Gas-Phase Transformation of Phosphatidylcholine Cations to Structurally Informative Anions via Ion/Ion Chemistry

Gas-phase transformation of synthetic phosphatidylcholine (PC) monocations to structurally informative anions is demonstrated via ion/ion reactions with doubly deprotonated 1,4-phenylenedipropionic acid (PDPA). Two synthetic PC isomers, 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (PC16:0/18:1) and 1-oleoyl-2-palmitoyl-sn-glycero-3-phosphocholine (PC18:1/16:0), were subjected to this ion/ion chemistry. The product of the ion/ion reaction is a negatively charged complex, \[PC + PDPA - H](-). Collisional activation of the long-lived complex causes transfer of a proton and methyl cation to PDPA, generating \[PC - CH3](-). Subsequent collisional activation of the demethylated PC anions produces abundant fatty acid carboxylate anions and low-abundance acyl neutral losses as free acids and ketenes. Product ion spectra of \[PC - CH3](-) suggest favorable cleavage at the sn-2 position over the sn-1 due to distinct differences in the relative abundances. In contrast, collisional activation of PC cations is absent of abundant fatty acid chain-related product ions and typically indicates only the lipid class via formation of the phosphocholine cation. A solution phase method to produce the gas-phase adducted PC anion is also demonstrated. Product ion spectra derived from the solution phase method are similar to the results generated via ion/ion chemistry. This work demonstrates a gas-phase means to increase structural characterization of phosphatidylcholines via ion/ion chemistry. Grant Number ARC/CE0561607, ARC/DP120102922

Effects of unique ion chemistry on thin-film growth by plasma–surface interactions

Plasma processing is a standard industrial method for the modification of material surfaces and the deposition of thin films. Polyatomic ions and neutrals larger than a triatomic play a critical role in plasma-induced surface chemistry, especially in the deposition of polymeric films from fluorocarbon plasmas. In this paper, low energy CF3+ and C3F5+ ions are used to modify a polystyrene surface. Experimental and computational studies are combined to quantify the effect of the unique chemistry and structure of the incident ions on the result of ion-polymer collisions. C3F5+ ions are more effective at growing films than CF3+, both at similar energy/atom of ≈6 eV/atom and similar total kinetic energies of 25 and 50 eV. The composition of the films grown experimentally also varies with both the structure and kinetic energy of the incident ion. Both C3F5+ and CF3+ should be thought of as covalently bound polyatomic precursors or fragments that can react and become incorporated within the polystyrene surface, rather than merely donating F atoms. The size and structure of the ions affect polymer film formation via differing chemical structure, reactivity, sticking probabilities, and energy transfer to the surface. The different reactivity of these two ions with the polymer surface supports the argument that larger species contribute to the deposition of polymeric films from fluorocarbon plasmas. These results indicate that complete understanding and accurate computer modeling of plasma–surface modification requires accurate measurement of the identities, number densities, and kinetic energies of higher mass ions and energetic neutrals.

Major ion chemistry of snow cores along a transect in central Dronning Maud Land, Antarctica

Among the large variety of particulates in the atmosphere, calcic mineral dust particles have highly reactive surfaces that undergo heterogeneous reactions with nitrogen oxides contiguously. The association between Ca2+, an important proxy indicator of mineral dust and NO3-, a dominant anion in the Antarctic snow pack was analysed. A total of 41 snow cores (~ 1 m each) that represent snow deposited during 2008-2009 were studied along coastal-inland transects from two different regions - the Princess Elizabeth Land (PEL) and central Dronning Maud Land (cDML) in East Antarctica. Correlation statistics showed a strong association (at 99 % significance level) between NO3- and Ca2+ at the near-coastal sections of both PEL (r = 0.72) and cDML (r = 0.76) transects. Similarly, a strong association between these ions was also observed in snow deposits at the inland sections of PEL (r = 0.8) and cDML (r = 0.85). Such systematic associations between Ca2+ and NO3- is attributed to the interaction between calcic mineral dust and nitrogen oxides in the atmosphere, leading to the possible formation of calcium nitrate (Ca(NO3)2). Forward and back trajectory analyses using HYSPLIT model v. 4 revealed that Southern South America (SSA) was an important dust emitting source to the study region, aided by the westerlies. Particle size distribution showed that over 90 % of the dust was in the range < 4 µm, indicating that these dust particles reached the Antarctic region via long range transport from the SSA region. We propose that the association between Ca2+ and NO3- occurs during the long range transport due to the formation of Ca(NO3)2. The Ca(NO3)2 thus formed in the atmosphere undergo deposition over Antarctica under the influence of anticyclonic polar easterlies. However, influence of local dust sources from the nunataks in cDML evidently mask such association in the mountainous region. The study indicates that the input of dust-bound NO3- may contribute a significant fraction of the total NO3- deposited in Antarctic snow.

