Quantitative measurement of different ceramide species from crude cellular extracts by normal-phase high-performance liquid chromatography coupled to atmospheric pressure ionization mass spectrometry

Normal-phase high-performance liquid chromatography (NP-HPLC) coupled to atmospheric pressure ionization mass spectrometry (APCI-MS) allows quantitative analysis of endogenous ceramide and dihydroceramide species from crude lipid extracts. Qualitative information for the species comes from observation of differences in chromatographic and mass spectrometric behavior between species (Pettus et al. Rapid Commun. Mass Spectrom. 2003; 17: 1017-1026). Quantitative analysis is achieved by (1) use of a synthetic internal standard as an extraction and injection control, (2) lack of salt adduction, ion suppression, or other matrix effects in APCI mode, and (3) consistent fragmentation and ionization of external standards across the physiologically relevant concentration range found in endogenous lipid samples. Application to the analysis and quantitation of ceramide and dihydroceramide from various cell lines is demonstrated. The results from APCI-MS analysis corroborate and enhance information acquired from use of the diacylglycerol kinase assay for total ceramide measurement. This technique readily allows simultaneous quantitation of ceramide and dihydroceramide species.     

Effect of non-significant proportional bias in the final measurement uncertainty

The trueness of an analytical method can be assessed by calculating the proportional bias of the method in terms of apparent recovery. If the apparent recovery does not differ significantly from one, the analytical method has not a significant bias. If this is the case, the bias is neglected and the uncertainty associated with this bias is included in the uncertainty budget of results. However, when assessing trueness there is always a probability of incorrectly concluding that the proportional bias is not significant. Therefore, the uncertainty of results may be underestimated. In this paper, we study how non-significant bias affects the uncertainty of analytical results. Moreover, we study how to avoid the underestimation of uncertainty by including the non-significant bias calculated in the uncertainty budget. To answer these questions, we have used the Monte-Carlo method to simulate the process of estimating the apparent recovery of a biased analytical method and, subsequently, the future results this method provides. The results of the simulation show that non-significant bias may underestimate the uncertainty of analytical results when bias contributes in more than 20% to the overall uncertainty. Uncertainty is specially underestimated when bias contributes in more than 50% to the overall uncertainty.     

Diffractively produced charm final states in 800-GeV/c pp collisions

We report the first observation of diffractively produced open charm in 800-GeV/c pp collisions of the type pp-->pD*X. We measure cross sections of sigma(diff)(D*+) = (0.185+/-0.044+/-0.054) (mu)b and sigma(diff)(D(*-)) = (0.174+/-0.034+/-0.029) (mu)b. Our measurements are based on 4.3x10(9) events recorded by FNAL E690 in the fixed-target run of 1991. We compare our results with previous fixed-target charm experiments.     

NMR phase noise in bitter magnets

We have studied the temporal instability of a high field resistive Bitter magnet through nuclear magnetic resonance (NMR). This instability leads to transverse spin decoherence in repeated and accumulated NMR experiments as is normally performed during signal averaging. We demonstrate this effect via Hahn echo and Carr--Purcell--Meiboom--Gill (CPMG) transverse relaxation experiments in a 23-T resistive magnet. Quantitative analysis was found to be consistent with separate measurements of the magnetic field frequency fluctuation spectrum, as well as with independent NMR experiments performed in a magnetic field with a controlled instability. Finally, the CPMG sequence with short pulse delays is shown to be successful in recovering the intrinsic spin--spin relaxation even in the presence of magnetic field temporal instability.     

27Al field-swept and frequency-stepped NMR for sites with large quadrupole coupling constants

Spectra of nonspinning samples with large quadrupole coupling constants, 16-32 MHz, are acquired by frequency-stepping. A series of spin-echoes are acquired at arbitrary frequency increments, frequency-shifted in the time domain, and co-added as magnitude spectra. This procedure is derived from a method in use for field-swept NMR. The two methods are compared.     

N‐(Tri­phenyl­methyl­sulfanyl)­phthal­imide

The title compound, C₂₇H₁₉NO₂S, contains chains of fused (19) rings formed by intermolecular C—H·O=C hydrogen bonds and running along the [011] and [01] directions. These chains are linked through short intermol­ecular C—H·π contacts, giving rise to sheets. The conformation of the title compound is dominated primarily by the nearly orthogonal lone‐pair orbitals on the N and S atoms.     

Involutive Brauer groups of a Krull domain

In this text, we introduce and study involutive class groups and Brauer groups of a Krull domain R. We derive some exact sequences, connecting these groups and linking them to classical invariants, thus allowing to calculate them in concrete situations. We provide a geometric interpretation in terms of etale cohomology with respect to the sheaf of square roots of unity on Spec(R), as another useful tool to calculate these invariants.