The effects of sample preparation methods on the variability of the electrospray ionization response for model drug compounds

A post-column infusion system was developed in order to analyze suppression of electrospray ionization (ESI) tandem mass spectrometry response in the presence of endogenous plasma interferences. By enabling direct detection of these interfering components, this experimental system was used to analyze the ability of several common extraction procedures to remove endogenous plasma components that cause changes in the ESI response of model drug substances. Methyl-t-butyl ether (MTBE) liquid-liquid, Oasis and Empore solid-phase, and acetonitrile (ACN) protein precipitation sample preparation methods were tested using the post-column infusion system. In all cases, ACN protein precipitation samples showed the greatest amount of ESI response suppression while liquid-liquid extracts demonstrated the least. In addition, the three test compounds, phenacetin, caffeine, and a representative Merck compound, demonstrated that ESI response suppression is compound dependent. Suppression was greatest with caffeine, the most polar analyte, and the smallest for the Merck compound, the least polar analyte. Copyright 1999 John Wiley & Sons, Ltd.     

Gamma-ray spectroscopy with relativistic exotic heavy-ions

Feasibility of gamma-ray spectroscopy at relativistic energies with exotic heavy-ions and new generation of germanium detectors (segmented Clover) is discussed. An experiment with such detector array and radioactive is discussed.     

Percolative transport in the vicinity of charge-order ferromagnetic transition in a hole-doped manganite

We report measurements of non-linear charge transport in epitaxial (La_1−x Pr _x )_0.7Ca_0.3MnO₃ thin films fabricated on (100) oriented SrTiO₃ single crystals by pulsed laser deposition. The end members of this series, namely Pr_0.7Ca_0.3MnO₃ and La_0.7Ca_0.3MnO₃ are canonical charge-ordered (CO) and ferromagnetic manganites, respectively. The onset of the CO state in Pr_0.7Ca_0.3MnO₃ is manifested by a pronounced insulating behavior below ∼ 200 K. The CO state remains stable even when a large (∼ 2×10⁵ V/cm) electric field is applied across the thin film samples. However, on substitution of Pr with La, a crossover from the highly resistive CO state to a state of metallic character is observed at relatively low electric fields. The current-voltage characteristics of the samples at low temperatures show hysteretic and history dependent effects. The electric field driven charge transport in the system is modelled on the basis of an inhomogeneous medium consisting of ferromagnetic metallic clusters dispersed in a CO background.     

Laser-sintered mesoporous TiO2 electrodes for dye-sensitized solar cells

Low-temperature laser sintering has been successfully demonstrated to improve the overall conversion efficiency of dye-sensitized solar cells. Mesoporous TiO₂ electrodes were prepared from a colloidal solution of TiO₂ nanopowders by a laser direct-write technique and then sintered by a quasi-continuous-wave UV laser (λ=355 nm) for the fabrication of dye-sensitized solar cells. The overall conversion efficiency of the cells based on the laser-sintered TiO₂ electrodes was double that of the devices with non-laser-treated TiO₂ electrodes. This enhancement is attributed to both the removal of organic additives and the improved inter-nanoparticle electrical contacts induced by the laser-sintering process, which led to an increase in porosity and dye-absorption sites in the TiO₂ electrodes. PACS 61.80.Ba; 61.46.+w; 73.22.-f; 84.60.Jt     

Optimization of F-doped SnO2 electrodes for organic photovoltaic devices

Fluorine-doped tin oxide (FTO) thin films have been investigated as an alternative to indium tin oxide anodes in organic photovoltaic devices. The structural, electrical, and optical properties of the FTO films grown by pulsed laser deposition were studied as a function of oxygen deposition pressure. For 400 nm thick FTO films deposited at 300°C and 6.7 Pa of oxygen, an electrical resistivity of 5×10⁻⁴ Ω-cm, sheet resistance of 12.5 Ω/□, average transmittance of 87% in the visible range, and optical band gap of 4.25 eV were obtained. Organic photovoltaic (OPV) cells based on poly(3-hexylthiophene)/[6,6]-phenyl-C₆₁-butyric acid methyl ester bulk heterojunctions were prepared on FTO/glass electrodes and the device performance was investigated as a function of FTO film thickness. OPV cells fabricated on the optimum FTO anodes (∼300–600 nm thick) exhibited power conversion efficiencies of ∼3%, which is comparable to the same device made on commercial ITO/glass electrodes (3.4%).     

