Systematic study of the transfer of amino acids across the water/l,2-dichloroethane interface facilitated by dibenzo-18-crown-6

Failitated ion transfer reactions of 20 amino acids with dibenzo-18-crown-6 (DB18C6) at the water/1,2-dichloroethane (W/DCE) interfaces supported at the tips of micro- and nano-pipets were investigated systematically using cyclic voltammetry. It was found that there were only 10 amino acids, that is, Leu, Val, lle, Phe, Trp, Met, Ala, Gly, Cys, Gln (in brief), whose protonated forms as cations can give well-defined facilitated ion transfer voltammograms within the potential window, and the reaction pathway was proven to be consistent with the transfer by interfacial complexation/dissociation (TIC/TID) mechanisms. The association constants of DB 18C6 with different amino acids in the DCE (β°), and the kinetic parameters of reaction were evaluated based on the steady-state voltammetry of micro- or nano-pipets, respectively. The experimental results demonstrated that the selectivity of complexation of protonated amino acid by DB18C6 compared with that of alkali metal cations was low, which can be attributed to the vicinal effect arising from steric hindrance introduced by their side group and the steric bulk effect by lipophilic stabilization. Moreover, the association constants and the standard rate constants for different amino acids showed good correlations with their hydrophobicity (π), except Gly and Met, which inferred that the selectivity of such heterogeneous complex reaction for different amino acids with DB18C6, was not only affected by discrimination in binding these ions to the crown ether macro-cycle, but also significantly modified by the ion transfer Gibbs energy which was closely related to the structure of the transferred ions, protonated amino acids.     

Anion transfer at a micro-water/1,2-dichloroethane interface facilitated by beta-octafluoro-meso-octamethylcalix[4]pyrrole

The facilitated transfer of four hydrophilic anions, i.e., Cl-, Br-, NO2-, and CH3CO2-, at the micro-water/1,2-dichloroethane interface supported at the tip of a micropipet has been observed successfully using beta-octafluoro-meso-octamethylcalix[4]pyrrole 2 as the receptor. We have also shown for the first time that the dynamics of this process can be studied by micropipet voltammetry. The standard kinetic rate constants (kdegrees) for facilitated anion transfer at such an interface were determined to be (2.11 +/- 0.90) x 10(-2) and (0.75 +/- 0.50) x 10(-2) cm/s in the case of Cl- and CH3CO2-, respectively. These values are much smaller than those associated with the facilitated transfer of analogous alkali metal ions. This difference is thought to reflect a number of underlying factors, including the higher hydration of anions as compared to similar sized cations. Studies such as these are expected to be useful in understanding the mechanism of anion transport at soft interfaces and for the design of yet-improved anion receptors and carriers.     

A facile interfacial reaction route to prepare magnetic hollow spheres with tunable shell thickness

Magnetic Fe3O4 hollow spheres were successfully synthesized with a water in oil in water (W/O/W) emulsion. During the facile procedure, no high pressure, high temperature, or other complex reaction conditions were required. Transmission electric microscope (TEM) images showed that all the hollow structural products have a good spherical morphology with an average diameter of 160 nm. The average size and the size distribution were further determined with dynamic light scattering (DLS), which reveals that the hollow nanospheres have a narrow size distribution. The average size from DLS was about 180 nm, which approximated that from TEM data. X-ray diffraction (XRD) demonstrates that the products were all Fe3O4 phase without any impurity. By increasing or decreasing the dosage of precipitate and precipitant sources, we controlled the shell thickness successfully in the tens of nanometers range. The formation mechanism of those hollow magnetic nanospheres was discussed by using the "reverse micelle transport" mechanism.     

C-dots assisted synthesis of gold nanoparticles as labels to catalyze copper deposition for ultrasensitive electrochemical sensing of proteins

We report an ultrasensitive protocol for electrochemical sensing using the hydroxyl-rich C-dots assisted synthesis of gold nanoparticles(C-dots@AuNP) as labels with copper depositon reaction. The C-dots catalyzing copper deposition reaction was implemented for the first time. We constructed a sandwich-type immunosensor on the chitosan modified glassy carbon electrode(GCE) by glutaraldehyde(GA) crosslinking, with C-dots@AuNP as biolabels. Copper was deposited on the catalytic surfaces of second antibody-conjugated C-dots@AuNP nanoparticles through CuSO_4-ascorbic acid reduction, because both C-dots and AuNPs could strongly catalyze the CuSO_4 and ascorbic acid to form Cu particles, which amplified the detection signal. Then the corresponding antigen was quantified based on simultaneous chemical-dissolution/cathodic-preconcentration of copper for insitu analysis using anodic stripping square wave voltammetry(ASSWV) directly on the modified electrode. Under optimized conditions, these electrodes were employed for sandwich-type immunoanaly sis, pushing the lower limits of detection(LODs)down to the fg mL~(-1) level for human immunoglobulin G(IgG) and cardiac troponin I(cTnI), a cardiac biomarker. These novel sensors have good stability and acceptable accuracy and reproducibility, suggesting potential applications in clinical diagnostics.     

