Female rats were fed a diet containing by weight 10% partially hydrogenated sunflower oil, 2% sunflower oil, and 1% rapeseed oil during gestation and lactation. The trans-18:1 isomer profile of the fat supplement was (in % of total trans 18:1 acids in the fat supplement): delta4, 0.5; delta5, 1.0; delta6-delta8, 18.0; delta9 (elaidic), 13.5; delta10, 22.2; delta11 (vaccenic), 16.0; delta12, 11.3; delta13-delta14, 12.8; delta15, 2.5; and delta16, 2.2 (total trans 18:1 acids in the fat supplement: 40.6%). The cis 18:1 isomer profile was (in % of total cis-18:1 isomers): delta6-delta8, 2.1; delta9 (oleic), 70.9; delta10, 6.1; delta11, 8.3; delta12, 4.0; delta13, 2.8; delta14, 4.6, and delta15, 1.2 (total cis-18:1 acids in the fat supplement: 32.6%). Suckling rats from four litters were sacrificed at day 17 or 18 after birth, and their stomach content (milk) was analyzed. The trans-18:1 isomer profile of milk was (relative proportions, in % of total): delta4, 0.3; delta5, 1.1; delta6-delta8, 16.8; delta9, 15.3; delta10, 22.0; delta11, 16.7; delta12, 11.8; delta13-14, 11.8; delta15, 2.5, and delta16, 1.9 (total trans 18:1 acids in milk: %). That of cis-18:1 isomers was (proportions in % relative to total cis-18:1 isomers): delta6-delta8, 4.7; delta9, 72.5; delta10, 4.0; delta11, 8.0; delta12, 7.1; delta13, 1.9; delta14, 1.0, and delta15, 0.7 (total cis-18:1 acids in milk: %). These results demonstrate that all isomeric acids, independent of the geometry and the position of the ethylenic bond, are incorporated into milk lipids. With regard to trans-18:1 isomers, the distribution profile in milk is identical to that in the dams' diet, i.e., there is no discrimination against any positional isomer between their ingestion and their deposition into milk lipids. As a consequence, this study indicates that the trans-18:1 isomer profile of milk reflects that in the dams' diet and supports our earlier hypothesis that the profile of trans-18:1 isomers in milk can be used to deduce the relative contribution of ruminant fats and partially hydrogenated oils in the diet to the total intake of trans-18:1 isomers. On the other hand, the cis-18:1 isomer profile in milk shows significant differences when compared to that in the dams' diet. Surprisingly, there are no major differences for the cis-delta9 (oleic) and the cis-delta11 (asclepic) isomers, which can be synthesized by the mother. However, there seems to be a significant positive selectivity for the group cis-delta6-delta8, and for the cis-delta12 isomer, whereas a negative selectivity occurs for the delta10 and delta13 to delta15 cis isomers.

In the present study, we investigated the alkenyl chains from sheep heart plasmalogens (1-O-alk-1′-enyl-2-acyl glycerophospholipids) after their conversion into trimethylene dioxyalkanyl (TMDOA) derivatives. Particular attention was given to monounsaturated alkenyl chains (C18 mainly). For this purpose, a combination of silver ion TLC and GLC on highly polar, very long capillary columns was applied to TMDOA derivatives. Approximately 30 different alkenyl chains could be separated, and the main observation was that the component previously reported as a cis-9 18∶1 alkenyl chain in plasmalogens embraces in fact a wide range of trans and cis isomers, in amounts equal to 7.9 and 5.6%, respectively, of total alkenyl chains. Concerning the trans-monoenoate fraction, isomers with their ethylenic bond spanning from Δ6–Δ8 to Δ16 were tentatively identified on the basis of their distribution profile, which was similar to that of trans-18∶1 acids prepared and isolated from sheep adipose tissue. The main trans-monoenoic C18 alkenyl chain in sheep heart plasmalogens would thus have its double bond in position 11, which seems logical, as alkenyl chains are derived from the corresponding alcohols, themselves issued from the corresponding FA, and in this particular case, vaccenic (trans-11 18∶1) acid. cis-Monoenoic C18 alkenyl chains also appear more complex than realized earlier, showing in particular isomers with their ethylenic bond farther than the Δ9 position, in addition to the main isomer derived from oleic acid. Several trans-16∶1 alkenyl chains could be observed (totaling ca. 1%), but cis-16∶1 isomers were present in trace amounts only.

