Observation of gas-phase molecular dications formed from neutral organics in solution via the controlled-current electrolytic process inherent to electrospray

This article reports the first electrospray (ES) mass spectrometry observation of molecular dications that were formed in solution by sequential one-electron oxidation of the neutral molecules [viz., nickel(II) and cobalt(II) octaethylporphyrin] via the controlled-current electrolytic (CCE) process inherent to electrospray. Dication formation was found to require (1) the addition of electrolyte to the sample solution, which increased the magnitude of the ES current and, therefore, increased the extent of analyte electrolysis in the ES capillary, (2) a relatively low solution flow rate, which increased the electrolysis time (i.e., the time the analyte remained in the capillary), thereby providing more time for the analytes to diffuse to the metal-solution interface and react, and (3) the use of a platinum ES capillary, which, because it is difficult to oxidize, increased the proportion of the faradaic current that might be provided by electrolysis of solution species compared to that proportion available when the typical stainless steel capillary is used. These interpretations of the data are made on the basis of the known characteristics of the CCE process inherent to ES, supplementary data obtained from direct solution-phase observation of the metalloporphyrin redox products formed within the different metal ES capillaries by means of a novel ES ion source, and off-line cyclic voltammetry studies of the metalloporphyrins performed by using platinum and stainless steel working electrodes

Discrimination of human cytotoxic lymphocytes from regulatory and B-lymphocytes by orthogonal light scattering

Light scattering properties of human lymphocyte subpopulations selected by immunofluorescence were studied with a flow cytometer. Regulatory and B-lymphocytes showed a low orthogonal light scatter signal, whereas cytotoxic lymphocytes identified with leu-7, leu-11 and leu-15 revealed a large orthogonal light scatter signal. Two populations in light scatter histograms could be observed with monoclonal antibodies directed against determinants present on both regulatory and cytotoxic lymphocytes. By analysis of the lymphocytes of 16 individuals we found a linear relation between the number of cells with a large orthogonal light scattering and the number of cytotoxic lymphocytes identified with leu-7, leu-11 and leu-15. These observations demonstrate physical differences between cytotoxic lymphocytes and regulatory and B lymphocytes. Moreover, the results suggest a method to estimate the amount of cytotoxic lymphocytes without using monoclonal antibodies

Geochemistry of post-tectonic mafic intrusions in the Central Gneiss Terrane of southwestern Newfoundland

South of Grand Lake, mafic igneous complexes of proven or probable Silurian age intruded quartzofeldspathic gneisses that had been deformed and raised to granulite fades in mid-Ordovician time. The mafic igneous complexes consist of gabbroic units, which locally exhibit igneous layering and contain ultramafic cumulate pods, that grade to and are cut by finer-grained hornblende gabbro. Compositions more felsic than diorite exhibit intrusive to co-mingling relationships with more mafic rocks. Chemical data for possible liquid-derived rocks exhibit characteristics suggesting derivation from diverse mantle sources, followed by varying combinations of fractionation, contamination, mixing and metasomatism by hydrous fluids during ascent and emplacement. The post-tectonic emplacement of the plutons suggests stabilisation of die Central Gneiss Terrane by late Ordovician or Silurian time, when the adjacent terrane to the southeast (Meelpaeg Terrane) was still undergoing deformation and granitic plutonism. RÉSUMÉ Au sud de Grand Lake, des complexes ignés mafiques, dont l’âge est assurément ou probablement silurien, firent intrusion dans desgneiss quartzofeldspathiques qui avaient été déforrnés avaient atteint le faciès des granulites au milieude l’Ordovicien. Les complexes ignés mafiques sont constitues d'unités gabbroiques (montrant localement un aspect rubanné et contenant des lentilles de cumulate ultramaflques) passant graduellement à un gabbro à hornblende moins grenu qui les recoupe aussi. Les compositions plus felsiques que la diorite sont en relation d'intrusion ou de mélange avec les roches plus mafiques. Les données chimiques concernant des roches possiblement derives du liquide montrent des caractéres suggèrant une dérivation à partir de diverses sources mantelliques, suivie d'une combinaison variée de fractionnement, contamination, mélange et métasomatisme par des fluides aqueux durant l'ascension et l’emplacement. L'emplacement post-tectonique des plutons suggère une stabilisation de la lanière Central Gneiss Terrane avant l'Ordovicien tardif ou le Silurien, au moment ou la lanière adjacente au sud-est (la Lanière de Meelpaeg) subissait encore une déformation et un plutonisme granitique. [Traduit par le journal

Worksite health promotion: Development and evaluation of a mindfulness-based intervention and ethical considerations

Beek, A.J. van der [Promotor]Bongers, P.M. [Promotor]Boot, C.R.L. [Copromotor]Proper, K.I. [Copromotor

Mixing in thermally stratified energy stores

Abstract-Two important aspects of short-term thermally stratified energy storage, thermocline mixing and thermocline thickness, are studied analytically, experimentally and numerically. The storage detrimental aspects are investigated for a simplified configuration, i.e. an adiabatic box containing a quasi-stationary thermocline. Numerical finite difference/volume simulations agree well with experiments. The dissipationfree 1D analytical model shows a large discrepancy. It appears that mixing inside thermally stratified stores is a two-stage process. First fluid is withdrawn from the thermocline by viscous drag. Subseauent mixing takes place bv stretching and folding of fluid particles, thereby enabling diffusion to become active. Copitight 0 1996 Elsevier S&nce Ltd.

Ion-ion proton transfer reactions of bio-ions involving noncovalent interactions: Holomyoglobin

Multiply protonated horse skeletal muscle holomyoglobin and apomyoglobin have been subjected to ion-ion proton transfer reactions with anions derived from perfluoro-1,3dimethylcyclohexane in a quadrupole ion trap operated with helium as a bath gas at 1 mtorr. Neither the apomyoglobin nor holomyoglobin ions show any sign of fragmentation associated with charge state reduction to the 1 + charge state. This is particularly noteworthy for the holomyoglobin ions, which retain the noncovalently bound heme group. For example, no sign of heme loss is associated with charge state reduction from the 9 + charge state of holomyoglobin to the 1 + charge state despite the eight consecutive highly exothermic proton transfer reactions required to bring about this charge change. This result is consistent with calculations that show the combination of long ion lifetime and the high ion-helium collision rate relative to the ion-ion collision rate makes fragmentation unlikely for high mass ions in the ion trap environment even for noncovalently bound complexes of moderate binding strength. The ion-ion proton transfer rates for holo- and apomyoglobin ions of the same charge state also were observed to be indistinguishable, which supports the expectation that ion-ion proton transfer rates are insensitive to ion structure and are determined primarily by the attractive Coulomb field