Alkaline isomerization of methyl crepenynate

Methyl crepenynate (methyl-cis-9-octadecen-12-ynoate) is readily isomerized by potassium hydroxide in ethylene glycol to an 8,10,12-octadecatrienoic acid in good yield. A reaction carried out at 120C for 1 hr in 10% base is sufficient to convert the nonconjugated enyne system completely to conjugated triene systems. Presented at AOCS Meeting in New Orleans, 1964. A laboratory of the No. Utiliz. Res. & Der. Div., ARS, USDA.     

2-Hydroxyhexadecanoic and 8,9,13-trihydroxydocosanoic acid accumulation by yeasts treated with fumonisin B1

Fumonisin B₁ is a sphingolipid-like compound that enhances the accumulation of yeast sphingolipids and 2-hydroxy fatty acids. These lipids occur both as freely extractable and cell bound components in yeast fermentations. Both free and bound 2-hydroxy fatty acids produced byPichia sydowiorum NRRL Y-7130 were increased when fumonisin B₁ (50 mg/L) was added to the usual growth medium containing yeast extract/malt extract/peptone/glucose. Fumonisin-treated cultures contained 38 mg/L more 2-hydroxyhexadecanoic and 15 mg/L more 2-hydroxyoctadecanoic acids than did untreated cultures. By contrast, fumonisin inhibited the accumulation of free 8,9,13-trihydroxydocosanoic acid inRhodotorula sp. YB-2501 cultures, leading to 240 mg/L lower trihydroxy acid production than by untreated cultures.     

Empirical analysis of anticipatory standardization processes: a case study

The processes followed for developing anticipatory standards such as those for web services are still not well-understood. In spite of the openness of the process, there are few analyses that shed light on the roles that different participants play or the actions they engage in during the development of these standards. We analyze archival documents that capture development of SOAP, a core web service standard. Our analysis shows that participants spend a bulk of their time discussing technical issues, identifying action items, and engaging in discussion to reach consensus. These activities reveal prototypical roles that participants take on such as: Advocate, Architect, Bystander, Critic, Facilitator, Guru, and Procrastinator. Together, the findings support the existence of three clusters in standards development processes: design activities performed by Architects, sense-making activities performed by Critics, and managerial activities performed by Facilitators; along with the important activity of coordinating the work of multiple participants. We discuss implications of our findings and identify opportunities for future work.     

Predicting cetane numbers of n-alcohols and methyl esters from their physical properties

Cetane numbers (C#) for the homologous series of straight-chain, saturated n-alcohols, C₅−C₁₂ and C₁₄, were determined according to ASTM D 613. Measured C# ranged from 18.2–80.8 and increased linearly with carbon number (CN). Regression analyses developed equations that related various physical properties or molecular characteristics of these alcohols to calculated C#. The degree of relationship between measured and calculated C# was expressed as R². The decreasing order of the precision with which these properties correlated with C# was: boiling point (bp)>melting point (mp)>CN>heat of combustion (HG)>refractive index (n²⁰ _D)>density (d). This ranking was based upon R² (0.99–0.96) and the Average % error (2.8–7.2%). C# were also determined for straight-chain homologs of saturated methyl esters with CN of 6, 10, 12, 14, 16 and 18. C# ranged from 18.0–75.6 and increased curvilinearly with CN. Equations were also developed that related physical properties of these esters to C#. The precision with which these properties correlated with C# was: bp>viscosity (V)>heat of vaporization (HV)>HG>CN>surface tension (ST)>mp>n²⁰ _D>d. R² ranged from 0.99 for bp to 0.98 for d. Equations for the alcohols were linear or quadratic, while equations for the esters were linear, quadratic or cubic based upon statistical considerations that included a Student’s t-test. With related physical properties and these equations, accurate predictions of C# can be made for saturated n-alcohols and methyl esters.     