In view of the increasing interest of lipid researchers in the biological effects of all-cis Delta5-unsaturated polymethylene-interrupted fatty acids (Delta5-UPIFA) from vegetable origin, this paper is concerned with their occurrence in practical sources (gymnosperm seeds), structures, and identification by gas-liquid chromatography (GLC) and mass spectrometry (MS). The use of equivalent chain lengths (ECL) determined by calculations based on available standards, in close agreement with data determined with easily available commercial gymnosperm seeds specific for each Delta5-UPIFA, allows identification of all Delta5-UPIFA. These tentative identifications are supported by GLC-MS of the appropriate (4,4-dimethyloxazoline and picolinyl ester) derivatives. ECL are particularly useful to identify Delta5-UPIFA in tissue lipids from animals experimentally fed oils containing these acids, with no interference with polyunsaturated fatty acids of endogenous origin.

LipidsVolume 37, Issue 12 p. 1149-1150 Letter to the Editor Reassessment of the contribution of bovine milk fats to the trans-18:1 isomeric acid consumption by European populations. Additional data for rumenic (cis-9,trans-11 18:2) acid Robert L. Wolff, Robert L. Wolff INRA, UNL, Dijon cedex, 21065 France Deceased.Search for more papers by this authorDietz Precht, Corresponding Author Dietz Precht [email protected] Federal Dairy Research Centre, Institute of Dairy Chemistry and Technology, P.O. Box 6069, Kiel, 24121 GermanyTo whom correspondence should be addressed at Institute of Dairy Chemistry and Technology, Federal Dairy Research Center, P.O. Box 6069, 24121 Kiel, Germany. E-mail: [email protected]Search for more papers by this author Robert L. Wolff, Robert L. Wolff INRA, UNL, Dijon cedex, 21065 France Deceased.Search for more papers by this authorDietz Precht, Corresponding Author Dietz Precht [email protected] Federal Dairy Research Centre, Institute of Dairy Chemistry and Technology, P.O. Box 6069, Kiel, 24121 GermanyTo whom correspondence should be addressed at Institute of Dairy Chemistry and Technology, Federal Dairy Research Center, P.O. Box 6069, 24121 Kiel, Germany. E-mail: [email protected]Search for more papers by this author First published: 01 December 2002 https://doi.org/10.1007/s11745-002-1013-0Citations: 20 Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article.Citing Literature Volume37, Issue12December 2002Pages 1149-1150 RelatedInformation

