minimum detectable limit of 0.3 pg sulfur/s was obtained, and response to sulfur in different sulfur species was nearly equimolar.     

The role of various binding materials for trace elemental analysis of powder samples using laser-induced breakdown spectroscopy

Study of various binding materials like potassium bromide, poly(vinyl alcohol), starch, silver and aluminum has been carried out using laser-induced breakdown spectroscopy (LIBS). The role of matrix effects using these five binders on LIBS signal intensity was investigated for better performance of LIBS technique as a quantitative analytical tool. For comparative study of different binders, the signal intensity of different Mg lines at 518.3, 517.2, 383.8 and 279.5 nm wavelengths were recorded for pellets prepared with known concentrations of Mg in these binders. The influence of laser energy on ablated mass under different binding materials and its correlation with LIBS signal intensity has been explored. Optical scanning microscopy images of the ablated crater were studied to understand the laser ablation process. The study revealed that the binding material plays an important role in the generation of LIBS signal. The relative signal intensity measured for a standard Mg line (at 518.3 nm) were 735, 538, 387, 227 and 130 for potassium bromide, starch, poly(vinyl alcohol), silver and aluminum as binders, respectively. This indicates clearly that potassium bromide is better as a binder for LIBS studies of powder samples.     

免疫亲和柱净化/柱前衍生化-高效液相色谱荧光检测法测定粮谷中的T-2毒素

建立了免疫亲和柱净化/柱前衍生化-高效液相色谱荧光检测器测定粮谷中T-2毒素含量的方法。样品经甲醇-水(体积比为80∶20)混合溶剂提取,通过免疫亲和柱(IAC)净化,以氰酸蒽(1-AN)为衍生化试剂、4-二甲基氨基吡啶(DMAP)为催化剂进行衍生,以ZORBAX Eclipse XDB-C18 柱为分离柱,乙腈-水(体积比为80∶20)为流动相进行高效液相色谱分离及荧光检测，荧光检测的激发波长为381 nm，发射波长为470 nm。T-2毒素的质量浓度为0.01~1.5 mg/L时与峰高呈良好的线性,相关系数为0.9985。在0.01~1.5 μg/g添加水平下，回收率为79.7%~94.5%,相对标准偏差小于7%；检出限（S/N＝3）为0.01 μg/g。该方法净化效果好,灵敏度高,操作简便快速。     

Indirect UV detection of carbohydrates in capillary zone electrophoresis

Summary A new system for the rapid and sensitive analysis of underivatized carbohydrates has been established using capillary zone electrophoresis with indirect UV detection. At an applied potential of 28 kV, sugars and sugar acids could be separated by the combined effects of electroendosmosis and electrophoresis within 20 minutes in a fused silica capillary of 50 m internal diameter and an effective length of 100 cm using 6mM sorbic acid, pH 12.1, as both carrier electrolytie and chromophore. The alkaline pH ensured ionization of the sugars and, hence, their detection by means of charge displacement. Furthermore, the chosen concentration of sorbic acid allowed the smallest fractional change in the background signal to be measured. While the electrophoretic mobilities of the sugars were found to increase within a pH range of 11.9 to 12.3, those of the sugar acids were not affected. Due to the increasing competition of hydroxide ions in the displacement of the chromophore with rising pH, a significant loss of sensitivity is observed at pH values higher than 12.1 and this pH was found to provide sufficient resolution, optimum sensitivity, and a acceptably short analysis time. Under these conditions, a lower detection limit of 2 pmol was obtained for glucose.     

Tweezer分子的合成和对有机阴离子的配位效应

本文报道新的Ｔｗｅｅｚｅｒ（１）的合成，用＾１ＨＮＭＲ研究了新的Ｔｗｅｅｚｅｒ分子和对硝基苯甲酸盐的配位效应，结果表明它兴通过氢键，静电引力和芳环夹心堆叠作用而自动缔合。     

BRCA1 mutation screening using restriction endonuclease fingerprinting-single-strand conformation polymorphism in an automated capillary electrophoresis system

Efficient mutation scanning techniques are needed for the rapid detection of novel disease-associated mutations and rare-sequence variants of putative importance. The large size of the breast cancer 1 gene (BRCA1) and the many mutations found throughout its entire coding sequence make screening for mutations in this gene particularly challenging. We have developed a method for screening exon 11 of the BRCA1 gene based on restriction enzyme digestion of fluorescence-labeled polymerase chain reaction (PCR) products followed by single-strand conformation polymorphism (SSCP) using an automated capillary electrophoresis system, denoted capillary restriction endonuclease fingerprinting (REF)-SSCP electrophoresis. Using this strategy on a control set of samples, we were able to detect 17 of 18 known sequence alterations. The method was then applied to screen 73 Norwegian females with family histories of breast and/or ovarian cancer. A total of 172 sequence alterations were detected, including substitutions, insertions, and deletions. One novel substitution of unknown function was identified. Sequencing of all samples negative in the capillary REF-SSCP system gave no additional mutations confirming the high sensitivity of the described methodology. Capillary REF-SSCP electrophoresis appeared as a technically convenient technique, requiring amplification of fewer PCR fragments than traditional SSCP. The novel strategy allows high-throughput mutation scanning without radioactive labeling and polyacrylamide gel electrophoresis (PAGE).     

Contactless Conductivity Detection in Capillary Electrophoresis: A Review

The popularity of contactless conductivity detection in capillary electrophoresis has been growing steadily over the last few years. Improvements have been made in the design of the detector in order to facilitate its handling, to allow easy incorporation into available instruments or to achieve higher sensitivity. The understanding of its fundamental working principles has been advanced and the detection approach has also been transferred to lab‐on‐chip devices. The range of applications has been extended greatly from the initial work on small inorganic ions to include organic species and biomolecules. Concurrent determination of cations and anions by dual injection from opposite ends has been demonstrated as well as sample introduction by using flow‐injection systems for easy automation of the process.