Improving quantitative gas chromatography-electron ionization mass spectrometry results using a modified ion source: demonstration for a pharmaceutical application

Gas chromatography-mass spectrometry is a well established analytical technique. However, mass spectrometers with electron ionization sources may suffer from signal drifts, hereby negatively influencing quantitative performance. To demonstrate this phenomenon for a real application, a static headspace-gas chromatography method in combination with electron ionization-quadrupole mass spectrometry was optimized for the determination of residual dichloromethane in coronary stent coatings. Validating the method, the quantitative performance of an original stainless steel ion source was compared to that of a modified ion source. Ion source modification included the application of a gold coating on the repeller and exit plate. Several validation aspects such as limit of detection, limit of quantification, linearity and precision were evaluated using both ion sources. It was found that, as expected, the stainless steel ion source suffered from signal drift. As a consequence, non-linearity and high RSD values for repeated analyses were obtained. An additional experiment was performed to check whether an internal standard compound would lead to better results. It was found that the signal drift patterns of the analyte and internal standard were different, consequently leading to high RSD values for the response factor. With the modified ion source however, a more stable signal was observed resulting in acceptable linearity and precision. Moreover, it was also found that sensitivity improved compared to the stainless steel ion source. Finally, the optimized method with the modified ion source was applied to determine residual dichloromethane in the coating of coronary stents. The solvent was detected but found to be below the limit of quantification.     

Application of thermal analysis in preservation and restoration of historic masonry materials

Thermal analysis techniques have been used in characterizing building materials from significant historic properties in the Charleston, South Carolina area. Determining the chemical and physical effects of deterioration resulting from long periods of exposure is a first step in formulating preservation strategies. In this regard, simultaneous thermal analysis coupled with evolved gas analysis has been used to study reactions between air, seawater, and masonry materials. Further, the traditional petrographic identification of mortar composition is greatly facilitated through use of thermal analysis. Simultaneous thermal analysis allows for an exact determination of the calcium carbonate content in mortars as an alternative to the use of an inferred value based on chemical analysis data. The partial dissolution of calcium carbonate in the presence of sea salt is a major deterioration process. Further, natural cements manufactured in the United States are identified, in part, based on their thermogravimetric (TG) traces and their evolved gases. The data indicates that natural cements form some carbonate phases in addition to the major hydrate phases. Clay bricks are found to exhibit interaction with sea water, with uptake of bicarbonate suggested. Additionally, there is evidence of re-hydroxylation in the 160 year old bricks. The bricks made in coastal zones contain a considerable free silica fraction that is composed of a small percentage of cristobalite. The silica content of the clay bricks is seen to result in very high thermal expansion coefficients in the area of 10 × 10⁻⁶ to 12 × 10⁻⁶ K⁻¹. These studies provide guidance in restoration efforts where authenticity of cements is important. In the event that replacement bricks are required, matching the thermal expansion coefficient of the original bricks is a requirement for preservation of the masonry structure.     

Fitting of transport measurements in polycrystalline La2/3Ca1/3MnO3

Using a previous qualitative explanation to describe the transport properties of polycrystalline La_2/3Ca_1/3MnO₃ thick films, we achieved a good fit of the temperature dependence of the resistance R(T). Depending on the sample, we have observed different metal–insulator (MI) transitions while the magnetic behavior is always similar. Small regions of depleted T_c adjacent to the grain boundary could have an important resistance contribution without affecting the magnetic properties in an appreciable manner. In this work, we achieve a quantitative explanation for the different transport behaviors that we have observed experimentally.     

Luminescent lanthanide complexes with liquid crystalline properties

Lewis-base adducts of tris( β-diketonato)lanthanide(III) complexes were prepared, where the β-diketone is para -alkoxy-substituted 1,3-diphenyl-1,3-propanedione. These compounds are the first examples of liquid crystalline lanthanide complexes in which the mesomorphism is introduced via a β-diketonate ligand. Depending on the type of the Lewis base, the metallomesogens exhibit a monotropic smectic A or a monotropic highly ordered smectic phase. Intense photoluminescence was observed for the europium(III) complexes at room temperature.     

Ablation of Transparent Materials Using Excimer Lasers for Photonic Applications

For many years, the development of effective ablation or laser machining techniques for making micro-optical components has been the key factor in the birth of new photonic devices and systems. In this article, the ablation characteristics of two types of the most important transparent materials, transparent polymers and glasses, are studied. Simple shaped microcavities are first machined for studying the fundamental ablation parameters, including threshold fluence, effective absorption coefficient, and ablation rate. In studying polymer ablation, five standard grades and five proprietary polymeric compounds are selected. Ablation techniques using these transparent polymers for making arrayed ferrules and curved microlenses are presented. Applications of these ablated microstructures for optical fiber connectors, optical fiber coupling and alignment, and transparent chip encapsulants, are introduced and demonstrated with emphasis on the quality of the ablated profiles and dimensions to satisfy the required performance. In glass ablation, borosilicate glasses are considered and their associated ablation behaviors are studied. The procedures to ablate glass-based arrayed microstructures with flat and curved surfaces are described. The utilizations of these arrayed microstructures for optical waveguide, wave absorber, and beam guider, are specifically discussed. Finally, concluding remakes for future trends are presented.     

The structures of some cycloalkane molecular ions by photodissociation and charge-transfer studies in an ICR-spectrometer

The photodissociation spectra of the molecular ions of some cycloalkanes are compared with those of the corresponding acyclic alkanes and alkenes. It is shown that the molecular ions of cyclohexane and cycloheptane are cyclic whereas the cyclopentane ring opens upon ionisation. This conclusion is supported by a study of the charge-transfer equilibria: C₆D₁₂^± + C₆H₁₂ ? C₆D₁₂ + C₆H₁₂^±, C₅D₁₀^± + C₅H₁₀ ? C₅D₁₀ + C₅H₁₀^±. It is furthermore shown that the maxima in the photodissociation spectra of the molecular ions of saturated hydrocarbons correspond to different dissociation processes.     

Diamino-benzo[1,2-d:4,5-d′]bistriazole (DABT), a new useful 1,4-dibenzyne equivalent

The title compound, when treated with two equivalents of lead tetraacetate, is the synthetic equivalent of 1,4-dibenzyne; bis-cycloadducts are formed with dienes and 1,3-dipoles.     

The formation and molecular structure of acetylcyclopentadienylsodium-tetrahydrofuranate

Acetylcyclopentadienylsodium has been isolated in crystalline form as a THF adduct from a reaction between cyclopentadienylsodium and methyl acetate in THF solution. The product has been characterized by means of a single-crystal X-ray diffraction study. {[C₅H₄CMeO]Na·THF}_n crystallizes in the monoclinic space group P2₁/c with unit cell parameters a 6.698(3), b 16.095(4), c 10.661(3) Å, β 92.93(3)° and D_c 1.17 g cm^?3 for Z = 4. Least-squares refinement led to a final R value of 0.080 based on 661 independent observed reflections. The coordination sphere around each sodium atom consists of the oxygen atoms from two C₅H₄CMeO ligands, the oxygen atom of the THF molecule, and an ion contact pair between the sodium and the five ring carbon atoms of the C₅H₄CMeO ligand.