LipidsVolume 37, Issue 12 p. 1147-1148 Letter to the Editor Are trans isomers of α-linolenic acid of nutritional significance for certain populations? Robert L. Wolff, Robert L. Wolff INRA, UNL, Dijon cedex, 21065 France Deceased.Search for more papers by this author Robert L. Wolff, Robert L. Wolff INRA, UNL, Dijon cedex, 21065 France Deceased.Search for more papers by this author First published: 01 December 2002 https://doi.org/10.1007/s11745-002-1012-1Citations: 8 Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onEmailFacebookTwitterLinkedInRedditWechat No abstract is available for this article. References 1Combe, N.A., and Boué, C. (2001) Apports alimentaires en Acides Linoléique et alpha-Linolénique d'une Population d'Aquitaine, Oléagineux, Corps Gras, Lipides 8, 118–121. 2Wolff, R.L. (1992) Trans-Polyunsaturated Fatty Acids in French Edible Rapeseed and Soybean Oils, J. Am. Oil Chem. Soc. 69, 106–110. 3Wolff, R.L. (1993) Further Studies on Artificial Geometrical Isomers of α-Linolenic Acid in Linolenic Acid-Containing Oils, J. Am. Oil Chem. Soc. 70, 219–224. 4Wolff, R.L. (1993) Occurrence of Artificial trans-Polyunsaturated Fatty Acids in Refined (deodorized) Walnut Oils, Sci. Aliments 13, 155–163. 5Wolff, R.L. (1997) Trans Isomers of α-Linolenic Acid in Deodorized Oils, Lipid Technol. Newslett. 3, 36–39. 6Bretillon, L., Chardigny, J.M., Sébédio, J.-L., Noël, J.P., Scrimgeour, C.M., Fernie, C.E., Loreau, O., Gachon, P., and Beaufrère, B. (2001) Isomerization Increases the Postprandial Oxidation of Linoleic Acid but Not α-Linolenic Acid in Men, J. Lipid Res. 42, 995–997. 7Brétillon, L., Chardigny, J.M., Noël, J.P., and Sébédio, J.-L. (1998) Desaturation and Chain Elongation of 1-14C Mono-trans Isomers of Linoleic and α-Linolenic Acids in Perfused Rat Liver, J. Lipid Res. 39, 2228–2239. 8Boué, C., Combe, N., Billeaud, C., Mignerot, C., Entressangles, B., Thery, G., Geoffrion, H., Brun, J.L., Dallay, D., and Leng, J.J. (2000) Trans Fatty Acids in Adipose Tissue of French Women in Relation to Their Dietary Sources, Lipids 35, 561–566. 9Sébédio, J.-L., Grandgirard, A., Septier, C., and Prevost, J. (1987) Etat d'Altération de Quelques Huiles de Friture Prélevées en Restauration, Rev. Fr. Corps Gras. 34, 15–18. 10Chardigny, J.M., Wolff, R.L., Mager, E., Sébédio, J.-L., Martine, L., and Juanéda, P. (1995) Trans Mono- and Polyunsaturated Fatty Acids in Human Milk, Eur. J. Clin. Nutr. 49, 523–531. 11Precht, D., and Molkentin, J. (1999) C18:1, C18:2 and C18:3 trans and cis Fatty Acid Isomers Including Conjugated cis Δ9, trans Δ11 Linoleic Acid (CLA) as Well as Total Fat Composition of German Human Milk Lipids, Nahrung 43, 233–244. 12Chardigny, J.M., Wolff, R.L., Mager, E., Bayard, C.C., Sébédio, J.-L., and Ratnayake, W.M.N. (1996) Fatty Acid Composition of French Infant Formulas with Emphasis on the Content and Detailed Profile of trans Fatty Acids, J. Am. Oil Chem. Soc. 73, 1595–1601. 13Ratnayake, W.M.N., Chardigny, J.M., Wolff, R.L., Bayard, C.C., Sébédio, J.-L., and Martine, L. (1997) Essential Fatty Acids and Their trans Geometrical Isomers in Powdered and Liquid Infant Formulas Sold in Canada, J. Pediatr. Gastroenterol. Nutr. 20, 400–407. Citing Literature Volume37, Issue12December 2002Pages 1147-1148 ReferencesRelatedInformation

LipidsVolume 37, Issue 6 p. 627-629 Letter to the Editor A critique of 50-m CP-Sil 88 capillary columns used alone to assess trans-unsaturated FA in foods: The case of the TRANSFAIR study Robert L. Wolff, Robert L. Wolff INRA, UNL, B.P. 86510, 17, rue Sully, Dijon Cedex, 21065 FranceSearch for more papers by this authorDietz Precht, Corresponding Author Dietz Precht [email protected] Institute of Dairy Chemistry and Technology, Federal Dairy Research Center, Kiel, 24121 GermanyTo whom correspondence should be addressed at INRA, UNL, 17, rue Sully, B.P. 86510, 21065 Dijon Cedex, France. E-mail: [email protected]Search for more papers by this author Robert L. Wolff, Robert L. Wolff INRA, UNL, B.P. 86510, 17, rue Sully, Dijon Cedex, 21065 FranceSearch for more papers by this authorDietz Precht, Corresponding Author Dietz Precht [email protected] Institute of Dairy Chemistry and Technology, Federal Dairy Research Center, Kiel, 24121 GermanyTo whom correspondence should be addressed at INRA, UNL, 17, rue Sully, B.P. 86510, 21065 Dijon Cedex, France. E-mail: [email protected]Search for more papers by this author First published: 01 June 2002 https://doi.org/10.1007/s11745-002-0942-yCitations: 24AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL No abstract is available for this article.Citing Literature Volume37, Issue6June 2002Pages 627-629 RelatedInformation

