Optimization of a comprehensive two-dimensional normal-phase and reversed-phase liquid chromatography system

The present investigation is based on the evaluation of the performance of a comprehensive two-dimensional liquid chromatography (LCxLC) system during method optimization. The LCxLC set-up, operated in normal phase (NP) mode (adsorption) in the first dimension (1D) and reversed-phase (RP) mode in the second dimension (2D), is equipped with a 1D microbore silica column and a 2D monolithic C(18) column with a 10-port two position valve as the interface. A photodiode array detector is used after the 2D separation. A possible cause of peak distorsion because of the immiscibility of the mobile phases employed in the two dimensions is resolved. The optimization of the analytical run time and flow rate for both dimensions and the initial gradient in the 2D is carried out with various standard compounds. The potential and versatility of this LCxLC approach is demonstrated through the separation of 11 standard components, most of them allergens. The latter, which are characterized by a scattered distribution on the 2D space plane, underwent separation on both a hydrophobicity and polarity basis.     

High-speed gas chromatography in doping control: fast-GC and fast-GC/MS determination of beta-adrenoceptor ligands and diuretics

In official doping controls, about 300 drugs and metabolites have to be screened for each sample. Moreover, the number of determinations to be routinely processed increases continuously as the number of both samples and potential illicit drugs keeps growing. As a consequence, increasingly specific, sensitive, and, above all, fast methods for doping controls are needed. The present study presents an efficient fast-GC/MS approach to the routine screening of two different classes of doping agents, namely beta-adrenoceptor ligands and diuretics (belonging to the S3, P2, and S5 groups of the WADA list of prohibited substances). Narrow bore columns (100 mm id) of different lengths and coated with apolar stationary phases were successfully used to separate the derivatized analytes; preliminary experiments (results not shown) showed better performances with OV-1701 for the separation of beta-adrenoceptor ligands. On the same stationary phase some diuretics required too high a temperature or a long isothermal time for elution, in which case a DB1-MS column was preferred. Two methods of sample preparation, derivatization, and analysis were used on aqueous standard mixtures of, respectively, (i) eight beta-adrenoceptor ligands, including five beta-antagonists (acebutolol, alprenolol, atenolol, metoprolol, pindolol) and three beta2-agonists (salbutamol, clenbuterol, terbutaline) and (ii) seventeen diuretic drugs (acetazolamide, althiazide, bendroflumethiazide, bumethanide, canrenone, chlorothiazide, chlortalidone, clopamide, ethacrinic acid, furosemide, hydrochlorothiazide, hydroflumethiazide, indapamide, indomethacine, spironolactone, triamterene, trichloromethiazide) and one masking agent (probenecid). The mixture of beta-adrenoceptor ligand derivatives was efficiently separated in about 5.6 min, while the one of 18 diuretics and masking agents required less than 5 min for analysis. Limits of detection were from 1 microg/L for pindolol, ethacrinic acid, furosemide, indomethacine, and trichloromethiazide, to 20 microg/L for terbutaline, salbutamol, and metoprolol, and 50 microg/L for clopamide; the instrumental repeatability proved to be excellent (area RSD% <2 for almost all analytes). For this work a quadrupole MS with inert ion source has been used, demonstrating that the quadrupole technology is perfectly adequate to provide precise integration of 400 ms-wide GC peaks.     

Noise adjusted principal component reconstruction to optimize infrared microspectroscopy of individual live cells

We have optimized an imaging methodology capable of monitoring individual live HeLa cells using non-synchrotron FTIR in an aqueous environment. This methodology, in combination with MATLAB based pre-processing techniques, allows fast and efficient collection of data with high signal-to-noise ratio in comparison with previous methods using point mode data collection, which required manual operation and more collection time. Also, presented are early results that illustrate interpretable spectral differences from live cells treated with chemotherapeutic drugs, demonstrating the potential of this methodology to develop more desirable modes of treatment for patients in their diagnoses and treatments for disease.     

All-optical simultaneous drop and wavelength conversion of DPSK data

We demonstrate an all-optical scheme for the simultaneous drop and wavelength conversion of bursts of data from a continuous stream of differential phase-shift keyed (DPSK) signals. This function is obtained in a single semiconductor optical amplifier Mach-Zehnder interferometer thanks to proper nonlinear interaction of the data stream and an optical gate signal at different wavelength. Fast switching-time enabling wavelength shifting operation on continuous DPSK data stream at 10 and 40 Gb/s without any bit loss is reported. Corresponding measured power penalties are negligible at 10 Gb/s and about 1.7 dB at 40 Gb/s.     

Synthesis,Crystal Structures and Thermal Analysis of Two New Silver(I)–Dithioether Lamellar Coordination Polymers

Abstract  Two new silver(I)–dithioether coordination polymers based on the self-assembly of the dithioether ligands L ^{n −R} = CH₃–S(CH₂) _n S–CH₃ (n = 1, 3) and AgX silver salts, where X = ClO₄ ⁻ (1) and PF₆ ⁻ (2), have been synthesized and characterized by single crystal X-ray diffraction and TGA. The crystallographic data of those complexes are: (1) Monoclinic P2₁/c; a = 16.5861(3) ?; b = 10.1048(2) ?; c = 15.7843(3) ?; β = 112.570(1)°; V = 2442.83(8) ?³; Z = 4. (2) Monoclinic P2₁/n; a = 8.6500(2) ?; b = 9.4053(2) ?; c = 24.0357(6) ?; β = 92.750(2)°; V = 1953.19(8) ?³; Z = 4. In both complexes, the dithioether building blocks propagated the silver(I) centers to build cationic lamellar coordination polymers, while ClO₄ ⁻ and PF₆ ⁻, which were sandwiched between silver-ligand sheets, counterbalance only the charge of the networks. The thermogravimetric investigation reveals that those complexes decompose in a single step respectively to metallic silver and silver salt. Index Abstract  Two new silver(I)–dithioether coordination polymers, obtained from the self-assembly of dithioether ligands and AgX salts with noncoordinating counteranions (X = ClO₄ ⁻ and PF₆ ⁻), were characterized by X-ray crystallography and thermogravimetric analysis (TGA).