Development of a broad toxicological screening technique for urine using ultra-performance liquid chromatography and time-of-flight mass spectrometry

Withdrawal of the support for the REMEDi HS drug profiling system has necessitated its replacement within our laboratories with an alternative broad toxicological screening technique. To this end, a novel method, based on ultra-performance liquid chromatography (UPLC) and time-of-flight (TOF) mass spectrometry, was developed for the routine analysis of urine samples. Identification was achieved by comparison of acquired data to libraries containing more than 300 common drugs and metabolites, and was based on a combination of retention time, exact mass and fragmentation patterns. Validation data for the method is presented and comprised an evaluation of the following parameters: precision; transferability of the methodology between the six collaborating laboratories; specificity; extraction recovery and stability of processed samples; matrix effects and sensitivity.This paper presents the benefits of supplementary fragmentation data with particular regard to increasing specificity and confidence of identification and its usefulness with overdosed samples. The utility of the method was assessed by the parallel analysis of 30 authentic urine samples using the REMEDi HS and UPLC-TOF. The latter provided enhanced detection, leading to the identification of twice as many drugs. Furthermore it did not miss any compounds that were identified by REMEDi HS. The UPLC-TOF findings were further verified by a combination of data from three other conventional screening techniques, i.e., GC-MS, HPLC-DAD and UPLC-MS/MS.     

Synthesis and Two‐Photon Absorption Property Characterizations of Small Dendritic Chromophores Containing Functionalized Quinoxaliniod Heterocycles

A series of star‐shaped multi‐polar chromophores (compounds 1 – 3 ) containing functionalized quinoxaline and quinoxalinoid (indenoquinoxaline and pyridopyrazine) units has been synthesized and characterized for their two‐photon absorption (2PA) properties both in the femtosecond and the nanosecond time domain. Under our experimental conditions, these model fluorophores are found to manifest strong and wide‐dispersed two‐photon absorption in the near‐infrared region. It is demonstrated that molecular structures with multi‐branched π frameworks incorporating properly functionalized quinoxalinoid units would possess large molecular nonlinear absorptivities within the studied spectral range. Effective optical‐power attenuation and stabilization behaviors in the nanosecond time domain of a selected representative dye molecule (i.e., compound 2 ) from this model compound set were also investigated and the results indicate that such structural motif could be a useful approach for the molecular design toward strong two‐photon‐absorbing material systems for quick‐responsive and broadband optical‐suppressing‐related applications, particularly to confront long laser pulses.     

Diastereoselective intermolecular cobalt-catalyzed reductive aldol reactions of alpha,beta-unsaturated amides with ketones

Under cobalt catalysis, diethylzinc mediates the conjugate reduction of alpha,beta-unsaturated amides to produce ethylzinc enolates that react with ketones in situ to produce tertiary alcohol-containing aldol products with up to >19:1 diastereoselectivity.     

Formation of free radicals in photoirradiated cellulose. VII. Radical decay

The ESR spectra of untreated and photosensitized celluloses irradiated with three different ultraviolet light sources, i.e., λ > 2537 Å, λ > 2800 Å, λ > 3400 Å, at 77°K under vacuum were studied. Based on the warm-up process, that is, warming the sample from 77°K to 273°K for a certain time and recorded at 77°K, the decay behavior of free radicals of celluloses was examined for changes of the pattern and the intensities of ESR spectra. For the untreated samples irradiated with light of λ > 2537 Å and λ > 2800 Å, beside the two doublet spectra originating from hydrogen atoms (508 gauss splitting) and formyl radicals (129 gauss splitting), the observed sevenline spectrum was resolved to be a superposition of a singlet (ΔH_msl = 16 gauss), a doublet (24 gauss splitting), a triplet (34 gauss splitting), and a quartet (overall width, 88 gauss) spectrum. For the photosensitized samples irradiated with light of λ > 3400 Å, the 1:1:1 three-line spectrum was resolved to be a superposition of a singlet (ΔH_msl = 27 gauss), a doublet (43 gauss splitting), and a triplet (34 gauss splitting) spectrum. The five-line spectra of the photosensitized samples irradiated with light of λ > 2537 Å and λ > 2800 Å were resolved to be a superposition of a singlet (ΔH_msl = 27 gauss), a doublet (43 gauss splitting), and a triplet (34 gauss splitting) spectrum. Based on these findings, the conclusion was drawn that at least six kinds of spectra, generated from six kinds of radical species, were formed in cellulose irradiated with ultraviolet light under appropriate experimental conditions.     