Biotransformation of saturated monohydroxyl fatty acids to 2-tetrahydrofuranyl acetic acid derivatives: Mechanism of formations and the biological activity of 5-n-hexyl-tetrahydrofuran-2-acetic acid

Transformation of 12-hydroxyoctadecanoic acid (12-HOA) to 5-n-hexyl-tetrahydrofuran-2-acetic acid (5-HTFA) byBacillus lentus NRRL B-14864 (B-14864) was carried out in the presence or absence of oligomycin, 2-bromooctanoic acid (2-BA), or sodium azide. In addition, several saturated and monounsaturated monohydroxyfatty acids, saturated monooxofatty acids, and monounsaturated fatty acid were used as substrates for transformation reactions by B-14864 or corynebacterium FUI-2. Methyl esters of the transformation products were analyzed by gas chromatography and gas chromatography/mass spectroscopy. Various γ-lactones and tetrahydrofuran fatty acid derivatives were conversion products when saturated monohydroxyfatty acids were used as substrates; the production of 5-HTFA from 12-HOA by B-14864 cells was completely inhibited in the presence of high concentration of oligomycin, 2-BA, or sodium azide; and fatty acid β-oxidation metabolic intermediates, 6-hydroxydodecanoic, 4-oxododecanoic, and 4-oxodecanoic acids were products when 12-HOA, 10-oxo-, and 12-oxooctadecanoic acids were used as substrates. Our results suggest that the production of 5-HTFA from 12-HOA by B-14864 was through the fatty acid β-oxidation pathway. Three-day-old driedfruit beetle pupae were topically treated with 5-HTFA to test for juvenile hormone activity, and 5-HTFA was found to possess juvenile hormone-like activity in pure form but not when it was diluted to 10%. Presented in part at the 37th West Central States Biochemistry Conference Annual Meeting, Columbia, Missouri, Oct. 1994.     

High oil- and polyphenol-producing species of the northwest

The examination of plant species for their potential as renewable sources of industrial raw materials, conducted at the Northern Regional Research Center, has been extended to include 110 species from North Dakota (ND), Colorado (CO), and Oregon (OR), U.S.A. Plant samples were collected and analyzed for yields of “oil,” “polyphenol,” “hydrocarbon” and crude protein as well as for botanical characteristics. Data are presented only for the relatively high-yielding species. Oil and hydrocarbon extracts of plants that yielded at least 3.0% oil (dry, ash-free, plant sample basis) and/or at least 0.4% hydrocarbon were analyzed for classes of constituents. Oils of such species were saponified to determine yields of fatty acids and unsaponifiable matter. Hydrocarbon was examined for the presence of rubber, gutta and/or waxes. Polyisoprenes were analyzed for average molecular weight and molecular weight distribution. Even when compared to about 1000 species previously analyzed in this program, seven of the species yielded high amounts of oil (7.1–11.1%) plus substantial amounts of polyphenol (10.0–19.7%). Of these, six are evergreen trees or shrubs and one is a nonwoody perennial. Another seven species yielded substantial amounts of oil (5.4–6.6%), of which five gave 17.1–24.7% polyphenol. The most notable oil-producing species wereJuniperus scopulorum (11.1%),Pinus albicaulis (10.1%),Pinus flexilis (9.3%),Pinus mugo (8.4%),Liatris punctata (8.0%) andJuniperus communis (7.8%). Crude protein contents for all 22 species were low (4.2%) to moderate (10.4%). Maximum hydrocarbon content for the 22 selected species reported was only 0.5%. The highest total amount of oil, polyphenol, hydrocarbon and crude protein was 38.9% forAcer ginnala. Data obtained in this study are discussed with respect to those from species previously analyzed in this program.     

Low-temperature properties of triglyceride-based diesel fuels: Transesterified methyl esters and petroleum middle distillate/ester blends

