Analysis of platelet-activating factor by gas chromatography-mass spectrometry: low-energy electron impact of the corresponding 3-acetyl-2-tert.-butyldimethylsilyl derivative.

A method for the analysis of platelet-activating factor in platelets employing gas chromatography and selected-ion monitoring mass spectrometry with low-energy electron impact and stable isotope dilution was developed. The procedure involved Bligh and Dyer extraction of the sample followed by thin-layer chromatographic purification. Platelet-activating factor is successively hydrolysed to the corresponding 2-acetyl-1-O-alkylglycerol by digestion with phospholipase C, and the product is allowed to isomerize to the more thermodynamically stable 3-acetyl-1-O-alkylglycerol before column purification and derivatization of the free OH with tert.-butyldimethylchlorosaline-imidazole. This reagent is of common use in platelet-activating factor derivatization, but is made to react with 2-acetyl instead of 3-acetyl isomer. The advantages of using the latter for the final derivatization are discussed and this method is compared with others currently available for gas chromatographic-mass spectrometric analysis of platelet-activating factor.     

A fully symmetric nonlinear biorthogonal decomposition theory for random fields

We present a general approach for nonlinear biorthogonal decomposition of random fields. The mathematical theory is developed based on a fully symmetric operator framework that unifies different types of expansions and allows for a simple formulation of necessary and sufficient conditions for their completeness. The key idea of the method relies on an equivalence between nonlinear mappings of Hilbert spaces and local inner products, i.e. inner products that may be functionals of the random field being decomposed. This extends previous work on the subject and allows for an effective formulation of field-dependent and field-independent representations. The proposed new methodology can be applied in many areas of mathematical physics, for stochastic low-dimensional modelling of partial differential equations and dimensionality reduction of complex nonlinear phenomena. An application to a transient stochastic heat conduction problem in a one-dimensional infinite medium is presented and discussed.     

Interplay between structure and size in a critical crystal nucleus

We study the kinetics of crystal nucleation of an undercooled Lennard-Jones liquid using various path-sampling methods. We obtain the rate constant and elucidate the pathways for crystal nucleation. Analysis of the path ensemble reveals that crystal nucleation occurs along many different pathways, in which critical solid nuclei can be small, compact, and face centered cubic, but also large, less ordered, and more body centered cubic. The reaction coordinate thus includes, besides the cluster size, also the quality of the crystal structure.     

Backbone-only restraints for fast determination of the protein fold: the role of paramagnetism-based restraints. Cytochrome b562 as an example

CH(alpha) residual dipolar couplings (Deltardc's) were measured for the oxidized cytochrome b562 from Escherichia coli as a result of its partial self-orientation in high magnetic fields due to the anisotropy of the overall magnetic susceptibility tensor. Both the low spin iron (III) heme and the four-helix bundle fold contribute to the magnetic anisotropy tensor. CH(alpha) Deltardc's, which span a larger range than the analogous NH values (already available in the literature) sample large space variations at variance with NH Deltardc's, which are largely isooriented within alpha helices. The whole structure is now significantly refined with the chemical shift index and CH(alpha) Deltardc's. The latter are particularly useful also in defining the molecular magnetic anisotropy parameters. It is shown here that the backbone folding can be conveniently and accurately determined using backbone restraints only, which include NOEs, hydrogen bonds, residual dipolar couplings, pseudocontact shifts, and chemical shift index. All these restraints are easily and quickly determined from the backbone assignment. The calculated backbone structure is comparable to that obtained by using also side chain restraint. Furthermore, the structure obtained with backbone only restraints is, in its whole, very similar to that obtained with the complete set of restraints. The paramagnetism based restraints are shown to be absolutely relevant, especially for Deltardc's.     

Symmetry-improved CJT effective action

The formalism introduced by Cornwall, Jackiw and Tomboulis (CJT) provides a systematic approach to consistently resumming non-perturbative effects in Quantum Thermal Field Theory. One major limitation of the CJT effective action is that its loopwise expansion introduces residual violations of possible global symmetries, thus giving rise to massive Goldstone bosons in the spontaneously broken phase of the theory. In this paper we develop a novel symmetry-improved CJT formalism for consistently encoding global symmetries in a loopwise expansion. In our formalism, the extremal solutions of the fields and propagators to a loopwise truncated CJT effective action are subject to additional constraints given by the Ward Identities due to global symmetries. By considering a simple O(2)$\mathbb{O}(2)$ scalar model, we show that, unlike other methods, our approach satisfies a number of important field-theoretic properties. In particular, we find that the Goldstone boson resulting from spontaneous symmetry breaking of O(2)$\mathbb{O}(2)$ is massless and the phase transition is a second-order one, already in the Hartree–Fock approximation. After taking the sunset diagrams into account, we show how our approach properly describes the threshold properties of the massless Goldstone boson and the Higgs particle in the loops. Finally, assuming minimal modifications to the Hartree–Fock approximated CJT effective action, we calculate the corresponding symmetry-improved CJT effective potential and discuss the conditions for its uniqueness for scalar-field values away from its minimum.     

A Volume Inequality for Quantum Fisher Information and the Uncertainty Principle

Let A ₁,…,A _N be complex self-adjoint matrices and let ρ be a density matrix. The Robertson uncertainty principle

Reflectometric measurement of birefringence rotation in single-mode optical fibers

We present a novel reflectometric technique for the measurement of orientation and modulus of the linear birefringence vector in single-mode optical fibers. The technique provides information also on circular birefringence, although this component, if present, appears as a rotation of the linear birefringence. A detailed theoretical analysis is reported and validated by experimental results.     

Hypernuclear production in the (K, π) reaction

Cross sections for the production of hypernuclei were measured in the reaction A(K⁻, π⁻) _ΛA. on light and heavy nuclear targets, using a separated K⁻ beam at the CERN Proton Synchrotron. The pions were detected in the forward direction. The results are compared with cross sections calculated under the assumption that the reaction took place on a single neutron. The good agreement between the measured and the calculated cross sections justifies the use of the (K⁻, π⁻) reaction in order to obtain spectroscopic information on hypernuclei.     

13C direct detected experiments: optimization for paramagnetic signals

To optimize 13C direct detected experiments for the observation of signals close to a paramagnetic center, we have assessed the sensitivity of different sequences based on CO-Cali coherence transfer. Features of CACO experiments were tested for Calbindin D9k, in which one of the two native Ca2+ ions is replaced by the paramagnetic Ce3+ ion. We have studied the comparison of single vs multiple quantum coherence transfer evolution as well as the influence of in-phase vs anti-phase detection of 13CO signals and finally the comparison of a coherence transfer step based on a CyO in plane with respect to a Cy ali in plane. The acquisition of the anti-phase component of the signal, accomplished by the removal of the last refocusing steps, allowed the identification of some signals unobserved with other pathways. The structural dependency of paramagnetism-induced nuclear relaxation is such that the identification of the most suitable coherence transfer pathway is not known "a priori" but it is driven by the relative proximity of Cali and CO to the paramagnetic center.