On information-processing abilities of chaotic dynamical systems

A mechanism is suggested to explain the information processing abilities of simple natural brains, which, by experimental evidence, display behavior like chaotic dynamical systems while at rest. The Lorenz system of equations is dealt with as a case study, and a comparison of the suggested mechanism with the standard theory of neural networks is made.     

Ways of selective polycondensation of L‐lysine towards linear α‐ and ε‐poly‐L‐lysine

Polylysines (PL) are highly interesting polymers due to their biocompatibility and their high number of reactive amino groups. So far it was not possible to synthesize them directly from L ‐lysine. Here, we describe two different synthesis routes to selectively polymerize lysine in one batch without the use of protection groups. Applying 1‐ethyl‐3‐(3‐dimethylaminopropyl) carbodiimide as activating agent for the polycondensation of L ‐lysine in water gave selectively linear ε‐PLL. In contrast to this, the polymerization of L ‐lysine in chloroform in the presence of dicyclohexyl carbodiimide and 18‐crown‐6 ether selectively afforded pure α‐PLL. We also assessed the capability of polylysine derivatization by polymer analog reactions with acetic anhydride, methyl iodide and 2,4,6‐trinitrobenzenesulfonic acid. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5053–5063, 2008     

Observation of plastic deformation in TiAlCN/a -C ceramic nanocomposite coating

Extensive plastic deformation of titanium aluminum carbonitride/amorphous carbon nanocomposite coating at room temperature was observed in this study. Nanoindentation measurement showed that the coating hardness was 24.4 GPa with the plasticity of 57.6%. The critical load of 1.3 m coating in scratch test was beyond 100 N. The depth of the 100 N scratch track identified by microstylus profilometer was 6.7 m, while the thickness of the coating in the center of the scratch track observed by scanning electron microscopy was 0.4 m, which is only about one third of that for the as-deposited coating. The amorphous carbon with sp² hybrid and -bonding is proposed to account for this unique plasticity. PACS 81.15.Gh; 81.07.Bc     

From Propagation to Structure: The Experimental Technique of Bombardment as a Contributing Factor to the Emerging Quantum Physics

I observe that quantum physics emerged at the turn of the last century when physics had shifted its concern from propagation phenomena to questions of structure. This transition materialized with the development of a new experimental technique, the bombardment method. The transition is well exemplified by the move from the experimental studies of Heinrich Hertz to those of Ernest Rutherford, and from those of Heinrich Hertz and Philipp Lenard to those of James Franck and Gustav Hertz. I trace the history of Rutherford's experimental bombardment method as it emerged from nineteenth-century propagation studies. I then demonstrate the use of the bombardment method in another experimental context, namely, in the celebrated experiment of Franck and Hertz. I locate the root of this experiment in Lenard's experimental studies and analyze Franck and Hertz's flawed interpretation of it. I conclude by underlining the crucial role that Bohr's quantum theory of the atom played in helping to establish these bombardment experiments as milestones of modern physics.     

Haupt-Abbau-Prozesse bei der Sonnenbestrahlung von Cellulose: ESR-Untersuchungen.

Ohne Zusammenfassung     

Crystallographic characterization of Kr@C60 in (0.09Kr@C60/0.91C60). (NiII(OEP)).2C6H6

A sample of C60 containing ca. 9% Kr@C60 has been used to form crystalline (0.09Kr@C60/0.91C60).(NiII(OEP)).2C6H6 whose X-ray crystal structure reveals that the Kr atom is centered within the carbon cage and does not produce a detectable change in the size of the fullerene.