Major ion chemistry and selected snow accumulation rates of snow cores along two transects in central Dronning Maud Land and Princess Elizabeth Land

This dataset includes basic information (location and depth) and major ion chemistry (Sodium, Chloride, Calcium, Nitrate) of snow cores from East Antarctic ice sheet. The snow cores were collected from two different regions - central Dronning Maud Land (cDML) and Princess Elizabeth Land (PEL) during the austral summer of 2008-09.

Enantiopure 3-substituted piperidines via an aziridinium ion ring expansion

Ce mémoire décrit le développement d’une nouvelle méthodologie d’expansion de cycle irréversible à partir de N-alkyl-3,4-déhydroprolinols pour former des N-alkyl tétrahydropyridines 3-substituées en passant par un intermédiaire aziridinium bicyclique. Cette méthode permet l’introduction d’un vaste éventail de substituants à la position 3 et tolère bien la présence de groupements aux positions 2 et 6, donnant accès à des pipéridines mono-, di- ou trisubstituées avec un excellent diastéréocontrôle. De plus, il est démontré que l’information stéréogénique du 3,4-déhydroprolinol de départ est totalement transférée vers le produit tétrahydropyridine. Additionnellement, une méthodologie fut dévelopée pour la préparation des produits de départ 3,4-déhydroprolinols en forme énantiopure, avec ou sans substituants aux positions 2 et 5, avec un très bon stéréocontrôle. Le premier chapitre présente un résumé de la littérature sur le sujet, incluant un bref survol des méthodes existantes pour la synthèse de pipéridines 3-substituées, ainsi qu’une vue d’ensemble de la chimie des aziridiniums. L’hypothèse originale ainsi que le raisonnement pour l’entreprise de ce projet y sont également inclus. Le second chapitre traite de la synthèse des N-alkyl-3,4-déhydroprolinols utilisés comme produits de départ pour l’expansion de cycle vers les tétrahydropyridines 3-substituées, incluant deux routes synthétiques différentes pour leur formation. Le premier chemin synthétique utilise la L-trans-4-hydroxyproline comme produit de départ, tandis que le deuxième est basé sur une modification de la réaction de Petasis-Mannich suivie par une métathèse de fermeture de cycle, facilitant l’accès aux précurseurs pour l’expansion de cycle. Le troisième chapitre présente une preuve de concept de la viabilité du projet ainsi que l’optimisation des conditions réactionnelles pour l’expansion de cycle. De plus, il y est démontré que l’information stéréogénique des produits de départs est transférée vers les produits. iv Au quatrième chapitre, l’étendue des composés pouvant être synthétisés par cette méthodologie est présentée, ainsi qu’une hypothèse mécanistique expliquant les stéréochimies relatives observées. Une synthèse énantiosélective efficace et divergente de tétrahydropyridines 2,3-disubstituées est également documentée, où les deux substituants furent introduits à partir d’un intermédiaire commun en 3 étapes.

EISCAT observations of ion composition and temperature anisotropy in the high-latitude F-region

The papers by Winser et al. [(1990) J. atmos. terr. Phys.52, 501] and Häggström and Collis [(1990) J. atmos. terr. Phys.52, 519] used plasma flows and ion temperatures, as measured by the EISCAT tristatic incoherent scatter radar, to investigate changes in the ion composition of the ionospheric F-layer at high latitudes, in response to increases in the speed of plasma convection. These studies reported that the ion composition rapidly changed from mainly O+ to almost completely (>90%) molecular ions, following rapid increases in ion drift speed by >1 km s−1. These changes appeared inconsisent with theoretical considerations of the ion chemistry, which could not account for the large fractions of molecular ions inferred from the obsevations. In this paper, we discuss two causes of this discrepancy. First, we reevaluate the theoretical calculations for chemical equilibrium and show that, if we correct the derived temperatures for the effect of the molecular ions, and if we employ more realistic dependences of the reaction rates on the ion temperature, the composition changes derived for the faster convection speeds can be explained. For the Winser et al. observations with the radar beam at an aspect angle of ϕ = 54.7° to the geomagnetic field, we now compute a change to 89% molecular ions in < 2 min, in response to the 3 km s−1 drift. This is broadly consistent with the observations. But for the two cases considered by Häggström and Collis, looking along the field line (ϕ = 0°), we compute the proportion of molecular ions to be only 4 and 16% for the observed plasma drifts of 1.2 and 1.6 km s−1, respectively. These computed proportions are much smaller than those derived experimentally (70 and 90%). We attribute the differences to the effects of non-Maxwellian, anisotropic ion velocity distribution functions. We also discuss the effect of ion composition changes on the various radar observations that report anisotropies of ion temperature.