Spherical nucleic acids

A historical perspective of the development of spherical nucleic acid (SNA) conjugates and other three-dimensional nucleic acid nanostructures is provided. This Perspective details the synthetic methods for preparing them, followed by a discussion of their unique properties and theoretical and experimental models for understanding them. Important examples of technological advances made possible by their fundamental properties spanning the fields of chemistry, molecular diagnostics, gene regulation, medicine, and materials science are also presented.     

Fabrication of terahertz metamaterials by laser printing

A laser printing technique was used to fabricate split-ring resonators (SRRs) on Si substrates for terahertz (THz) metamaterials and their resonance behavior evaluated by THz time-domain spectroscopy. The laser-printed Ag SRRs exhibited sharp edge definition and excellent thickness uniformity, which resulted in an electromagnetic response similar to that from identical Au SRR structures prepared by conventional photolithography. These results demonstrate that laser printing is a practical alternative to conventional photolithography for fabricating metamaterial structures at terahertz frequencies, since it allows their design to be easily modified and optimized.     

A novel laser transfer process for direct writing of electronic and sensor materials

MAPLE direct write (MAPLE DW) is a new laser-based direct-write technique which combines the basic approach employed in laser-induced forward transfer (LIFT) with the unique advantages of matrix-assisted pulsed-laser evaporation (MAPLE). MAPLE DW utilizes an optically transparent substrate coated on one side with a matrix consisting of the material to be transferred mixed with a polymer or organic binder. As in LIFT, the laser is focused through the transparent substrate onto the matrix. When a laser pulse strikes the matrix, the binder decomposes and aids the transfer of the material of interest to an acceptor substrate placed parallel to the matrix surface. MAPLE DW is a maskless deposition process which operates in air and at room temperature. Powders of Ag, BaTiO₃, SrTiO₃, and Y₃Fe₅O₁₂ with average diameters of 1 7m were transferred onto the surfaces of alumina, glass, silicon, and printed circuit board substrates. Parallel-plate and interdigitated capacitors and flat inductors were produced by MAPLE DW over Rogers RO4003 substrates. MAPLE DW was also used to transfer polymer composites for the fabrication of gas sensor chemoresistors. One such composite chemoresistor fabricated with polyepichlorohydrin/graphite was used to detect organic vapors with a sensitivity of parts per million.     

Self-chemical ionization of diethylzinc

The self-chemical ionization of diethylzinc is examined by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and semiempirical molecular orbital calculations. Electron impact of diethylzinc neutral produces the radical cation, C(4)H(15)Zn(+) (m/z x 122), which reacts further with the neutral (C(2)H(5))(2)Zn to give the following product ions: Zn(+) (m/z x 64), C(2)H(5)Zn(+) (m/z x 93), C(4)H(9)Zn(+) (m/z x 121), C(4)H(11)Zn(2)(+) (m/z x 187), and C(6)H(15)Zn(2)(+) (m/z x 215). To determine the structure and pathways for production of these ions, monoisotopic (12)C(4)H(15)(64)Zn(+), (64)Zn(+) and (12)C(2)H(5)(64)Zn(+) were individually isolated and reacted with the neutral background. We also performed semiempirical molecular orbital calculations (ZINDO/1). The molecular orbital calculations and experimental data are consistent in predicting that the ethyl group on the diethylzinc cation carries the positive charge. Copyright 1999 John Wiley & Sons, Ltd.     

Multiple harmonic conversion of pulsed CO2 laser radiation in Tl3AsSe3

The nonlinear material Tl₃AsSe₃ is used to convert pulsed 9.6 m CO₂ laser radiation into its second, third, fourth and fifth harmonic. Internal (external) conversion efficiencies of 28, 14(6.7), 3.6(3.1), and 0.5(0.3)% from the pump fundamental are achieved in 4.8, 3.2, 2.4, and 1.9 m generation respectively.