Separation and determination of podophyllum lignans by micellar electrokinetic chromatography

A micellar electrokinetic chromatography method was established for the quantitative analysis of seven podophyllum lignans in Podophyllum emodi Wall. var. chinesis sprague. The optimum buffer system was 10 mM NaH2PO4-5 mM borate-100 mM sodium dodecylsulfate-30% isopropanol (pH 7.20). Voltage was 18 kV and detection at 214 nm. The second derivative chromatogram was used to determine a low-content component and those not fully separated from adjacent ones. The RSD values of migration times and peak areas were <2.2 and <5.5%, respectively. The effects of several CE parameters on the resolutions were studied systematically.     

Study of the Fluorescence System of Europium–Enoxacin and its Applications

 This paper is the study of the fluorescence enhancement of Eu³⁺-1-ethyl-6-fluoro-4-oxo-7-(1-piperazinyl)-1,8-naphthyridin-3-carbonic acid (enoxacin, EFLX) system by surfactants. It was found that sodium dodecylbenzenesulfonate (SDBS) exhibits great enhancement on the fluorescence of the Eu-EFLX system. The molar ratio is 1:2:1 for Eu:EFLX: SDBS. Under the optimum conditions, the fluorescence intensity is a linear function of europium in the range of 1.0 × 10⁻⁸ ∼ 5.0 × 10⁻⁶ mol/L, the detection limit is 1.0 × 10⁻⁹ mol/L. The application of the Eu-EFLX-SDBS system for the determination of trace europium in rare earth samples gave satisfactory results. Received October 19, 2000. Revision August 10, 2001.     

Stereocontrolled synthesis of bicyclic lactone derivatives via tungsten-mediated [3 + 2] cycloaddition of epoxides with a tethered alkynyl group

In the presence of BF3*Et2O, alkynyltungsten complexes underwent [3 + 2] cycloaddition with tethered epoxides to give bicyclic -lactones efficiently. Only one diastereomeric product was formed despite the presence of three stereogenic centers. A mechanism is proposed that involves formation of a tungsten-vinylidenium species via an SN2 attack of the epoxide carbon by an alkynyltungsten group to give a tungsten-enol ether species via counterattack at the central tungsten-vinylidenium carbon by the OBF3- terminus. Most of the tungsten enol ether species were too unstable for isolation and underwent hydrolysis to give only cis-fused -bicyclic lactones. This cyclization works for both cis- and trans-epoxides and tolerates various functional groups. In the case of trans-phenyl epoxide, the reaction led to an addition product via a 6-endo attack of epoxide by the tungsten fragment. This method provides a simple enantiospecific synthesis of complex bicyclic lactones if a chiral epoxide is used in the cyclization. It is also applicable to the one-pot synthesis of bicyclic unsaturated gamma-lactones if a suitable alkynyltungsten functionality is used.     

A modular nanoparticle-based system for reagentless small molecule biosensing

Metalloprotein tethered CdSe nanoparticles have been generated to provide selective and reagentless maltose biosensing. As opposed to cell or protein detection by semiconducting nanoparticle bioconjugates, a modular method for small-molecule detection using semiconducting nanoparticle bioconjugates has been difficult. Here we report a method for reagentless protein-based semiconducting nanoparticle biosensors. This method uses Ru(II) complex-CdSe nanoparticle interactions and the maltose-induced conformation changes of maltose binding protein to alter the CdSe nanoparticle fluorescence emission intensity. In this proof-of-principle system, the maltose-induced protein conformation changes alter the Ru(II) complex-CdSe nanoparticle interaction, which increases the CdSe emission intensity. Altered CdSe emission intensity effects are best described as electron transfer from the Ru(II) complex to the CdSe excited state forming the nonfluorescent CdSe anion. Four surface-cysteine, Ru(II) complex-attached maltose-binding proteins have been studied for maltose dependent alteration of CdSe emission intensities. With 3.0-3.5 nm diameter CdSe nanoparticles, all ruthenated maltose-binding proteins display similar maltose-dependent increases (1.4-fold) in CdSe emission intensity and maltose binding affinities (KA = 3 x 106 M-1). For these four systems, the only difference was the sample-to-sample variation in maltose-dependent responses. Thus, very few surface cysteine mutations need to be examined to find a successful biosensor, as opposed to analogous systems using organic fluorophores. This strategy generates a unimolecular, or reagentless, semiconducting nanoparticle biosensor for maltose, which could be applied to other proteins with ligand-dependent conformation changes.     

Gradient corrections in density functional theory calculations for surfaces: Co on Pd{110}

Ab initio total energy calculations have been performed for CO chemisorption on Pd{110}. Local density approximation (LDA) calculations yield chemisorption energies which are significantly higher than experimental values but inclusion of the generalised gradient approximation (GGA) gives better agreement. In general, sites with higher coordination of the adsorbate to surface atoms lead to a larger degree of overbinding with LDA, and give larger corrections with GGA. The reason is discussed using a first-order perturbation approximation. It is concluded that this may be a general failure of LDA for chemisorption energy calculations. This conclusion may be extended to many surface calculations, such as potential energy surfaces for diffusion.     

Adsorptive stripping measurements of germanium(IV) in the presence of pyrogallol

The adsorptive stripping voltammetric determination of germanium(IV) based on the adsorptive accumulation of the germanium(IV)-pyrogallol complex on a hanging mercury drop electrode is reported. The reduction current of the adsorbed germanium complex is measured by differential-pulse cathodic stripping voltammetry. The peak potential is at -0.42 V vs. Ag AgCl (saturated KCL). The effects of various parameters (ligand concentration, supporting electrolytic composition and concentration, accumulation potential and collection time) on the response are discussed. With controlled accumulation for 3 min, the detection limit is 1.2 x 10(-9) M germanium. The relative standard deviation (at 1.2 x 10(-8) M germanium) is 3.6%. Possible interferences are evaluated. The applicability of the method to the determination of germanium(IV) in ore samples was also successfully carried out.     

Native and stearic acid modified ceria-zirconia supports in normal and reversed-phase HPLC

Porous ceria-zirconia composite with narrow particle size distribution and large specific surface area was synthesized by a sol-gel process. Chromatographic properties of the native supports was investigated in normal phase mode for the separation of test mixtures of basic, neutral and acidic compounds. The new packing material exhibited polar and basic properties, which are suitable for the separation of basic compounds. Lypophilic packing has been obtained by the modification of the ceria-zirconia with stearic acid, which exhibited strong hydrophobicity relative to the native packing. Therefore, the modified ceria-zirconia behaves as a reversed-phase packing material. Different selectivity towards basic compounds was observed on the new packing compared to the native ceria-zirconia and conventional ODS stationary phase.