Chemistry of interstitial waters of ODP Leg 112 samples

Two distinct hydrogeochemical regimes currently dominate the Peruvian continental margin. One, in shallower water (150-450 m) shelf to upper-slope regions, is characterized by interstitial waters with strong positive chloride gradients with depth. The maximum measured value of 1043 mM chloride at Site 680 at ITS corresponds to a degree of seawater evaporation of ~2 times. Major ion chemistry and strontioum isotopic composition of the interstitial waters suggest that a subsurface brine that has a marine origin and is of pre-early Miocene "age," profoundly influences the chemistry and diagenesis of this shelf environment. Site 684 at ~9°S must be closest to the source of this brine, which becomes diluted with seawater and/or interstitial water as it flows southward toward Site 686 at ~13?S (and probably beyond) at a rate of approximately 3 to 4 cm/yr, since early Miocene time. The other regime, in deep water (3000-5000 m) middle to lower-slope regions, is characterized by interstitial waters with steep negative and nonsteady-state chloride gradients with depth. The minimum measured value of 454 mM chloride, at Site 683 at ITS, corresponds to ~20% dilution of seawater chloride The most probably sources of these low-chloride fluids are gas hydrate dissociation and mineral (particularly clay) dehydration reactions. Fluid advection is consistent with (1) the extent of dilution shown in the chloride profiles, (2) the striking nonsteady-state depth profiles of chlorides at Sites 683 and 688 and of 87Sr/86Sr ratios at Site 685, and (3) the temperatures resulting from an average geothermal gradient of 50°C/km and required for clay mineral dehydration reactions. Strontium isotope data reveal two separate fluid regimes in this slope region: a more northerly one at Sites 683 and 685 that is influenced by fluids with a radiogenic continental strontium signature, and a southerly one at Sites 682 and 688 that is influenced by fluids with a nonradiogenic oceanic signatures. Stratigraphically controlled fluid migration seems to prevail in this margin. Because of its special tectonic setting, Site 679 at ITS is geochemically distinct. The interstitial waters are characterized by seawater chloride concentrations to -200 mbsf and deeper by a significantly lower chloride concentration of about two-thirds of the value in seawater, suggesting mixing with a meteoric water source. Regardless of the hydrogeochemical regime, the chemistry and isotopic compositions of the interstitial waters at all sites are markedly modified by diagenesis, particularly by calcite and dolomite crystallization.

Reactions of atomic and molecular ions with acetone, 1,1,1- trifluoroacetone, and hexafluoroacetone: An investigation of the effects of molecular structure on the dynamics and kinetics of ion-molecule reactions

A selected ion flow tube study of the reactions of a series of gas-phase atomic cations (S⁺, Xe⁺, O⁺, Kr⁺, N⁺, Ar⁺ and Ne⁺) and molecular ions (SF _n⁺ (n = 1-5), CF_n⁺ (n = 1-3), CF₂Cl⁺, H₃O⁺, NO⁺, N ₂O⁺, CO₂⁺, CO⁺, and N₂⁺) spanning a large range of recombination energies (6.3-21.6 eV), with acetone, 1,1,1-trifluoroacetone, and hexafluoroacetone has been undertaken with the objective of exploring the nature of the reaction ion chemistry as the methyl groups in acetone are substituted for CF₃. The reaction rate coefficients and product ion branching ratios for all 66 reactions, measured at 298 K, are reported. The experimental reaction rate coefficients are compared to theoretically calculated collisional values. Several distinct reaction processes were observed among the large number of reactions studied, including charge transfer (non-dissociative and dissociative), abstraction, ion-molecule associations and, in the case of the reactions involving the reagent ion H₃O⁺, proton transfer. 

