NMR chemical shift reagents in structural determination of lipid derivatives: III. Methyl ricinoleate and methyl 12‐hydroxystearate

Wineburg, John P.; Swern, Daniel

doi:10.1007/bf02640467

Cited by 12 publications

(2 citation statements)

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“…Information for unsaturated lipid derivatives can be obtained by the introduction of additional functional groups which are CSR active. Thus, successful CSR studies were published on methyl ricinoleate (methyl 12-hydroxy- cis -Δ 9,10 -octadecenoate) and methyl 12-hydroxy stearate (methyl 12-hydroxy-9,10-octadecanoate) [ 104 ]. For methyl ricinoleate, individual signals were observed for each of the olefinic protons 9 and 10 and their induced shifts were related to the proximity of the OH group.…”

Section: Nmr Methods For Assignmentmentioning

confidence: 99%

High Resolution NMR Spectroscopy as a Structural and Analytical Tool for Unsaturated Lipids in Solution

et al. 2017

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Mono- and polyunsaturated lipids are widely distributed in Nature, and are structurally and functionally a diverse class of molecules with a variety of physicochemical, biological, medicinal and nutritional properties. High resolution NMR spectroscopic techniques including 1H-, 13C- and 31P-NMR have been successfully employed as a structural and analytical tool for unsaturated lipids. The objective of this review article is to provide: (i) an overview of the critical 1H-, 13C- and 31P-NMR parameters for structural and analytical investigations; (ii) an overview of various 1D and 2D NMR techniques that have been used for resonance assignments; (iii) selected analytical and structural studies with emphasis in the identification of major and minor unsaturated fatty acids in complex lipid extracts without the need for the isolation of the individual components; (iv) selected investigations of oxidation products of lipids; (v) applications in the emerging field of lipidomics; (vi) studies of protein-lipid interactions at a molecular level; (vii) practical considerations and (viii) an overview of future developments in the field.

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Section: Nmr Methods For Assignmentmentioning

confidence: 99%

High Resolution NMR Spectroscopy as a Structural and Analytical Tool for Unsaturated Lipids in Solution

et al. 2017

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“…Methyl Ricinoleate has been analyzed by nuclear magnetic resonance (NMR) spectroscopy (Wineburg and Swern 1973) and gas-liquid chromatography (Paulus and Champion 1972).…”

Section: Methyl Ricinoleatementioning

confidence: 99%

Final Report on the Safety Assessment of Ricinus Communis (Castor) Seed Oil, Hydrogenated Castor Oil, Glyceryl Ricinoleate, Glyceryl Ricinoleate SE, Ricinoleic Acid, Potassium Ricinoleate, Sodium Ricinoleate, Zinc Ricinoleate, Cetyl Ricinoleate, Ethyl Ricinoleate, Glycol Ricinoleate, Isopropyl Ricinoleate, Methyl Ricinoleate, and Octyldodecyl Ricinoleate1

2007

Int J Toxicol

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The oil derived from the seed of the Ricinus communis plant and its primary constituent, Ricinoleic Acid, along with certain of its salts and esters function primarily as skin-conditioning agents, emulsion stabilizers, and surfactants in cosmetics, although other functions are described. Ricinus Communis (Castor) Seed Oil is the naming convention for castor oil used in cosmetics. It is produced by cold pressing the seeds and subsequent clarification of the oil by heat. Castor oil does not contain ricin because ricin does not partition into the oil. Castor oil and Glyceryl Ricinoleate absorb ultraviolet (UV) light, with a maximum absorbance at 270 nm. Castor oil and Hydrogenated Castor Oil reportedly were used in 769 and 202 cosmetic products, respectively, in 2002; fewer uses were reported for the other ingredients in this group. The highest reported use concentration (81%) for castor oil is associated with lipstick. Castor oil is classified by Food and Drug Administration (FDA) as generally recognized as safe and effective for use as a stimulant laxative. The Joint Food and Agriculture Organization (FAO)/World Health Organization (WHO) Expert Committee on Food Additives established an acceptable daily castor oil intake (for man) of 0 to 0.7 mg/kg body weight. Castor oil is hydrolyzed in the small intestine by pancreatic enzymes, leading to the release of glycerol and Ricinoleic Acid, although 3,6-epoxyoctanedioic acid, 3,6-epoxydecanedioic acid, and 3,6-epoxydodecanedioic acid also appear to be metabolites. Castor oil and Ricinoleic Acid can enhance the transdermal penetration of other chemicals. Although chemically similar to prostaglandin E(1), Ricinoleic Acid did not have the same physiological properties. These ingredients are not acute toxicants, and a National Toxicology Program (NTP) subchronic oral toxicity study using castor oil at concentrations up to 10% in the diet of rats was not toxic. Other subchronic studies of castor oil produced similar findings. Undiluted castor oil produced minimal ocular toxicity in one study, but none in another. Undiluted castor oil was severely irritating to rabbit skin in one study, only slightly irritating in another, mildly irritating to guinea pig and rat skin, but not irritating to miniature swine skin. Ricinoleic Acid was nonirritating in mice and in one rabbit study, but produced well-defined erythema at abraded and intact skin sites in another rabbit study. Zinc Ricinoleate was not a sensitizer in guinea pigs. Neither castor oil nor Sodium Ricinoleate was genotoxic in bacterial or mammalian test systems. Ricinoleic Acid produced no neoplasms or hyperplasia in one mouse study and was not a tumor promoter in another mouse study, but did produce epidermal hyperplasia. Castor oil extract had a strong suppressive effect on S(180) body tumors and ARS ascites cancer in male Kunming mice. No dose-related reproductive toxicity was found in mice fed up to 10% castor oil for 13 weeks. Female rats injected intramuscularly with castor oil on the first day after estrus had supp...

