Lesquerolic Acid. A New Hydroxy Acid from Lesquerella Seed Oil<sup>1a</sup>

Smith, Craig R.; Wilson, T. L.; Miwa, Tamotsu; Zobel, Henning; Lohmar, R. L.; Wolff, I. A.

doi:10.1021/jo01066a067

Cited by 62 publications

(17 citation statements)

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“…Although this bias could be attributed to differential metabolism of the hydroxy fatty acids, the fact that both of these ratios follow the same trend within the series of Lesquerella variants (more hydroxylation for LFAH-N149I, less hydroxylation for LFAH-N149T; data in 9 by LFAH gave the expected products. Nonetheless, the available data indicate that the stereospecificity of the FAD2 variants is consistent with that of the characterized FAD2 (19), LFAH (20), and CFAH (21).…”

Section: Analysis Of Variant Fad2 Genes-as Illustrated Insupporting

confidence: 69%

“…The Lesquerella enzyme must also share this same stereospecificity, as the seed oil-derived lesquerolic acid retains the same optical rotation properties as ricinoleic acid derived from castor seed oil (20). The knowledge that these enzymes are highly homologous (1,2) and that the enzymes catalyze both desaturation and hydroxylation, just with differing product ratios, implies that these enzymes employ closely related catalytic mechanisms.…”

Section: Discussionmentioning

confidence: 99%

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Desaturation and Hydroxylation

Broadwater

Whittle

Shanklin³

2002

Journal of Biological Chemistry

156

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Exchanging the identity of amino acids at four key locations within the Arabidopsis thaliana oleate desaturase (FAD2) and the Lesquerella fendleri hydroxylase/ desaturase (LFAH) was shown to influence partitioning between desaturation and hydroxylation (Broun, P., Shanklin, J., Whittle, E., and Somerville, C. (1998) Science 282, 1315-1317). We report that four analogous substitutions in the FAD2 sequence by their equivalents from the castor oleate hydroxylase result in hydroxy fatty acid accumulation in A. thaliana to the same levels as for the wild-type castor hydroxylase. We also describe the relative contribution of these substitutions, both individually and in combination, by analyzing the products resulting from their expression in A. thaliana and/or Saccharomyces cerevisiae. Yeast expression showed that M324V, a change reachable by a single point mutation, altered the product distribution ϳ49-fold, and that residue 148 is also a predominant determinant of reaction outcome. Comparison of residues at position 148 of FAD2, LFAH, and the Ricinus oleate hydroxylase prompted us to rationally engineer LFAH-N149I, a variant with ϳ1.9-fold increase in hydroxylation specificity compared with that of wild-type LFAH. Control experiments showed that the wild-type Arabidopsis thaliana FAD2 desaturase has inherent, low level, hydroxylation activity. Further, fatty acid desaturases from different kingdoms and with different regiospecificities exhibit similar intrinsic hydroxylase activity, underscoring fundamental mechanistic similarities between desaturation and hydroxylation. For LFAH mutants the hydroxylation:desaturation ratio is 5-9-fold higher for 18-carbon versus 16-carbon substrates, supporting our hypothesis that substrate positioning in the active site plays a key role in the partitioning of catalytic specificity.Hydroxy fatty acids are unusual fatty acids that are incorporated into seed triacylglycerols in several species of plants, the best characterized being Ricinus communis (castor) and Lesquerella fendleri (1, 2). In both of these plants, an oleate hydroxylase enzyme catalyzes the hydroxylation chemistry that converts oleate (cis-9-octadecenoic acid, or 18:1⌬ 9 ) to rici- (1), and Lesquerella, LFAH (2), are closely related to the common plant oleate desaturase enzyme (FAD2), which converts oleate (18:1 ⌬ 9 ) into linoleate (18:2⌬ 9,12 ). Indeed, LFAH actually retains both hydroxylase and desaturase activity, indicating that these two oxidation reactions can be catalyzed by the same enzyme. Amino acid sequence alignments (Table I) of these two oleate hydroxylases with several oleate desaturases indicated that there are only a few conserved desaturase residues that are not conserved in the hydroxylases (3). These seven residues (Arabidopsis thaliana FAD2 residues 63, 104, 148, 217, 295, 322, and 324) 3 were replaced with the corresponding residues of LFAH, and the resulting enzyme (designated m7FAD2 in Ref.3) was found to be sufficient to convert the desaturase into a bifunctional desaturase/hydroxylase. ...