The seed fatty acid (FA) compositions of Abietoids (Abies, Cedrus, Hesperopeuce, Keteleeria, Pseudolarix, and Tsuga) are reviewed in the present study in conclusion to our survey of Pinaceae seed FA compositions. Many unpublished data are given. Abietoids and Pinoids (Pinus, Larix, Ficea, and Pseudotsuga)—constituting the family Pinaceae—are united by the presence of several Δ5-olefinic acids, taxoleic (5,9–18∶2), pinolenic (5,9,12–18∶3) coniferonic (5,9,12,15–18∶4), keteleeronic (5,11–20∶2), and sciadonic (5,11,14–20∶3) acids, and of 14-methyl hexadecanoic (anteiso-17∶0) acid. These acids seldom occur in angiosperm seeds. The proportions of individual Δ5-olefinic acids, however, differ between Pinoids and Abietoids. In the first group, pinolenic acid is much greater than taxoleic acid, whereas in the second group, pinolenic acid is greater than or equal to taxoleic acid. Moreover, taxoleic acid in Abietoids is much greater than taxoleic acid in Pinoids, an apparent limit between the two subfamilies being about 4.5% of that acid relative to total FA. Tsuga spp. appear to be a major exception, as their seed FA compositions are much like those of species from the Pinoid group. In this respect, Hesperopeuce mertensiana, also known as Tsuga mertensiana, has little in common with Abietoids and fits the general FA pattern of Pinoids well. Tsuga spp. and H. mertensiana, from their seed FA compositions, should perhaps be separated from the Abietoid group and their taxonomic position revised. It is suggested that a “Tsugoid” subfamily be created, with seed FA in compliance with the Pinoid pattern and other botanical and immunological criteria of the Abietoid type. All Pinaceae genera, with the exception of Pinus, are quite homogeneous when considering their overall seed FA compositions, including Δ5-olefinic acids. In all cases but one (Pinus), variations from one species to another inside a given genus are of small amplitude. Pinus spp., on the other hand, have highly variable levels of Δ5-olefinic acids in their FA compositions, particularly when sections (e.g., Cembroides vs. Pinus sections) or subsections (e.g., Flexiles and Cembrae subsections from the section Strobus) are compared, although they show qualitatively the same FA patterns characteristic of Pinoids. Multicomponent analysis of Abietoid seed FA allowed grouping of individual species into genera that coincide with the same genera otherwise characterized by more classical botanical criteria. Our studies exemplify how seed FA compositions, particularly owing to the presence of Δ5-olefinic acids, may be useful in sustaining and adding some precision to existing taxonomy of the major family of gymnosperms, Pinaceae.

GC analysis was performed to determine regiospecific distribution and FA composition in seed oils of the Aceraceae species, Acer saccharum and A. saccharinum. The oil content in the seeds was low at 5.0% in A. saccharum and 5.8% in A. saccharinum, and the main FA were linoleic (30.8 and 29.4%), oleic (21.3 and 27.6%), palmitic (10.1 and 10.5%), and cis-vaccenic (9.4 and 7.9%) acids, respectively. In addition, both oils contained long-chain monoenes of the n−9 and n−7 groups, including 11-eicosenoic, 13-docosenoic, 15-tetracosenoic, 13-eicosenoic, and 15-docosenoic acids, whereas γ-linolenic acid accounted for 0.8% of total FA in A. saccharum, and 0.5% in A. saccharinum. Regiospecific analysis, performed using the methodology of dibutyroyl derivatives of MAG, indicated that linoleic, oleic, and linolenic acids were mainly esterified at the internal position of TAG in both seed oils, whereas long-chain monoenes of the n−7 group were almost exclusively esterified on the external positions.

