Fully automated micro- and nanoscale one- or two-dimensional high-performance liquid chromatography system for liquid chromatography-mass spectrometry compatible with non-volatile salts for ion exchange chromatography

A one- or two-dimensional high performance liquid chromatography system for electrospray ionization mass spectrometers has been developed that is optimized for ion exchange and reversed phase separations. A unique and simple valve configuration permits the use of a variety of non-volatile salts; ammonium sulfate was used in an example of strong cation exchange separations. The system was designed and evaluated for both micro- and nanoflow chromatography. The peptide detection limit was approximately 100 fmol for micro- and 20 fmol for nanoflow, demonstrating the concentration and mass sensitivity improvements expected with nanoelectrospray ionization. The 1D/2D-HPLC MS system is fully automated for routine peptide analyses, compatible with direct injection of proteolytic digests, and exhibits chromatographic reproducibility and sensitivity. Software permits operator selection of either a 1D or 2D configuration with corresponding system parameters as required for individual samples. The hardware elements and resulting performance are described in this paper.     

Liquid chromatography particle beam-mass spectrometry with massive cluster impact

A new liquid chromatography-mass spectrometry technique is described that utilizes a particle beam interface to transport and deposit desolvated analyte molecules onto a target surface that is bombarded by a primary beam of massive multiply charged glycerol cluster ions to generate secondary ions for mass analysis. The massive cluster ion beam is generated by electrohydrodynamic emission from a solution of 1. 5-M ammonium acetate in glycerol. In the present instrumental configuration the massive cluster ion gun is placed above the target probe and the particle beam interface is connected through a side port of the mass spectrometer. The massive cluster ion beam and particle beam are intercepted by a target surface substituted for a conventional ion volume. The target surface is positioned such that it is ～ 45 ° to the primary cluster ion beam, the particle beam, and the mass analyzer axis. This geometric orientation represents a compromise among the performances of these three elements. The feasibility of this liquid chromatography-particle beam on-line with massive cluster impact is demonstrated by flow injections of acetylcholine chloride and gramicidin S. Spectra generated from this preliminary study indicate promise for routine liquid chromatography-mass spectrometry of polar compounds by using a robust inlet and an effective generation of secondary ions without an added matrix.     

Self-injection length in La0.7Ca0.3MnO3-YBa2Cu3O7-δ ferromagnet-superconductor multilayer thin films

We have carried out extensive studies on the self-injection problem in barrierless heterojunctions between La_0.7Ca_0.3MnO₃ (LCMO) and YBa₂Cu₃O_7-δ (YBCO) thin films. The heterojunctions were formed in situ by sequentially growing LCMO and YBCO films on 〈100〉 LaAlO₃ (LAO) substrate using a pulsed laser deposition (PLD) system. YBCO micro-bridges with 64 μm width were patterned both on the LAO (control) and LCMO side of the substrate. Critical current, I _c, was measured at 77 K on both the control side as well as the LCMO side for different YBCO film thickness. It was observed that while the control side showed a J _c of ∼ 2 × 10⁶ A/cm², the LCMO side showed about half the value for the same thickness (1800 ?). The difference in J _c indicates that a certain thickness of YBCO has become ‘effectively’ normal due to self-injection. From the measurement of J _c at two different thicknesses (1800 ? and 1500 ?) of YBCO films both on the LAO as well as the LCMO side, the value of self-injection length (at 77 K) was estimated to be ∼ 900 ?. To the authors’ best knowledge, this is the first time that self-injection length has been quantified. A control experiment carried out with LaNiO₃ deposited by PLD on YBCO did not show any evidence of self-injection.     

Study of magnetoresistance and conductance of bicrystal grain boundary in La0.67Ba0.33MnO3 thin film

La_0.67Ba_0.33MnO₃ (LBMO) thin film is deposited on a 36.7°C SrTiO₃ bicrystal substrate using laser ablation technique. A microbridge is created across bicrystal grain boundary and its characteristics are compared with a microbridge on the LBMO film having no grain boundary. Presence of grain boundary exhibits substantial magnetoresistance ratio (MRR) in the low field and low temperature region. Bicrystal grain boundary contribution in MRR disappears at temperature T>175 K. At low temperature, I-V characteristic of the microbridge across bicrystal grain boundary is nonlinear. Analysis of temperature dependence of dynamic conductance-voltage characteristics of the bicrystal grain boundary indicates that at low temperatures (T<175 K) carrier transport across the grain boundary in LBMO film is dominated by inelastic tunneling via pairs of manganese atoms and tunneling through disordered oxides. At higher temperatures (T>175 K), magnetic scattering process is dominating. Decrease of bicrystal grain boundary contribution in magnetoresistance with the increase in temperature is due to enhanced spin-flip scattering process.     

Molar extinction coefficients of some carbohydrates in aqueous solutions

Molar extinction coefficients of some carbohydrates viz. l-arabinose (C₅H₁₀O₅), d-glucose (C₆H₁₂O₆), d-mannose (C₆H₁₂O₆), d-galactose (C₆H₁₂O₆), d(-) fructose (C₆H₁₂O₆) and maltose (C₁₂H₂₄O₁₂) in aqueous solutions have been determined at 81, 356, 511, 662, 1173 and 1332 keV by gamma ray transmission method in a narrow beam good geometry set-up. These coefficients have been found to depend upon the photon energy following a 4-parameter polynomial. These extinction coefficients for different sugars having the same molecular formula have same values varying within experimental uncertainty. Within concentration ranges studied, Beer-Lambert law is obeyed very well.