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Section: Analysis Of Variant Fad2 Genes-as Illustrated Insupporting

confidence: 69%

Section: Discussionmentioning

confidence: 99%

Desaturation and Hydroxylation

Broadwater

Whittle

Shanklin³

2002

Journal of Biological Chemistry

156

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“…The goal of the screening program was to find new or unusual kinds of oils that will not compete with vegetable oils [10]. The unique hydroxy fatty acids (HFA) from lesquerella seeds were identified [10][11][12] and the crop's potential for high yield was likewise recognized. During the 1960s when no Lesquerella species had been cultivated, it is reported that the original plant collectors of Lesquerella species used a combine method in deserts of Texas to collect large quantities of seed from wild populations for initial research activities [13].…”

Section: Introductionmentioning

confidence: 99%

“…Lesquerolic acid (14-hydroxy-eicosa-11-enoic, 14-OH-20:1) content in the seed oil of P. fendleri and other species is between 45 and 55 % of the total HFA [15]. Lesquerolic acid was first isolated and identified in P. fendleri's sister species P. lasiocarpa and P. lindheimeri [11]. The species P. lindheimeri has about 89 % lesquerolic acid content.…”

Section: Introductionmentioning

confidence: 99%

Germplasm Improvement to Develop Commercially Viable Lines of the New Oilseed Crop Lesquerella

Cruz

Dierig

2014

Handbook of Plant Breeding

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Lesquerella (Physaria fendleri) is a new oilseed crop that is being domesticated as an alternative crop for arid regions in the United States. As a member of the Brassica family, the species exhibits a high seed-oil content that can provide a source of hydroxy fatty acids for industrial use as source of bioenergy and by-products that can be utilized in livestock production. Germplasm evaluation and breeding activities on the crop have been done by the University of Arizona and the US Department of Agriculture (USDA). Lesquerella and other Physaria and Paysonia species have a substantial germplasm collection that is well characterized for phenotypic traits and oil profiles. There are several improved germplasm released by the USDA with higher oil content and seed yield, enhanced oil profile, abiotic stress tolerance, and harvest index which can be directly utilized for commercial production or used for crop improvement. Additional technologies that can aid breeding, such as molecular marker systems and genetic transformation systems, have been established. A few challenges remain to be surmounted for the crop to be commercialized. A continued concerted effort by public and private institutions may hasten the process of bringing this new crop to commercial production.

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“…analysis of the acidic oxidation products obtained from unsaturated fatty acids and esters has confirmed the quasi-quantitative oxidation t o predictable end products (5)(6)(7). This aspect has made the reagent highly successful in routine analysis of lipids (6)(7)(8)(9)(10) as well as in locating the position of double bonds in unknown or isomeric unsaturated fatty acids (6,7,(11)(12)(13)(14).…”

Section: Introductionmentioning

confidence: 99%

Permanganate–periodate Oxidation: Vi. The Oxidation of Various Aliphatic Compounds

Rudloff¹

1965

Can. J. Chem.

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A study was made of the reaction of the permangallateperiodate reagent with a wide variety of aliphatic alcohols, polyols, aldehydes, acids, oxy-acids, ketones, ethers, and esters. Saturated monols, ketones, and ethers, as well as acetic, pelargonic, pyruvic, lactic, and oxalic acids reacted only very slowly. Glycols, olefinic alcohols, and unsaturated acids were cleaved to give predictable end products. Activated alcohols and ethyl acetoacetate reacted a t relatively high rates. Formic, glyoxylic, lactic, and malonic acids as well as 1,3-propanediol and 2,5-hexane dione reacted extensively and diethyl tartrate consumed as much oxidant as did tartaric acid. The oxidation of tetrahydrofurfuryl alcohol gave succinic acid instead of the expected tetrahydro-2-furoic acid. Saturated mono-and di-carboxylic acids, 3-hydroxy propionic acid, yvalero lactone, and saturated esters were stable towards the reagent.

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Lesquerolic Acid. A New Hydroxy Acid from Lesquerella Seed Oil^1a

Abstract: A major constituent of Lesquerella lasiocarpa seed oil is characterized as (+)-14-hydroxy-cz's-l 1-eicosenoic acid. For convenience, it is called lesquerolic acid.

Cited by 62 publications

References 0 publications

Desaturation and Hydroxylation

Desaturation and Hydroxylation

Germplasm Improvement to Develop Commercially Viable Lines of the New Oilseed Crop Lesquerella

Permanganate–periodate Oxidation: Vi. The Oxidation of Various Aliphatic Compounds

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Lesquerolic Acid. A New Hydroxy Acid from Lesquerella Seed Oil1a

Abstract: A major constituent of Lesquerella lasiocarpa seed oil is characterized as (+)-14-hydroxy-cz's-l 1-eicosenoic acid. For convenience, it is called lesquerolic acid.

Cited by 62 publications

References 0 publications

Desaturation and Hydroxylation

Desaturation and Hydroxylation

Germplasm Improvement to Develop Commercially Viable Lines of the New Oilseed Crop Lesquerella

Permanganate–periodate Oxidation: Vi. The Oxidation of Various Aliphatic Compounds

Contact Info

Product

Resources

About

Lesquerolic Acid. A New Hydroxy Acid from Lesquerella Seed Oil^1a