Dibutyrate derivatives of monoacylglycerols of oleic, petroselinic, and cis-vaccenic acids were prepared by diesterification of monoacylglycerols with n-butyryl chloride. The resulting triacylglycerols were analyzed by gas chromatography (GC) with a 65% phenyl methyl silicone capillary column and separated on the basis of both fatty acid composition and regiospecific position. The petroselinic acid derivatives eluted first, followed sequentially by the oleic and cis-vaccenic acid derivatives, with the sn−2 positional isomer eluting before the sn−1(3) isomer in each case. Separation of the peaks was almost baseline between petroselinic and oleic acids as well as between oleic and cis-vaccenic acids. To assess the accuracy of the method, mixtures of triolein, tripetroselinin, and tri-cis-vaccenin in various known proportions were partially deacylated with the use of ethyl magnesium bromide and derivatized and analyzed as above. The results showed that this method compares favorably to the existing methods for analysis of oleic, petroselinic, and cis-vaccenic fatty acids by GC with respect to peak separation and accuracy, and it also provides information on the regiospecific distribution of the fatty acids. The method was applied to basil (Ocimum basilicum) and coriander (Coriandrum sativum) seed oils. cis-Vaccenic, oleic, and linoleic acids were mainly distributed at the sn−2 position in basil seed oil, and higher proportions of linolenic, palmitic, and stearic acids were distributed at the sn−1(3) position than at the sn−2 position. In coriander seed oil, petroselinic acid was mainly distributed at the sn−1(3) position, and both oleic and linoleic acids were mostly located at the sn−2 position, whereas palmitic, stearic, and cis-vaccenic acids were located only at the sn−1(3) position.

Minor uncommon FA from Hesperopeuce mertensiana (a gymnosperm species of the Pinaceae family) seed oil were characterized through a combination of silver ion TLC of their FAME, and GLC coupled with MS of their picolinyl derivatives. These uncommon components have the structures 16-methyloctadecanoic (anteiso-19∶0), 16-methyl-cis-9-octadecenoic (anteiso-19∶1), and 16-methyl-cis-9,cis-12-octadecadienoic (anteiso-19∶2) acids. These branched C19 acids were identified earlier in the wood of Picea abies, which would indicate that such acids could be widespread, though minor, components of Pinaceae lipids.

Background Conifer seeds are used for food preparation in several countries. Aim of the study To assess the lipid-lowering and antiatherogenic properties of maritime pine (Pinus pinaster) seed oil. Methods The effects of maritime pine oil supplementation (20 % w/w) for 2 weeks were compared to those of coconut and sunflower oil in mice expressing human apolipoprotein B (hApoB). Atherosclerosis lesion development was measured in hApoB mice fed 1.25 % (w/w) cholesterol and 0.05 % (w/w) sodium cholate and either coconut, sunflower or maritime pine oil (20 % w/w) for 8 weeks. Results After 2 weeks of dietary treatment, plasma cholesterol (p < 0.0001), triglyceride (p < 0.0003), phospholipid (p < 0.0001) and apolipoprotein B (p < 0.0001) levels were lower in mice supplemented with maritime pine oil than in those treated with coconut oil. These effects were accounted for by a lowering of LDL-cholesterol, LDL-phospholipids and LDL-triglycerides, as well as a decrease in HDL-cholesterol and HDL-phospholipids. After 8 weeks of dietary treatment cholesterol and cholate, the mean area of aortic lesions was not statistically different between fat groups. Conclusions Feeding maritime pine oil is associated with major changes of lipid and lipoprotein levels in hApoB mice. However, in the long term, maritime pine oil has no preventive effect on cholesterol-induced aortic lesion development in hApoB mice.

