Biogenic halocarbons from the Peruvian upwelling region during METEOR cruise M91

Halocarbons, halogenated short-chained hydrocarbons, are produced naturally in the oceans by biological and chemical processes. They are emitted from surface seawater into the atmosphere, where they take part in numerous chemical processes such as ozone destruction and the oxidation of mercury and dimethyl sulfide. Here we present oceanic and atmospheric halocarbon data for the Peruvian upwelling obtained during the M91 cruise onboard the research vessel Meteor in December 2012. Surface waters during the cruise were characterized by moderate concentrations of bromoform (CHBr3) and dibromomethane (CH2Br2) correlating with diatom biomass derived from marker pigment concentrations, which suggests this phytoplankton group as likely source. Concentrations measured for the iodinated compounds methyl iodide (CH3I) of up to 35.4 pmol L-1, chloroiodomethane (CH2ClI) of up to 58.1 pmol L-1 and diiodomethane (CH2I2) of up to 32.4 pmol L-1 in water samples were much higher than previously reported for the tropical Atlantic upwelling systems. Iodocarbons also correlated with the diatom biomass and even more significantly with dissolved organic matter (DOM) components measured in the surface water. Our results suggest a biological source of these compounds as significant driving factor for the observed large iodocarbon concentrations. Elevated atmospheric mixing ratios of CH3I (up to 3.2 ppt), CH2ClI (up to 2.5 ppt) and CH2I2 (3.3 ppt) above the upwelling were correlated with seawater concentrations and high sea-to-air fluxes. The enhanced iodocarbon production in the Peruvian upwelling contributed significantly to tropospheric iodine levels.

Production of Gaseous Radiotracers Ch3i and I2 Through Na123i Salt

The objective of the present work was to develop, separately, methodology for production of two gaseous tracers through the sodium iodide NaI marked with 123I. Found in the nature in form different, the iodine has been used in diverse works in the area of the industry and health. These two forms of the gaseous iodine, the methyl iodide, CH3I, and molecular iodine, I2, are very unstable and volatile in the ambient temperature and presents different problems in clean-up and monitoring systems. The syntheses were processed with sodium iodide (NaI) 1M aqueous solution marked with 123I. The production of gas I2 was realized with in chlorine acid (HCl) and sodium iodate salt (NaIO3) and the CH3I was used, the salt of NaI and the reagent (CH3)2SO4. The production of gases was initially realized through in unit in glass with an inert material and the purpose was to study the kinetic of reaction and to determine the efficiency of production. The two synthesis occurs in the reaction bottle and after of produced, the gas is stored in the collect bottle that contains a starch solution for fixed the I2, and in syntheses of CH3I contains a silver nitrate solution for your fixation. To determine the efficiency of production of gases, analytic tests were realized, where the consumption of iodide ions of the bottle of reaction are measured. The optimization of production of the each gaseous tracer was studied varying parameter as: concentration of iodide, concentration of acid and temperature. After, the syntheses of the radiotracers were realized in the compact unit, having been used as main reagent the salt radiated of sodium iodide, Na123I. The transportation of elementary iodine and methyl iodine was studied by a scintillation detector NaI (2 x 2)” positioned in the reaction bottle.

Intramolecular Reactivity - Keto Participation in the Hydrolysis of N-Methyl-N-(9-Oxobicyclo[3.3.1]Nonan-2-Alpha-YL) Morpholinium Iodide, and A Cannizzaro-Type Reaction of 3-(2-Oxocyclohexyl)Propanal

Mechanistic studies of two intramolecular processes, nucleophilic displacement of N-methylmorpholinium in N-methyl-N-{9-oxobicyclo[3,3,1]nonan-2 alpha-yl}morpholinium iodide, anchimerically assisted by keto carbonyl, and a Cannizzaro-type reaction of 3-(2-oxocyclohexyl)propanal, occurring via axial hydride transfer onto the cyclohexanone, are reported.