This work examines low-temperature properties of triglyceride-based alternate fuels for direct-injection compression-ignition engines. Methyl esters from transesterified soybean oil were studied as neat fuels and in blends with petroleum middle distillates (No. 1 or No. 2 diesel fuel). Admixed methyl esters composed of 5–30 vol% tallowate methyl esters in soyate methyl esters were also examined. Pour points, cloud points, and kinematic viscosities were measured; viscosities at cooler temperatures were studied to evaluate effects of sustained exposure. Low-temperature filterability studies were conducted in accordance with two standard methodologies. The North American standard was the low-temperature flow test (LTFT), and its European equivalent was the cold-filter plugging point (CFPP). With respect to cold-flow properties, blending methyl esters with middle distillates is limited to relatively low ester contents before the properties become preclusive. Under most conditions, cold-flow properties were not greatly affected by admixing the methyl esters with up to 30 vol% tallowate (before blending). Least squares analysis showed that both LTFT and CFPP of formulations containing at least 10 vol% methyl esters are linear functions of cloud point. In addition, statistical analysis of the LTFT data showed a strong 1:1 correlation between LTFT and CP. This result may prove crucial in efforts to improve low-temperature flow properties of alternate diesel fuels that contain methyl esters derived from triglycerides.     

Preparative chromatographic isolation of hydroxy acids fromLesquerella fendleri andL. gordonii seed oils

To conduct product development research onLesquerella seed oils, we explored methods to obtain >100 g quantities of lesquerolic (14-hydroxy-cis-11-eicosenoic) acid. Preliminary experiments with open-column silica gel chromatography showed thatL. fendleri oil could be separated into 3 triglyceride (TG) fractions. The first (10%) contained nonhydroxy 16-(13%) and 18-carbon acids (65% 18∶1,2,3). The second fraction (15%) contained monolesquerolins (39% lesquerolic acid). The major TG fraction (73%) was mainly dilesquerolins (66% lesquerolic acid) showing that a hydroxy acid-enriched TG oil was obtainable by this procedure. Silica gel chromatography easily separatedL. fendleri fatty acid methyl esters (FAME) into a hydroxy-free ester fraction (40–44%) consisting largely of 18∶1 (39%), 18∶2 (19%) and 18∶3 (31%), and a hydroxy ester fraction (56–60%) that was largely methyl lesquerolate (94%) with small amounts of auricolate (5%) (14-hydroxy-cis-11,cis-17-eicosadienoate) and traces of 18-carbon hydroxy esters. This process for isolating the hydroxy FAME ofLesquerella oil was scaled up 15-to 100-fold with a preparative high performance liquid chromatograph. Thirty-gram samples ofL. gordonii FAME were dissolved in eluting solvent, pumped onto the high performance liquid chromatography (HPLC) silica column and eluted with 97∶3 hexane/ethyl acetate. In an 8-hr period, up to 200 g of methyl lesquerolate could be obtained with a purity >98%, the only contaminants being methyl auricolate and methyl ricinoleate. Presented at the AOCS meeting in Phoenix, AZ, May 1988. The mention of firm names or trade products does not imply that they are endorsed or recommended by the U.S. Department of Agriculture over other firms or similar products not mentioned.     

Assessing and interpreting personality change and continuity in patients treated for major depression.

Structural, mean- and individual-level, differential, and ipsative personality continuity were examined in 599 patients treated for major depression assigned to 1 of 6 forms of a 6-month pharmaco-psychotherapy program. Covariation among traits from the Five Factor model remained invariant across treatment, and patients described themselves as slightly more extraverted, open to experience, agreeable and conscientious, and substantially more emotional stable after treatment. Trait changes were only to a small extent explained by changes in depression severity. There was evidence for differential, individual-level, and ipsative stability, with stable personality profiles in terms of shape and to a lesser extent in terms of scatter and elevation. Traits remain relatively stable, except for emotional stability, despite the depressive state and the psychopharmacological interventions. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

A novel compound, 7,10-dihydroxy-8(E)-octadecenoic acid from oleic acid by bioconversion

Sixty-two cultures from the Agricultural Research Service (ARS) Culture Collection and 10 cultures isolated from soil and water samples in Illinois were screened for their ability to convert agricultural oils to value-added industrial chemicals. A new compound, 7,10-dihydroxy-8(E)-octadecenoic acid (DOD), was produced from oleic acid at a yield of greater than 60% by bacterial strain PR3 which was isolated from a water sample in Morton, IL. To our knowledge, DOD has not been previously reported. The optimum time, pH and temperature for the production of DOD were 2 days, 7.0, and 30°C, respectively. The production of DOD is unique in that it involves hydroxylation at two positions and rearrangement of the double bond of the substrate molecule.