A novel polyacrylonitrile-based porous structure gel polymer electrolyte composited by incorporating polyhedral oligomeric silsesquioxane by phase inversion method

A novel polyhedral oligomeric silsesquioxane (POSS) composite polyacrylonitrile (PAN)-based porous structure gel polymer electrolyte (GPE) is prepared by phase inversion method. The POSS additive filler is firstly obtained in the dehydration condensation reaction of vinyltrimethoxysilane (VTMS) and 3-methacryloxypropyltrimethoxysilane (MPTMS). The composition and structure of synthetic POSS and the prepared POSS composite PAN-based GPEs are investigated. It is found that compared with pure PAN-based GPE, the POSS composite PAN-based GPE with 8 wt.% POSS presents the homogeneous pore distribution and abundant electrolyte uptake (540.4 wt.%), which endows GPE-8% with the excellent comprehensive performances: the highest ionic conductivity of 2.62?×?10^?3 S cm^?1 at room temperature, the higher lithium ion transference number of 0.38, the good compatibility with lithium anode, and the higher electrochemical stability window of 5.7 V (vs. Li/Li⁺). At 0.2 C, the GPE-8%-based lithium ion battery produces a satisfactory discharge capacity of 140 mAh g^?1.

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药物磁靶向定位释放模拟装置的设计与应用

采用蠕动泵、钕铁硼永磁铁、聚乙烯管、恒温水浴锅和玻璃管组装了一种模拟人体血液循环的磁靶向装置,并应用于模型磁性载药粒子Fe3O4@DFUR-LDH（DFUR：去氧氟尿苷;LDH：硝酸根插层水滑石）的磁靶向定位和药物释放性能的分析。 研究发现,该装置对磁性载药粒子的滞留量最高可达85.3%,并随载药粒子与磁场的间距增大而减小,随释放介质的流速增大而减小。 而装置中模型磁性载药粒子的药物释放速率随释放介质的流速增大而增大。 同时,通过修改该装置的管路系统模拟了药物在治疗过程中不断被消耗情形下的磁靶向治疗过程。 该装置不但可以实现磁性载药粒子的滞留,还可以分析磁性载药粒子被滞留后的定位释放行为,是磁性载药粒子临床试验前性能分析测试的有效工具。     

Influence of Lu2O3 on electrical and microstructural properties of CaCu3Ti4O12 ceramics

In this work, the influence of Lu₂O₃ doped on the dielectric and electrical properties of CaCu₃Ti₄O₁₂ was reported. Lu₂O₃-doped CCTO was prepared by a conventional solid state technique using CuO, TiO₂, and CaCO₃ as starting materials. The samples were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM); dielectric measurements were measured in the 10² Hz–10⁷ Hz frequency range at room temperature; and the nonlinear behavior of all samples was measured. The doping of Lu₂O₃ resulted in an increase in the dielectric constant of CCTO, but decreased the stability of the frequency dependence. Increasing concentrations of Lu₂O₃ resulted in decreasing nonlinear coefficients.     

Polyether macrocycles from intramolecular cyclopropanation and ylide formation. Effect of catalyst and coordination

The use of catalytic metal carbene methodology with diazoacetates for the construction in high yield of polyether macrocycles having ring sizes greater than 25 has been achieved by preventing access to gamma-C-H positions for intramolecular insertion. Cyclopropanation is the exclusive outcome of reactions performed with dirhodium(II) catalysts, and product yields of greater than 70% are obtained without resorting to high dilution with solvents. With copper(I) catalysts having multiple sites for polyether coordination, intramolecular oxonium ylide formation occurs at the terminal oxygen, followed by [2,3]-sigmatropic rearrangement of the pendant allyl group, in competition with cyclopropanation. Sodium ion coordination with the reactant diazo compound inhibits oxonium ylide formation in copper-catalyzed reactions. The composite results are consistent with copper serving as a template for the substrate as well as the site in the ether complex for diazo decomposition and subsequent metal carbene reactions.