A previously undescribed fatty acid, all-cis 7,11-20:2 (dihomotaxoleic acid, DHT), has been characterized by gas chromatography-mass spectrometry as being present (approximately 0.1%) in seed oils of two Taxaceae containing high levels (11-16%) of taxoleic acid (all-cis 5,9-18:2). This compound was absent from oils of 10 other conifer genera, as well as from one member of Taxaceae containing very low amounts of taxoleic acid, suggesting that DHT is a taxoleic acid elongation product.

Following our previous review on Pinus spp. seed fatty acid (FA) compositions, we recapitulate here the seed FA compositions of Larix (larch), Picea (spruce), and Pseudotsuga (Douglas fir) spp. Numerous seed FA compositions not described earlier are included. Approximately 40% of all Picea taxa and one-third of Larix taxa have been analyzed so far for their seed FA compositions. Qualitatively, the seed FA compositions in the three genera studied here are the same as in Pinus spp., including in particular the same Δ5-olefinic acids. However, they display a considerably lower variability in Larix and Picea spp. than in Pinus spp. An assessment of geographical variations in the seed FA composition of P. abies was made, and intraspecific dissimilarities in this species were found to be of considerably smaller amplitude than interspecific dissimilarities among other Picea species. This observation supports the use of seed FA compositions as chemotaxonomic markers, as they practically do not depend on edaphic or climatic conditions. This also shows that Picea spp. are coherently united as a group by their seed FA compositions. This also holds for Larix spp. Despite a close resemblance between Picea and Larix spp. seed FA compositions, principal component analysis indicates that the minor differences in seed FA compositions between the two genera are sufficient to allow a clear-cut individualization of the two genera. In both cases, the main FA is linoleic acid (slightly less than one-half of total FA), followed by pinolenic (5,9,12-18:3) and oleic acids. A maximum of 34% of total Δ5-olefinic acids is reached in L. sibirica seeds, which appears to be the highest value found in Pinaceae seed FA. This apparent limit is discussed in terms of regio- and stereospecific distribution of Δ5-olefinic acids in seed triacylglycerols. Regarding the single species of Pseudotsuga analyzed so far (P. menziesii), its seed FA composition is quite distinct from that of the other two genera, and in particular, it contains 1.2% of 14-methylhexadecanoic (anteiso-17:0) acid. In the three genera studied here, as well as in most Pinus spp., the C18Δ5-olefinic acids (5,9-18:2 and 5,9,12-18:3 acids) are present in considerably higher amounts than the C20Δ5-olefinic acids (5,11-20:2 and 5,11,14-20:3 acids).

The distribution profiles of individual trans- as well as cis-18∶1 isomers from the fat prepared from the hump adipose tissue and the milk from Camelus dromedarius (the single-humped Arabian species) are described. Gas-liquid chromatography on two capillary columns with different polarities and lengths were used for this purpose in combination with argentation thin-layer chromatography. A comparison of the profiles established is made with that of true ruminant fats. In the fats from the dromedarius as well as from true ruminants, the trans-18∶1 isomers have their ethylenic bonds in all positions between Δ4 and Δ16. The prominent trans isomer is the 11–18∶1 (vaccenic) acid in all species, and the complete distribution profiles are quite similar. Concerning the cis isomers, the prominent isomer is oleic acid, followed by cis-vaccenic acid, as in true ruminant fats. Other cis isomers encompass the Δ6–8 and the Δ12 to Δ15 isomers. Camelidae (suborder Tylopoda) and Bovidae (suborder Ruminantia) have evolved independently since the Eocene, that is for approximately 50 million years. Despite this considerable period, and the profound differences in anatomy, morphology, physiology, ecological and dietary habits between the extant species of these suborders, the rumen microflora has continued to synthesize the same trans- and cis-octadecenoic acid isomers, in comparable proportions, at least as deduced from their composition profiles. We conclude that the trans-18∶1 acid profile is not intrinsically species-dependent, but it can be affected by the nature and the proportions of dietary unsaturated fatty acids that themselves depend on the feed, and that may be species-specific.

