Experimental and Theoretical Investigation of the Proton-Bound Dimer of Lysine

The structure of the proton-bound lysine dimer has been investigated by infrared multiple photon dissociation (IRMPD) spectroscopy and electronic structure calculations. The structures of different possible isomers of the proton-bound lysine dimer have been optimized at the B3LYP/6-31 + G(d) level of theory and IR spectra calculated using the same computational method. Based on relative Gibbs free energies (298 K) calculated at the MP2/aug-cc-pVTZ//B3LYP/6-31 + G(d) level of theory, LL-CS01, and followed closely (1.1 kJ mol^–1) by LL-CS02 are the most stable non-zwitterionic isomers. At the MP2/aug-cc-pVTZ//6-31 + G(d) and MP2/aug-cc-pVTZ//6-31 + (d,p) levels of theory, isomer LL-CS02 is favored by 3.0 and 2.3 kJ mol^–1, respectively. The relative Gibbs free energies calculated by the aforementioned levels of theory for LL-CS01 and LL-CS02 are very close and strongly suggest that diagnostic vibrational signatures found in the IRMPD spectrum of the proton-bound dimer of lysine can be attributed to the existence of both isomers. LL-ZW01 is the most stable zwitterionic isomer, in which the zwitterionic structure of the neutral lysine is well stabilized by the protonated lysine moiety via a very strong intermolecular hydrogen bond. At the MP2/aug-cc-pVTZ//B3LYP/6-31 + G(d), MP2/aug-cc-pVTZ//6-31 + G(d) and MP2/aug-cc-pVTZ//6-31 + G(d,p) levels of theory, the most stable zwitterionic isomer (LL-ZW01) is less favored than LL-CS01 by 7.3, 4.1 and 2.3 kJ mol^–1, respectively. The experimental IRMPD spectrum also confirms that the proton-bound dimer of lysine largely exists as charge-solvated isomers. Investigation of zwitterionic and charge-solvated species of amino acids in the gas phase will aid in a further understanding of structure, property, and function of biological molecules.     

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.     

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.     

Photon regeneration from pseudoscalars at X-ray laser facilities

Recently, the PVLAS Collaboration reported an anomalously large rotation of the polarization of light in the presence of a magnetic field in vacuum. As a possible explanation, they consider the existence of a light spin-zero particle coupled to two photons. We propose here a method of independently testing this result using a high-energy photon regeneration experiment (the x-ray analogue of "invisible light shining through walls") using the synchrotron x rays from a free-electron laser. With such an experiment the region of parameter space implied by PVLAS could be probed in a matter of minutes.     

Benzothiadiazole- and pyrrole-based polymers bearing thermally cleavable solubilizing groups as precursors for low bandgap polymers

We report the design, synthesis and characterization of new benzothiadiazole- and pyrrole-based copolymers whose solubility and bandgap drastically change after thermal treatment of their thin films.