Construction of interstellar cumulenes and heterocumulenes : Mass spectrometric studies

The last few years have brought an increasing interest in the chemistry of rite interstellar and circumstellar environs. Many of the molecular species discovered in remote galactic regions have been dubbed 'non-terrestrial' because of their unique structures (Thaddeus et al, 1993). These findings have provided a challenge to chemists in many differing fields to attempt to generate these unusual species in the laboratory of particular recent interest have been the unsaturated hydrocarbon families, CnH and CnH2, which have been pursued by a number of diverse methodologies. A wine range of heterocumulenes, including CnO, HCnO, CnN, HCnN, CnS, HCnS, CnSi and HCnSi have also provided intriguing targets for laboratory experiments. Strictly the term cumulene refers to a class of compounds that possess a series of adjacent double bonds, with allene representing the simplest example (H2C=C=CH2). However for many of the non-terrestrial molecules presented here, the carbon chain cannot be described in terms of a single simple valence structure, and so we use the terms cumulene and heterocumulene in a more general sense: to describe molecular species that contain an unsaturated polycarbon chain. Mass spectrometry has proved an invaluable tool in the quest for interstellar cumulenes and heterocumulenes in the laboratory it has the ability in its many forms, to (i) generate charged analogs of these species in the gas phase, (ii) probe their connectivity, ion chemistry, and thermochemistry, and (iii) in some cases, elucidate the neutrals themselves. Here, we will discuss the progress of these studies to this time. (C) 1999 John Wiley & Sons, Inc.

Controls on intense silicate weathering in a tropical river, southwestern India

The Silicate Weathering Rate (SWR) and associated Carbon dioxide Consumption Rate (CCR) in tropical silicate terrain is assessed through a study of the major ion chemistry in a small west flowing river of Peninsular India, the Nethravati River. The specific features of the river basin are high mean annual rainfall and temperature, high runoff and a Precambrian basement composed of granitic-gneiss, charnockite and minor metasediments. The water samples (n = 56) were collected from three locations along the Nethravati River and from two of its tributaries over a period of twelve months. Chemical Weathering Rate (CWR) for the entire watershed is calculated by applying rainwater correction using river chloride as a tracer. Chemical Weathering Rate in the Nethravati watershed is estimated to 44 t.km(-2).y(-1) encompassing a SWR of 42 t.km(-2).y(-1) and a maximum carbonate contribution of 2 t.km(-2).y(-1). This SWR is among the highest reported for granito-gneissic terrains. The assessed CCR is 2.9 . 10(5) mol.km(-2).y(-1). The weathering index (Re). calculated from molecular ratios of dissolved cations and silica in the river, suggests an intense silicate weathering leading to kaolinite-gibbsite precipitation in the weathering covers. The intense SWR and CCR could be due to the combination of high runoff and temperature along with the thickness and nature of the weathering cover. The comparison of silicate weathering fluxes with other watersheds reveals that under similar morpho-climatic settings basalt weathering would be 2.5 times higher than the granite-gneissic rocks. (C) 2012 Elsevier B.V. All rights reserved.

Sources of major ions and processes affecting the geochemical and isotopic signatures of subsurface waters along a tropical river, Southwestern India

Systematic monitoring of subsurface hydrogeochemistry has been carried out for a period of one year in a humid tropical region along the Nethravati-Gurupur River. The major ion and stable isotope (delta O-18 and delta H-2) compositions are used to understand the hydrogeochemistry of groundwater and its interaction with surface water. In the study, it is observed that intense weathering of source rocks is the major source of chemical elements to the surface and subsurface waters. In addition, agricultural activities and atmospheric contributions also control the major ion chemistry of water in the study area. There is a clear seasonality in the groundwater chemistry, which is related to the recharge and discharge of the hydrological system. On a temporal scale, there is a decrease in major cation concentrations during the monsoon which is a result of dilution of sources from the weathering of rock minerals, and an increase in anion concentrations which is contributed by the atmosphere, accompanied by an increase in water level during the monsoon. The stable isotope composition indicates that groundwater in the basin is of meteoric origin and recharged directly from the local precipitation during the monsoonal season. Soon after the monsoon, groundwater and surface water mix in the subsurface region. The groundwater feeds the surface water during the lean river flow season.