The trans- as well as the cis-18∶1 isomer profiles were established in cow, goat, and ewe cheese fats, with the assumption that these are representative of the corresponding milks. Argentation thin-layer chromatography was combined with low-temperature high-resolution gas-liquid chromatography on 100-m highly polar capillary columns, thus adding precision to earlier data for these species. Despite differences in the absolute content of trans-18∶1 isomers between species, the relative profiles were essentially similar. Except for the minor trans Δ6–Δ8 group, all trans-18∶1 isomers with their ethylenic bonds between positions Δ4 and Δ16 (including the resolved critical pair Δ13/Δ14) were separated and quantitated individually. As expected, vaccenic (trans Δ9−18∶1) acid was the main isomer, accounting for as much as 37 to 50% of the total fraction. It was observed that the goat trans-18∶1 isomer profile was usually rather close to that of cows in winter (barn feeding), whereas that of the ewe shows a seasonal dependence. The trans-18∶1 profile of ewe milk fats from this study resembles that of cows in the transition period between winter and summer (pasture) feeding. Regarding the cis-18∶1 acid fraction, two isomers (oleic and cis-vaccenic acids) accounted for ca. 97% of that fraction for the three species, with the cis-Δ12 isomer ranked third. The analytical procedure employed here appears a convenient alternative to oxidative-based procedures (generally ozonolysis), taking less time and alleviating some draw-backs of the latter procedure.

Dibutyroyl derivatives of monoacylglycerols (DBMAG) from conifer seed oil triacylglycerols (TAG) were prepared by partial deacylation of TAG with ethylmagnesium bromide followed by diesterification with n-butyryl chloride. The resulting mixtures were analyzed by gas-liquid chromatography (GCL) with 65% phenylmethyl silicon open tubular fused-silica capillary column operated under optimal conditions and separated according to both their fatty acid structures and their regiospecific distribution. Seed oils of 18 species from 5 conifer families (Pinaceae, Taxaceae, Cupressaceae, Cephalotaxaceae, and Podocarpaceae) were analyzed. The chromatograms showed a satisfactory resolution of DBMAG containing palmitic (16∶0) stearic (18∶0), taxoleic (cis-5, cis-9 18∶2), oleic (cis-9 18∶1), cis-vaccenic (cis-11 18∶1), pinolenic (cis-5, cis-9, cis-12 18∶3), linoleic (cis-9, cis-12 18∶2), α-linolenic (cis-9 cis-12, cis-15 18∶3), and an almost baseline resolution of DBMAG containing gondoic (cis-11 20∶1), cis-5, cis-11 20∶2, sciadonic (cis-5, cis-11, cis-14 20∶3), dihomolinoleic (cis-11 cis-14 20∶2), juniperonic (cis-5, cis-11, cis-14, cis-17 20∶4), and dihomo-α-linolenic (cis-11, cis-14, cis-17 20∶3) acids. We have observed that results for Pinus pinaster and P. koraiensis seed oils obtained with this new simple method compared favorably with literature data established with other usual regiospecific analytical techniques. Δ5-Olefinic acids are esterified mainly at the external positions of the glycerol backbone in all cases, in agreement with data obtained by other methodologies allowing validation of the GLC regiospecific method. To date, 45 gymnosperm species (mostly Coniferophytes) from 21 genera belonging to 9 families have been analyzed, all of them showing a definite enrichment of Δ5-olefinic acids in the external positions of TAG. These fatty acids (FA), with one exception only, represent between-2 and 8% of FA esterified to the internal positions. For some species, i.e., P. koraiensis and P. pinaster, this asymmetrical distribution was established by at least three analytical procedures and confirmed by stereospecific analysis of their seed TAG.

