Quantitative determination of major platelet activating factors from human plasma

Platelet activating factor (PAF) is a potent lipid mediator that is involved in many important biological functions, including platelet aggregation and neuronal differentiation. Although an ELISA assay has been used to measure PAF levels, it cannot distinguish between its isoforms. To achieve this, liquid chromatography-tandem mass spectrometry (LC-MS/MS) has been used instead. However, isobaric lysophosphatidylcholine (lyso PC), which is often present in large amounts in complex biological samples and has similar retention times in many LC conditions, can affect the accurate measurement of PAF. The present study examined the fragmentation behavior of major PAF and lyso PC during various MS/MS conditions. Fragment ions at m/z 184 and at m/z 104 were abundantly observed from MS/MS of lyso PCs. PAF provided a dominant fragment ion at m/z 184, but a fragment ion at m/z 104 was almost never produced, regardless of the collision energy. Thus, the two fragment ions at m/z 184 and m/z 104 were used to accurately measure PAF levels. First, the fragment ion at m/z 184 and the retention time of PAF in LC-MS/MS were used to identify and quantitate PAF. However, if there were small retention time shifts, which are common in multiple sample runs, and lipid composition in a sample is very complicated, the fragment ion at m/z 104 was used to confirm whether the fragment ion at m/z 184 belonged to PAF. This novel method accurately determined the major PAF (C16:0 PAF, C18:0 PAF, and C18:1 PAF) levels in human plasma.     

Asymmetric methoxyselenenylations and cyclizations with 3-camphorseleno electrophiles containing oxime substituents at C-2. Formation of an unusual oxaselenazole from an oxime-substituted selenenyl bromide.

Di[(1R)-2-Oximo-endo-3-bornyl] diselenide (4) and its benzoate derivative 5 were prepared from the corresponding known 2-keto diselenide 1. Treatment of 4 and 5 with bromine, followed by silver triflate in methanol-dichloromethane, generated the corresponding selenenyl triflates 6b and 7b. The latter reagents reacted with a variety of mono-, di-, and trisubstituted alkenes to afford the corresponding 1,2-addition products (beta-methoxy selenides) in a highly diastereoselective manner. The free oxime 6b was particularly effective in such methoxyselenenylations, giving diastereomeric ratios (d.r.s) ranging from 86:14 to > 98:2. Even cis-disubstituted alkenes, which typically give poor d.r.s in similar additions with other chiral selenium electrophiles, underwent highly stereoselective additions with this reagent. Reductive deselenizations of the adducts obtained from styrene and cis- and trans-stilbene provided the corresponding methyl ethers, whose absolute configurations were determined by comparison with authentic samples. As expected, the dominant enantiomers thus obtained from cis- and trans-stilbene, using either 6b or 7b, had opposite configurations. Moreover, each geometrical isomer of stilbene produced methyl ethers with the same configuration when treated with either the oxime 6b or the benzoate 7b. Coordination effects between the substituents at the 2-position of the camphor molecule and the positive selenium atoms in the intermediate seleniranium ions are believed to play an important role in determining the stereochemical outcome of methoxyselenenylations. Selenenyl triflate 6b and selenenyl chloride 7c were also investigated in the electrophilic cyclizations of several unsaturated alcohols and carboxylic acids. However, diastereoselectivities were typically much lower than in the methoxyselenenylations. When the selenenyl bromide 6a, derived from the addition of bromine to the corresponding diselenide 4, was allowed to stand in the absence of an alkene, it underwent intramolecular cyclization with the oxime hydroxyl group, followed by further bromination, to afford the unusual oxaselenazole 11, whose structure was determined by spectroscopic means as well as by X-ray crystallography.     

Nuclear orientation of136Cs: Reorientation in the 0.3S 7-isomer of136Ba

Properties of the decay of¹³⁶Cs to¹³⁶Ba are deduced from low temperature nuclear orientation studies. Of particular interest is the observation of attenuated anisotropy in transitions from the 7- 0.3s isomer at 2031 keV. This is ascribed to the presence of mixed electric/magnetic interaction in this state which is not collinear with the parent¹³⁶Cs quantisation axis. the ISOLDE collaboration     

The oxidation of N-acylhydrazines by benzeneseleninic acid - a novel synthesis of selenolesters

The reaction of N-acylhydrazines with benzeneseleninic acid in the presence of triphenylphosphine affords high yields of diverse selenolesters.     

