Influence of Chain Length and Double Bond on the Aqueous Behavior of Choline Carboxylate Soaps

Langmuir ◽  
2013 ◽  
Vol 29 (8) ◽  
pp. 2506-2519 ◽  
Author(s):  
Doris Rengstl ◽  
Olivier Diat ◽  
Regina Klein ◽  
Werner Kunz
Keyword(s):  
Double Bond ◽  
Chain Length

scholarly journals Nighttime oxidation of surfactants at the air–water interface: effects of chain length, head group and saturation

2018 ◽  
Vol 18 (5) ◽  
pp. 3249-3268 ◽  
Author(s):  
Federica Sebastiani ◽  
Richard A. Campbell ◽  
Kunal Rastogi ◽  
Christian Pfrang
Keyword(s):  
Oleic Acid ◽  
Double Bond ◽  
Methyl Ester ◽  
Reaction Kinetics ◽  
Chain Length ◽  
Rate Coefficients ◽  
Head Group ◽  
Water Interface ◽  
Organic Monolayers ◽  
Air Water Interface

Abstract. Reactions of the key atmospheric nighttime oxidant NO3 with organic monolayers at the air–water interface are used as proxies for the ageing of organic-coated aqueous aerosols. The surfactant molecules chosen for this study are oleic acid (OA), palmitoleic acid (POA), methyl oleate (MO) and stearic acid (SA) to investigate the effects of chain length, head group and degree of unsaturation on the reaction kinetics and products formed. Fully and partially deuterated surfactants were studied using neutron reflectometry (NR) to determine the reaction kinetics of organic monolayers with NO3 at the air–water interface for the first time. Kinetic modelling allowed us to determine the rate coefficients for the oxidation of OA, POA and MO monolayers to be (2.8±0.7) × 10−8, (2.4±0.5) × 10−8and (3.3±0.6) × 10−8 cm2 molecule−1 s−1 for fitted initial desorption lifetimes of NO3 at the closely packed organic monolayers, τd, NO3, 1, of 8.1±4.0, 16±4.0 and 8.1±3.0 ns, respectively. The approximately doubled desorption lifetime found in the best fit for POA compared to OA and MO is consistent with a more accessible double bond associated with the shorter alkyl chain of POA facilitating initial NO3 attack at the double bond in a closely packed monolayer. The corresponding uptake coefficients for OA, POA and MO were found to be (2.1±0.5) × 10−3, (1.7±0.3) × 10−3 and (2.1±0.4) × 10−3, respectively. For the much slower NO3-initiated oxidation of the saturated surfactant SA we estimated a loss rate of approximately (5±1) × 10−12 cm2 molecule−1 s−1, which we consider to be an upper limit for the reactive loss, and estimated an uptake coefficient of ca. (5±1) × 10−7. Our investigations demonstrate that NO3 will contribute substantially to the processing of unsaturated surfactants at the air–water interface during nighttime given its reactivity is ca. 2 orders of magnitude higher than that of O3. Furthermore, the relative contributions of NO3 and O3 to the oxidative losses vary massively between species that are closely related in structure: NO3 reacts ca. 400 times faster than O3 with the common model surfactant oleic acid, but only ca. 60 times faster with its methyl ester MO. It is therefore necessary to perform a case-by-case assessment of the relative contributions of the different degradation routes for any specific surfactant. The overall impact of NO3 on the fate of saturated surfactants is slightly less clear given the lack of prior kinetic data for comparison, but NO3 is likely to contribute significantly to the loss of saturated species and dominate their loss during nighttime. The retention of the organic character at the air–water interface differs fundamentally between the different surfactant species: the fatty acids studied (OA and POA) form products with a yield of  ∼ 20 % that are stable at the interface while NO3-initiated oxidation of the methyl ester MO rapidly and effectively removes the organic character ( ≤ 3 % surface-active products). The film-forming potential of reaction products in real aerosol is thus likely to depend on the relative proportions of saturated and unsaturated surfactants as well as the head group properties. Atmospheric lifetimes of unsaturated species are much longer than those determined with respect to their reactions at the air–water interface, so they must be protected from oxidative attack, for example, by incorporation into a complex aerosol matrix or in mixed surface films with yet unexplored kinetic behaviour.

Structural Homogeneity in Unsaturated Fatty Acids of Marine Lipids. A Review

1964 ◽  
Vol 21 (2) ◽  
pp. 247-254 ◽  
Author(s):  
R. G. Ackman
Keyword(s):  
Fatty Acids ◽  
Double Bond ◽  
Polyunsaturated Fatty Acids ◽  
Chain Length ◽  
Unsaturated Fatty Acids ◽  
Analytical Data ◽  
Double Bonds ◽  
Marine Origin ◽  
Methyl Group ◽  
Marine Lipids

Consideration of recent analytical data supports the conclusion that the longer-chain polyunsaturated fatty acids of marine origin are all structurally homogeneous in that the double bonds are cis, the double bonds methylene interrupted, and that, with the exception of the C16 chain length, the ultimate double bond will normally be three, six or nine carbon atoms removed from the terminal methyl group.