Maritime pine (Pinus pinaster)-seed oil contains two Delta5 unsaturated polymethylene interrupted fatty acids (all cis-5,9, 12-18:3 and all cis-5,11,14-20:3 acids) one of which resembles eicosapentaenoic acid. The goal of the present study was to test whether maritime pine-seed oil consumption affects HDL and apolipoprotein (Apo) A-I levels as well as the ability of serum to promote efflux of cholesterol from cultured cells. To this end, wild type (WT) non-transgenic mice and transgenic mice expressing human ApoA-I (HuA-ITg) were fed on isoenergetic diet containing either 200 g maritime pine-seed oil/kg or 200 g lard/kg for 2 weeks. WT and HuA-ITg mice fed maritime pine-seed oil had lower cholesterol, HDL-cholesterol, LDL-cholesterol and HuA-ITg mice had lower human ApoA-I than those fed lard. The differences in cholesterol (P < 0.0001) and HDL-cholesterol (P < 0.003) levels between mice fed on the two diets were more pronounced in the HuA-ITg than in the WT mice. The ability of HuA-ITg serum to promote cholesterol efflux in cultured cells was greater (P < 0.008) than that of WT animals. However, the maritime pine-seed oil diet was associated with lower (P < 0.005) in vitro cholesterol efflux ability than the lard diet in both mice genotypes. This suggests a negative effect of the maritime pine-seed oil on reverse cholesterol transport. Cholesterol efflux was correlated with serum free or esterified cholesterol and phospholipid levels. The slope of the regression line was smaller in the HuA-ITg than in the WT mice indicating that overexpression of human ApoA-I reduces the negative impact of maritime pine-seed oil on cholesterol efflux. In conclusion, maritime pine-seed oil diet lowers HDL-cholesterol and diminishes in vitro cholesterol efflux. This potentially detrimental effect is attenuated by overexpression of human ApoA-I in mice.

Low-temperature gas-liquid chromatography (GLC) was applied to study the distribution profiles of isomeric trans-and cis-hexadecenoic acids in ruminant (cow, goat, and ewe) milk fat after their fractionation by argentation thin-layer chromatography (Ag-TLC). The fat was extracted from cheeses (12 samples of each species), the most common foods made with goat and ewe milks. The predominant trans-16∶1 isomer is palmitelaidic acid (the Δ9 isomer), but it does not exceed one-third of the total group, which itself represents 0.17% (cow), 0.16% (goat), and 0.26% (ewe) of the total fatty acids. The trans-Δ3 16∶1 isomer, which is reported for the first time in ruminant lipids and which likely comes from the animals' feed, is present at a level of ca. 10% of the trans-16∶1 acid group. Otherwise, all isomers with their ethylenic bond between positions Δ4 and Δ14 are observed in the three species studied, roughly showing the same relative distribution pattern. Quantitatively, the trans-16∶1 isomers only represent ca. 5% of the sum of the trans-16∶1 plus trans-18∶1 isomers, and they appear of little importance in comparison. It is inferred from this and recent studies that some previously reported data that were established for consumption assessments dealt in fact mainly with iso-17∶0 acid, which was confused with (and added to) trans-Δ9 (palmitelaidic) acid; consequently, these results were large overestimates. Regarding the cis-16∶1 acids, the Δ9 isomer is the prominent constituent as expected, but the second-most important isomer is the Δ13 isomer. It does not appear that trans-16∶1 isomers are from ruminant milk fats of great nutritional importance as compared with trans-18∶1 isomeric acids. As for trans-18∶1 isomers, the combination Ag-TLC/GLC is a necessary procedure to quantitate trans-16∶1 acids accurately and reliably. Ag-TLC allows removal of interfering branched 17∶0 acids and cis-16∶1 acids, and low-temperature GLC permits an accurate measurement of all individual isomers most of which with baseline resolution.

The goal of this study was to compare the lipid lowering properties of maritime pine and fish oils in apolipoprotein E-deficient (KOE) mice, an animal model of hyperlipidemia. KOE mice were supplemented with either lard, fish or maritime pine oil (10% w/w) for one month. Compared to lard, fish and maritime pine oils decreased cholesterol (−31% and −52% respectively) and phospholipid (−41 and −52%) levels and increased triglyceride (+182% and +123%) levels. These lipid changes resulted in an enrichment in triglycerides and a depletion in cholesterol of VLDL+IDL plasma fraction as compared to lard-fed mice. These findings suggest that VLDL-triglyceride lipolysis is impaired in KOE mice fed fish or maritime pine oil.