Ab initio calculations, Raman and NMR investigation of the plastic crystal di-methyl pyrrolidinium iodide

Above 110 °C the symmetric di-methyl-pyrrolidinium iodide salt forms a plastic crystal phase of interest in the area of new electrolyte materials. In this study ab initio calculations of this material has been conducted in order to assign the vibrational spectra. Raman spectroscopy measurements on the solid salt as well as on the salt dissolved in different solvents has been performed and these have been compared to the theoretical spectra. Furthermore, Raman spectra as a function of temperature have been recorded to investigate possible changes in inter-ionic interaction and/or structure through the phase transition. 1H NMR linewidth measurements as a function of temperature showed a large decrease in linewidth above 100 °C, attributed here to an increase in mobility in agreement with a previously reported phase transition at ~110 °C.

Methyl ethyl ketone plus water plus secondary butyl alcohol: A potential system for the exploration of a quadruple critical point

We report preliminary experiments on the ternary-liquid mixture, methyl ethyl ketone (MEK)+water (W)+secondary butyl alcohol (sBA)-a promising system for the realization of the quadruple critical point (QCP). The unusual tunnel-shaped phase diagram shown by this system is characterized and visualized by us in the form of a prismatic phase diagram. Light-scattering experiments reveal that (MEK+W+sBA) shows near three-dimensional-Ising type of critical behavior near the lower critical solution temperatures, with the susceptibility exponent (gamma) in the range of 1.217 <=gamma <= 1.246. The correlation length amplitudes (xi(o)) and the critical exponent (nu) of the correlation length (xi) are in the ranges of 3.536 <=xi(o)<= 4.611 A and 0.619 <=nu <= 0.633, respectively. An analysis in terms of the effective susceptibility exponent (gamma(eff)) shows that the critical behavior is of the Ising type for MEK concentrations in the ranges of 0.1000 <= X <= 0.1250 and X >= 0.3000. But, for the intermediate range of 0.1750 <= X < 0.3000, the system shows a tendency towards mean-field type of critical behavior. The advantages of the system (MEK+W+sBA) over the system (3-methylpyridine+water+heavy water+potassium Iodide) for the realization of a QCP are outlined.

N-Methyl-N-Allylpyrrolidinium Based Ionic Liquids for Solvent-Free Dye-Sensitized Solar Cells

We prepared four new ionic liquids consisting of N-methyl-N-allylpyrrolidinium cation in conjunction with anions including iodide, nitrate, thiocyanate, and dicyanamide, respectively, and measured their physical properties of density, viscosity, and conductivity. Owing to the relatively lower melting point of electroactive N-methyl-N-allylpyrrolidinium iodide, in combination with three other nonelectroactive ionic liquids, we could construct solvent-free electrolytes possessing high iodide concentrations for dye-sensitized solar cells. We correlated temperature-dependent electrolyte viscosity with molar conductivity and triiodide mobility through applying an empirical Walden's rule and a modified Stokes-Einstein equation, respectively. We have further found that these anions (nitrate, thiocyanate, and dicyanamide) have different influences on surface states and electron transport in the mesoporous titania film, resulting in different photovoltages and photocurrents of dye-sensitized solar cells.

ELECTROCHEMICAL-BEHAVIOR OF N-METHYL-N'-HEXADECYLVIOLOGEN MONOLAYERS ON SILVER ELECTRODES - EFFECTS OF COUNTERIONS

N-Methyl-N'-hexadecylviologen (C16MV) has been the subject of several electrochemical and spectroelectrochemical studies which characterized the species present in various redox states for C16MV monolayers on silver electrode surfaces. Both self-assembled monolayers (SA) and Langmuir-Blodgett (LB) transferred systems have been studied. These indicated inconsistencies regarding the presence or absence of splitting of the first reduction peak in its cyclic voltammogram (CV). The present study demonstrates the important influence of the specific anionic species present in the supporting electrolyte. Splitting may or may not take place, depending on the size and relative strength of the adsorption of specific anions contributed by the supporting electrolyte. Small, strongly adsorbing anions such as iodide produced peak splitting in the CV of C16MV monolayers; bulky but weakly adsorbing anions such as perchlorate may disrupt the ordered structure of monolayers but produce no splitting. Ancillary data provided by surface enhanced Raman spectroscopy (SERS) was consistent with the electrochemical measurements.