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Lanthanide chemical shift reagents as tools for determining isomer distributions in 2,4‐hexadienoates and related compounds

MacMillan¹,

Washburne²

1974

Org. Magn. Reson.

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Abstract-Quantitative analysis of geometrical isomers of unsaturated esters and alcohols is facilitated with Eu(fod),. Commercial sorbic acid exists in the all-kuns form, while sorbyl alcohol contains c. 10% of the c&4,5 isomer.NMR CHEMICAL shift reagents continue to find widening application in elucidating coupling constants and geometric configurations1 of organic molecules. Esters,2 alcohols and ketones 3 give greatly simplified spectra with Eu(fod), 1 at Eu/substrate concentrations c. 0.2 to 0.5. Recently Swern and Wineburg demonstrared the utility of 1 in elucidating possible branching in the structures of long chain fatty acids. We wish to report that 1 is a useful reagent for qualitative and quantitative estimations of isomer distributions in sorbate esters and sorbyl alcohol.In a related study5 we wished to determine the isomer distribution of 2,4-hexadienoic (sorbic) acid obtained from various natural and commercial sources. Since acids decompose shift reagents,6 commercial sorbic acid (Aldrich) was treated with diazomethane. The resulting ester gave a complex, non-analyzable olefinic (CH,, d). The same spectrum was obtained from ester prepared from sorbic acid, methanol and sulfuric acid. However, when ester prepared from sorboyl chloride and methanol was so analyzed, new multiplets appeared in the spectrum, indicating the presence of another isomer. A second OCH, singlet appeared upfield together with second upfield patterns for both H, and H,. These exhibited the same multiplicity and coupling constants as above. However, the H, and Hs patterns still overlapped with those from all-tram isomer. The terminal CH, showed a new doublet downfield from the corresponding all-trans isomer doublet, with long range doublet splitting,7 in accord with H, and Hb being cis. Integration showed a 17 % concentration of the 2-truns-kis isomer.The induced shift ratio concept elaborated by Swern and Wineburg is of utility in analyzing these data. The induced shift ratio E is independent of shift reagent concentration, and depends only on the relative shifts of a particular proton H, and a standard proton H, in * To whom enquiries should be addressed. 250the same molecule, which in esters, alcohols and ketones is defined as the proton most proximate to the functional group. ZZ = (aEn -~o>,/(~E, -dOL, where bu and do are respectively the chemical shifts with and without the presence of shift reagent. The induced shift ratios of the two sorbic acid isomers, together with the relative chemical shifts of the protons in the two isomers, are given in Table 1. As E in long chain alcohols and esters is a function monotonically decreasing with increasing distance from the complexation site,4 it is of interest to note the inversion of E,, and &oH3 in the isomers 2a and 2b. Examination of structure diagrams shows that H, and C-CH, exchange their spatial locations relative to the ester function as the 4,5-double bond inverts configuration.Although the criteria of lanthanide induced shifts obeying a r-3 'distance only' relationship h...

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NMR chemical shift reagents in structural determination of lipid derivatives: III. Methyl ricinoleate and methyl 12‐hydroxystearate

Cited by 12 publications

References 4 publications

High Resolution NMR Spectroscopy as a Structural and Analytical Tool for Unsaturated Lipids in Solution

High Resolution NMR Spectroscopy as a Structural and Analytical Tool for Unsaturated Lipids in Solution

Lanthanide chemical shift reagents as tools for determining isomer distributions in 2,4‐hexadienoates and related compounds

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