Free Radical Chemistry. Part 9.1 Approaches to Fluorinated Polyethers—Model Compound Studies

Using peroxide, γ-, and UV-irradiation, free radical addition reactions of hexafluoropropene to diethers and to 18-crown-6 have been investigated and mono-, di-, and poly-adducts have been obtained. Factors influencing these additions, especially polar characteristics of intermediate radicals, have been elucidated. Adducts of 18-crown-6 retain a capacity to complex to alkali-metal ions.     

Lipids in vascular function

Physiological and pathological vascular responses depend on the action of numerous intercellular mediators, ranging from hormones to gases like nitric oxide, proteins, and lipids. The last group consists not only of the different types of lipoproteins, but also includes a broad array of other lipophilic signaling molecules such as fatty acids, eicosanoids, phospholipids and their derivatives, sphingolipids and isoprenoids. Due to space limitations, it is impossible to discuss all the vascular effects of lipophilic mediators or compounds. Therefore, we will focus on one of the most important lipid-mediated diseases, atherosclerosis. Lipoproteins and especially their native or oxidized lipid compounds affect vascular function in many different ways, and these effects do not only modulate atherogenesis but are of paramount physiological and pathophysiological importance in other diseases, such as inflammation, tumor metastasis, or normal wound healing.     

COMPLEX FORMATION AND LIQUID-LIQUID EXTRACTION OF SILVER WITH CYCLIC AND OPEN-CHAIN OXATHIA ALKANES

The complex forming and extraction properties of various open-chain and two cyclic oxathia alkanes towards silver have been studied. The investigations confirm the direct proportionality between extraction constants and related complex stability constants.The extraction of silver by open-chain oxethie alkenee is greeter than by structurally analogoue thicacrown compounds. This fact and the determined stability constants show an absence of a macrocyclic effect during complex formation. The differences of extraction power between the various open-chain compounds can be interpreted on the basic o f the coordinative saturation and stereochemiatry of the silver ion, on the size o f the poesible chelate rings, and on the complexing capability o f the ether oxygen atoms.     

LIQUID-LIQUID EXTRACTION STUDIES OF METAL IONS WITH DIAZACROWN AND STRUCTURE ANALOGOUS OPEN-CHAIN COMPOUNOS

1,10-diaze [8]crown-6, their N,N'-dibutyl- and dioctyl-substituted derivatives and the structure analogous open-chein tetreoxedieza slkanee have been synthesized in order to examine the extraction properties for Na⁺, K⁺, Sr²⁺ and Hg²⁺. It wes found, that the extraction of strontium, potassium and sodium picratee with azacrown compounds ie much higher than that with open-chein oxaaze alkanes. 1,10-diaze [18] erown-6 has a good selectivity for the extraction of Sr²⁺ over K⁺ and Na in alkaline solution. In the case of Sr²⁺ the diffarencea between tha various azacrown compounds are email, whereea in the caee of K⁺ and Na the substituted derivativee are better extractante. Theserssulte correspond qualitativsly with tha order of stebility conetantB in protic solvsnts. The extrectebility of N,N'-dioctyl-l, 10-dieze[18]crown-6 for HgCl₂ is very high. Contrerv to the order of stability conetants the uneubetituted conpound do not extract mercury under the choeen experimental condition*. The extraction power of open-chain conpounde ie aleo high and strong Influenced by the alkyl eubatltuente at the nitrogen donor stons,     

A Device for Generating Singly Charged Particles in the 0.1–1.0-μm Diameter Range

In this paper an aerosol charger that largely avoids the production of multiply charged particles in the 0.1–1.0 μm diameter range is described. The input aerosol is first passed through an electrostatic condenser to remove all charged particles and ions. The remaining neutral aerosol then flows into a 23-cm-long, 2.1-cm inner diameter cylindrical tube; the inner surface of this tube is uniformly coated with 0.09 μCi⁶³ Ni, a 0.067 MeV β-emitter with a half-life of 92 years. At typical airflow rates of 0.2–1.0 lpm, this low-activity source of ionizing radiation produces bipolar ion concentrations ranging from 1 × 10⁴ to 9 × 10⁴ ion/cm³, which is much lower than levels required to bring the aerosol to Boltzmann charge equilibrium. At a flow rate of 1.0 lpm, particles smaller than about 1.0 μm typically interact with no more than one ion en route through the charger. Therefore, particles at the charger exit are mostly either neutral or singly charged. Charge distributions of initially-neutral mono-disperse polystyrene latex particles were measured at the exit from the charger for particle diameters ranging in size from 0.09 to 1.09 μm. It was found that, at an airflow rate of 1.0 lpm and particle size 1.09 μm, the ratios of singly, doubly, and triply charged to total positively charged concentrations were 0.75, 0.19, and 0.06 respectively; particles with more than three charges were not detected. In contrast, the analogous charge ratio at Boltzmann equilibrium is 0.28 (+ 1), 0.24 (+ 2), 0.19 (+ 3), 0.13 (+ 4), 0.08 (+ 5), 0.05 (+ 6), and 0.7 (+ 02).     