Vibrational intensities VIII: CH3- and CD3- chloride, bromide and iodide

Absolute intensity measurements have been made on the fundamental vibrations of methyl chloride, bromide, and iodide, and their fully deuterated derivatives, by integrating the optical density over the absorption bands. The bands were fully pressure broadened by using up to 80 atmos of foreign gas. Band separations were made graphically. The results are analyzed in terms of the dipole moment derivatives with respect to symmetry coordinates in the molecule, (∂p/∂Si). The data on the different isotopic species are shown to yield consistent results, and this requirement of consistency has also been used as an aid in the analysis. In the E‐class vibrations the signs of the dipole moment derivatives have been determined unambiguously by assuming the permanent dipole to be directed CH3+☒X—.

N-methyl-N-alkylpyrrolidinium hexafluorophosphate salts : novel molten salts and plastic crystal phases

A new series of salts, based on the N-methyl-N-alkylpyrrolidinium cation and the PF₆- anion, are reported and their thermal properties described for alkyl = Me, Et, Pr, Bu, Hx, and Hp. X-ray structures of several of the salts are also reported. The N,N-dimethylpyrrolidinium hexafluorophosphate has a melting point greater than 390 °C; however, the N-methyl-N-butylpyrrolidinium derivative melts at 70 °C. Most of the PF₆- salts were observed to have lower melting points in comparison with the analogous iodide salts. Most of the salts exhibit one or more thermal transitions prior to melting and a final entropy of melting less than 20 J K^-1 mol^-1, behavior which has previously been associated with the formation of plastic crystal phases. Good crystal structure solutions were obtained at low temperatures in the case of the alkyl = propyl and heptyl derivatives. The loss of diffraction peaks and changes in symmetry at higher temperatures indicated the presence of dynamic rotational disorder, supporting the understanding that the plastic properties arise from rotational motions in the crystal.

A new family of ionic liquids based on the 1-alkyl-2-methyl pyrrolinium cation

Five new salts based on 1-alkyl-2-methyl pyrrolinium ion are reported, two involving the iodide ion and three involving the bis(trifluoromethanesulfonyl) amide ion. The iodide salts have melting points around 100 °C, while the amide salts have melting points around room temperature. Two of the amide salts can be easily quenched into the glassy state and exhibit glass transition temperatures around −70 °C. The 2-methyl pyrrolinium cation bears structural similarities to the aromatic imidazolium cations on one hand and the cyclic ammonium cation family based on the pyrrolidinium cation on the other. The properties of the salts reported here are compared within these two related families of salts.

The preparation and characterization of tin(IV) complexes of 2-quinolinecarboxaldehyde Schiff bases of S-methyl- and S-benzyldithiocarbazates and the X-ray crystal and molecular structures of the 2-quinolinecarboxaldehyde Schiff base of S-benzyldithi

New tin(IV) complexes of empirical formula, Sn(NNS)I-3 (NNS = anionic forms of the 2-quinolinecarboxaldehyde Schiff bases of S-methyl- and S-benzyldithiocarbazate) have been prepared and characterized by a variety of physico-chemical techniques. In the solid state, the Schiff bases exist as the thione tautomer but in solution and in the presence of tin(IV) iodide they convert to the thiol tautomer and coordinate to the tin atom in their deprotonated thiolate forms. The structures of the free ligand, Hqaldsbz and its triiodotin(IV) complex, [Sn(qaldsbz)I-3] have been determined by X-ray diffraction. The complex, [Sn(qaldsbz)I-3] has a distorted octahedral structure with the Schiff base coordinated to the tin atom as a uninegatively charged tridentate chelating agent via the quinoline nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom. The three iodo ligands are coordinated meridionally to the tin atom. The distortion from an ideal octahedral geometry of [Sn(qaldsbz)I-3] is attributed to the restricted bite size of the tridentate Schiff base ligand. (C) 2004 Elsevier Ltd. All rights reserved.