Diels-Alder Reaction Curing of Chlorobutyl Rubber by bis-Maleimides

1989 ◽  
Vol 62 (1) ◽  
pp. 42-54 ◽  
Author(s):  
K. Ho ◽  
R. Steevensz
Keyword(s):  
Zinc Oxide ◽  
Double Bond ◽  
Chain Length ◽  
Crosslinking Agent ◽  
Alder Reaction ◽  
Diels Alder ◽  
Diels Alder Reaction ◽  
Electronic Distribution ◽  
Curing Agents ◽  
Chlorobutyl Rubber

Abstract Different bis-maleimides are found to have different efficiencies and reactivities in the crosslinking of CIIR in the presence of zinc oxide. Although the degrees of crosslinking of CIIR by bis-maleimides cannot be defined absolutely, some trends concerning the efficiencies of the crosslinking are evident. In general, the aromatic bis-maleimides gave higher degrees of crosslinking than the aliphatic analogs. The reactivity and crosslinking efficiency of an individual bis-maleimide is very much affected by its end-to-end chain length and its electronic distribution, resulting from the interaction between the maleimide groups, and from the interaction between the maleimide groups and other functional groups present in the same molecule. The longer the bis-maleimide molecule and the more electron deficient the maleimido double bond, the greater its effectiveness as a crosslinking agent. Other curing mechanisms, possibly including polymerization of the maleimido groups, appear to be operative when using aromatic bis-maleimides as curing agents for CIIR.

Study of the Reaction of Buna Rubbers with Aliphatic Thiols

1949 ◽  
Vol 22 (1) ◽  
pp. 148-154
Author(s):  
G. E. Serniuk ◽  
F. W. Banes ◽  
M. W. Swaney
Keyword(s):  
Double Bond ◽  
Chain Length ◽  
Thioglycolic Acid ◽  
Benzene Solution ◽  
Polymer Chains ◽  
Double Bonds ◽  
Mild Conditions ◽  
Acid Addition ◽  
Aliphatic Thiols

Abstract Thioglycolic acid added exothermally to butadiene polymers and copolymers in benzene solution under mild conditions to give apparent double-bond saturation values of 38 to 47 per cent. When the same polymers reacted with aliphatic thiols of C2 to C16 chain length, in mass or latex reactions, saturation values were obtained which were in accord with those found by thioglycolic acid addition. It is suggested that the double bonds in butadiene polymers and copolymers which were readily saturated by the above thiols are predominately those present in the polymer chains as vinyl side groups.

Structure-response Relationships in Noctuid Sex Pheromone Reception An Introductory Report

1975 ◽  
Vol 30 (3-4) ◽  
pp. 283-293 ◽  
Author(s):  
Ernst Priesner ◽  
Martin Jacobson ◽  
Hans Bestmann
Keyword(s):  
Double Bond ◽  
Chain Length ◽  
Olfactory Receptors ◽  
Response Spectra ◽  
Double Bond Position ◽  
Structure Response ◽  
Optimum Position ◽  
Methylene Groups ◽  
Pheromone Reception ◽  
End Group

Abstract Pheromones, Olfactory Receptors, Structure-response Relationships, Lepidoptera Electroantennogram (EAG) data reflecting response spectra of male pheromone receptors have been analyzed for 16 species of Noctuidae (Lepidoptera). The test compounds included 100 phero­ mone analogues, altered in chain length, in position and configuration of double bond(s), and in the functional end groups. On comparison of amounts of substance required to elicit an equivalent EAG response, a single compound was determined to be most effective on a given species; these structures, either known or proposed as the natural sex pheromones of the species, were cis-1-dodecen-1-yl acetate, cis-7-tetradecen-1-yl acetate, cts-9-tetradecen-1-yl acetate, Jrarcs-9-tetradecen-1-yl acetate, cis-ll-hexadecen-l-yl acetate, cis-9, trans-12-tetradecadien-l-yl acetate, cis-9-tetradecen-1-yl formate, and cts-9-tetradecen-1-ol, respectively. Elongation (shortening) of the chain by 1 or 2 methylene groups, the movement of a double bond 1 carbon from the optimum, a change to the opposite geometrical isomer, or the introduction of a second double bond invariably reduced EAG responses to 1.8 to 56 times below that observed with the most stimulating compound, in all 16 species. Further alterations in chain length or in double bond position caused even greater reduc­ tion in activity, as did certain changes in end group (Tables I and II). A set of distinct rules could be derived from these structure-response relationships; one of these rules concerns the optimum position of the double bond(s) in relation to chain length, and another one the ratios in activity values produced by end group variations, irrespective of chain length. The same rules described here for 16 noctuid species held also for the structure-response relationships observed within various additional groups of Lepidoptera. From EAG values determined in this study, an attempt has been made to calculate physico­ chemical propteries of underlying acceptor structures.

Long-Range Effect of 17-Substituents in 3-Oxo Steroids on 4,5-Double Bond Hydrogenation

1998 ◽  
Vol 63 (10) ◽  
pp. 1528-1542 ◽  
Author(s):  
Romana Šídová ◽  
Karel Stránský ◽  
Alexander Kasal ◽  
Barbora Slavíková ◽  
Ladislav Kohout
Keyword(s):  
Acetic Acid ◽  
Double Bond ◽  
Carboxylic Acids ◽  
Chain Length ◽  
Long Range ◽  
Alkyl Chain ◽  
Platinum Catalyst ◽  
Alkyl Chain Length ◽  
Range Effect ◽  
Bond Hydrogenation

The long-range effect of substituents in the 17-position on the hydrogenation of double bond of the steroidal ∆4-3-ketones in acetic acid on a platinum catalyst is described in a series of testosterone (1) and epitestosterone (5) esters with carboxylic acids of varying alkyl chain length. The ratio 5α- to 5β-products is affected by the nature of substituents in the position 17.

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