The History of Condensation Nucleus Counters

Condensation of supersaturated vapors has been used for more than a century to grow small aerosol particles to sizes that can be detected optically. This paper discusses the history of instruments that use condensation to detect particles. I divide this history into two main sections. The first of these focuses on the development of expansion-type instruments including the ''dust counters'' in which John Aitken played the decisive role and ''photoelectric nucleus counters'' primarily by L. W. Pollak and coworkers. The second section deals with the development of steady-flow condensation nucleus counters (CNCs) in which Jean Bricard and coworkers played the decisive role. The importance of calibration methodologies is also pointed out. Refinements by instrumentation manufacturers and many aerosol scientists have led to the reliable, accurate instruments that are widely used today.     

Investigation of a Novel Condensation Aerosol Generator: Solute and Solvent Effects

Part I of this article presents results of an experimental study on gas-phase nucleation for three model solutes and their solvent, propylene glycol (PG), with variables being solute concentration and the nature of the solute substance. A single manifestation of an aerosol generator, which forms condensation aerosols by cooling of hot vapor issuing from an electrically heated, pumped capillary, is described and used for all experiments. The effects of solute concentration and solute type were studied for deoxycorticosterone (DOC), benzil (BZ), and phenyl salicylate (PhS). Suppression of homogeneous nucleation and occurrence of heterogeneous condensation of the solvent was observed at different solute concentrations for BZ, PhS, and DOC. The nature and concentration of the solute dissolved in the solvent was shown to determine the final particle size distribution of the condensed aerosol. In the case of the least volatile solute, DOC, solute aerosol and total aerosol size distributions were identical at low solute concentrations. A transitional concentration region then existed in which a bimodal solute aerosol was formed, followed at high concentrations by increasing separation of the solvent-dominated aerosol size distribution and that of the solute. In Part II of this article, the effect of DOC dissolution in different solvents was studied at fixed solute concentration. The effects of six glycol solvents--i.e., PG, ethylene glycol (EG), dipropylene glycol (DPG), diethylene glycol (DEG), triethylene glycol (TEG), and tetraethylene glycol (TetEG)--and three nonglycol solvents--i.e., dimethyl sulfoxide (DMSO), formamide (FORM), and oleyl alcohol (OA)--were studied, as these affected the resultant aerosol sizes. Suppression of total aerosol mass median aerodynamic diameter (MMAD) was observed on dissolution of 0.5% w/w DOC in each solvent, although suppression occurred to different extents. It was shown that the boiling point or volatility of the solvent used to dissolve the less volatile DOC had an effect on the final particle size distribution of the condensed aerosol and whether the aerodynamic size distributions for the solute and the total aerosol were the same or different.     

Processing of Soot by Controlled Sulphuric Acid and Water Condensation—Mass and Mobility Relationship

The effects of atmospheric processing on soot particle morphology were studied in the laboratory using the Differential Mobility Analyzer-Aerosol Particle Mass Analyzer (DMA-APM) and the DMA-DMA (Tandem DMA) techniques. To simulate atmospheric processing, combustion soot agglomerates were altered by sulphuric acid vapor condensation, relative humidity (RH) cycling, and evaporation of the sulphuric acid and water by heating. Primary investigated properties were particle mobility size and mass. Secondary properties, derived from these, include effective density, fractal dimension, dynamic shape factor, and the mass fraction of condensed material. A transformation of the soot particles to more compact forms occurs as sulphuric acid and water condense onto fresh soot. The particle mass increases and initially the mobility diameter decreases, indicating restructuring of the soot core, likely due to surface tension forces. For a given soot source and condensing liquid, the degree of compaction depends strongly on the mass (or volume) fraction of condensed material. For water and sulphuric acid condensing on combustion soot, a mass increase of 2–3 times is needed for a transformation to spherical particles. In the limit of spherical particles without voids, the effective density then approaches the inherent material density, the fractal dimension approaches 3 and the dynamic shape factor approaches 1. Our results indicate that under typical atmospheric conditions, soot particles will be fully transformed to spherical droplets on a time scale of several hours. It is expected that the morphology changes and addition of soluble material to soot strongly affect the optical and hygroscopic properties of soot.