Novel 5-HT7 ligands as antidepressants:automated synthesis of N-substituted-N-[1-methyl-3-(4-methylpiperidin-1-yl)propyl]-arylsulfon amides

The 5-HT7 receptor is linked with various CNS disorders. Using an automated solution phase synthesis a combinatorial library of 384 N-substituted N-[1-methyl-3-(4-methylpiperidin-1-yl)propyl]-arylsulfonamides was prepared with 24 chemically diverse amines 1-24 and 16 sulfonyl chlorides A-P. The chemical library of alkylated sulfonamides was evaluated in a receptor binding assay with [3]H-5-CT as ligand. The key synthetic step was the alkylation of a sulfonamide with iodide E, which was prepared from butanediol in 4 synthetic steps. The target compounds 1A, 1B .....24A ... 24P were purified by solvent extraction on a Teacan liquid handling system. Sulfonamide J20, B23, D23, G23, G23, J23 , I24 and O24 displayed a binding affinity IC50 between 100 nM and 10 nM. The crystalline J20 (IC50=39 nM) and O24 (IC50=83 nM) were evaluated further in the despair swimming test and the tail suspension assay. A significant antidepressant activity was found in mice of a greater magnitude than imipramine and fluoxetine at low doses. © 2006 Bentham Science Publishers Ltd.

Molecular mechanisms of salt effects on carbon nanotube dispersions in an organic solvent (N-methyl-2-pyrrolidone)

We consider the effects of salt (sodium iodide) on pristine carbon nanotube (CNT) dispersions in an organic solvent, N-methyl-2-pyrrolidone (NMP). We investigate the molecular-scale mechanisms of ion interactions with the nanotube surface and we show how the microscopic ion-surface interactions affect the stability of CNT dispersions in NMP. In our study we use a combination of fully atomistic Molecular Dynamics simulations of sodium and iodide ions at the CNT-NMP interface with direct experiments on the CNT dispersions. In the experiments we analyze the effects of salt on the stability of the dispersions by photoluminescence (PL) and optical absorption spectroscopy of the samples as well as by visual inspection. By fully atomistic Molecular Dynamics simulations we investigate the molecular-scale mechanisms of sodium and iodide ion interactions with the nanotube surface. Our simulations reveal that both ions are depleted from the CNT surface in the CNT-NMP dispersions mainly due to the two reasons: (1) there is a high energy penalty for the ion partial desolvation at the CNT surface; (2) NMP molecules form a dense solvation layer at the CNT surface that prevents ions to come close to the CNT surface. As a result, an increase of the salt concentration increases the "osmotic" stress in the CNT-NMP system and, thus, decreases the stability of the CNT dispersions in NMP. Direct experiments confirm the simulation results: addition of NaI salt into the NMP dispersions of pristine CNTs leads to precipitation of CNTs (bundle formation) even at very small salt concentration (∼10 -3 mol L -1). In line with the simulation predictions, the effect increases with the increase of the salt concentration. Overall, our results show that dissolved salt ions have strong effects on the stability of CNT dispersions. Therefore, it is possible to stimulate the bundle formation in the CNT-NMP dispersions and regulate the overall concentration of nanotubes in the dispersions by changing the NaI concentration in the solvent. © 2012 The Royal Society of Chemistry.

Electrophilic substitution of acetyltrimethylsilane with tellurium(IV) halides: A synthetic route to 3-methyl-5-(trimethylsilyl)-1,2-oxatellurol-1-ium halides

The reaction of tellurium tetrahalides, TeX4 (XCl. Br) with acetyltrimethylsilane in CCl4 at ambient temperature, unlike that of the aryltellurium trichlorides, ArTeCl3 that give the expected electrophilic substitution products, Ar(Me3SiCOCH2)TeCl2, (Ar = 1-C10H7, 2; 2,4,6-Me3C6H2, 3), afforded novel silylated heterocycles, 3-methyl-5-(trimethylsilyl)-1,2-oxatellurol-1-ium halides 1a and 1b. These Te(II) heterocyclic compounds undergo halide exchange with sodium iodide and also add dihalogens oxidatively to afford the corresponding iodide, 1c and the Te(IV) trihalides, 5a and 5b respectively. A large lowering of ν(CO) is indicative of strong Te⋯OC interactions among these heterocycles, and is also substantiated by single-crystal X-ray diffraction data for 3-methyl-5-(trimethylsilyl)-1,2-oxatellurol-1-ium chloride. The ¹²⁵Te chemical shifts for the new 10-Te-3 telluranes and 12-Te-5 pertelluranes that involve tellurium bound to two highly electronegative atoms (O, X) are among the highest (downfield) reported for organotellurium(II) and (IV) compounds.