Rheology of polymers that are initially in the disentangled state

An attempt was made to measure the effects of molecular entanglements on the rheological properties of polymer melts. Two classes of polymers were studied; glassy atactic polystyrene polymers covering a 60-fold range in molecular weight, and semicrystalline high-density polyethylene from two sources covering about a twofold range in molecular weight. The entanglements initially present were removed or greatly reduced in number by freeze drying the polystyrene polymers from dilute solutions below and above C*, the critical overlap concentration, and by slowly crystallizing the polyethylene from very dilute solutions. Since only minor rheological changes were observed with polystyrene, it would appear that the initially isolated coils interpenetrate more rapidly than is indicated by the results of Liu and Morawetz, or that the rheological behavior is rather insensitive to whether the flow obstacles are intermolecular or intramolecular. The enhancement of the viscosity and elasticity observed with polyethylene polymers indicate the importance of the crystallization step on the local melt topology of the polymer chains.     

Magnetic hyperfine field at caesium in iron

We report temperature dependence of nuclear orientation (NO), and the first observation of NMR/ON on Cs in iron.^{132, 136}Cs were implanted at room temperature into polycrystalline and single crystal iron. NO values for the (average) magnetic hyperfine field B_hf (CsFe) are close to 34T, intermediate between the value of 40.7T found in on-line samples made at mK temperatures and the NMR/ON value of 27.8 (2)T. The latter studies. The site/field distribution is briefly discussed. ISOLDE Collaboration, CERN     

Kinetics of the formation of cyclobutane from ethylene

The rate of the thermal reaction of ethylene to form cyclobutane has been measured over the temperature range 723°–786°K and at pressures between 300 and 1300 torr. The equilibrium constant for the system \documentclass{article}\usepackage{amssymb}\pagestyle{empty}\begin{document}$${\rm 2C}_{\rm 2} {\rm H}_{\rm 4}\mathop {\leftrightharpoons}\limits_{kf}^{kr} c - {\rm C}_{\rm 4} {\rm H}_{\rm 8}$$\end{document} was calculated both from the initial rate data and from measurements of the equilibrium concentration of cyclobutane. Agreement with the reported thermodynamic quantities for cyclobutane was satisfactory. The initial rate data gave the following epxression for k_f: while the measurements of the equilibrium concentration of cyclobutane gave the expression for K, .     

Neutron strength functions in rare earth nuclei

The coupling of the single particle motion of the neutron to other degrees of freedom is studied by the (d, p) reaction leading to highly excited states in rare earth nuclei. Experimental spectra have been obtained with a telescope counter system for 13 rare earth isotopes of Gd, Dy, Er and Yb. The results are compared with calculations based upon the single particle model in a deformed Saxon-Woods potential. The spreading of the single particle strength resulting from the coupling to other degrees of freedom is taken into account in a simple phenomenological way. A qualitative similarity between the experimental and calculated spectra is observed, and the total integrated (d, p) cross section up to the neutron binding energy is reproduced quite closely by the calculations. For a given excitation energy, the amount of structure in the experimental spectrum seems to decrease with neutron number for each element investigated.     

Fill-tube-induced mass perturbations on x-ray-driven, ignition-scale, inertial-confinement-fusion capsule shells and the implications for ignition experiments

On the first inertial-confinement-fusion ignition facility, the target capsule will be DT filled through a long, narrow tube inserted into the shell. microg-scale shell perturbations Delta m' arising from multiple, 10-50 microm-diameter, hollow SiO2 tubes on x-ray-driven, ignition-scale, 1-mg capsules have been measured on a subignition device. Simulations compare well with observation, whence it is corroborated that Delta m' arises from early x-ray shadowing by the tube rather than tube mass coupling to the shell, and inferred that 10-20 microm tubes will negligibly affect fusion yield on a full-ignition facility.     

Microwave assisted switching of single domain Ni80Fe20 elements

We study the switching behavior of thin single domain magnetic elements in the presence of microwave excitation. The application of a microwave field strongly reduces the coercivity of the elements. We show that this effect is most profound at the ferromagnetic resonance frequency of the elements. Observations using time-resolved magneto-optic Kerr microscopy in combination with pulsed microwave excitation further support that the microwave assisted switching process is indeed based on the coherent motion of the magnetization.