Esterified alkan-1-ols and alkan-2-ols in barley epicuticular wax

The epicuticular wax on all barley organs is characterized by the presence of long chain esters which have alkan-1-ols as their alcohol moiety (mainly C₃₈−C₄₈). A second type of long chain ester in which alkan-2-ols serve as the alcohol moiety has been identified in the wax from all organs except the awns and leaf blades (mainly C₃₃−C₃₅). Utilizing Silica Gel H column chromatography, a 95% separation of the two ester types was achieved. Unlike alkan-1-ols, the alkan-2-ols (primarily C₁₃ and C₁₅) do not occur free in the wax. Esters isolated from spike minus awn wax consisted of 62% alkan-2-ol and 38% alkan-1-ol containing esters. The isomeric composition of each ester was determined with the aid of gas liquid chromatography-mass spectrometry. In the mass spectra of the alkan-2-ol containing esters, mass ions were absent and the relative intensities of the RCO₂H₂ ⁺, RCO₂H⁺, [R′-1]⁺, and RCO⁺ ions were markedly different from those characteristic for alkan-1-ol containing esters. Since esterified alkan-2-ols occur only in those waxes having β-diketones, a close biosynthetic relationship between these two lipid classes is suggested.     

Regioisomers of octanoic acid-containing structured triacylglycerols analyzed by tandem mass spectrometry using ammonia negative ion chemical ionization

Tandem mass spectrometry based on ammonia negative ion chemical ionization and sample introduction via direct exposure probe was applied to analysis of regioisomeric structures of octanoic acid containing structured triacylglycerols (TAG) of type MML, MLM, MLL, and LML (M, medium-chain fatty acid; L, long-chain fatty acid). Collision-induced dissociation of deprotonated parent TAG with argon was used to produce daughter ion spectra with appropriate fragmentation patterns for structure determination. Fatty acids constituting the TAG molecule were identified according to [RCO₂]⁻ ions in the daughter ion spectra. With the standard curve for ratios of [M-H-RCO₂H-100]⁻ ions corresponding to each [RCO₂]⁻ ion, determined with known mixtures of sn-1/3 and sn-2 regioisomers of structured TAG, it was possible to determine the proportions of different regioisomers in unknown samples. The method enabled quantification of MML- and MLM-type structured TAG. In the case of MLL- and LML-type TAG, it was possible to determine the most abundant regioisomer in the unknown mixture and estimate the proportions of regioisomers when there were more than 50% MLL-type isomers in the mixture.     

Compositional analysis of natural wax ester mixtures by tandem mass spectrometry

Tandam mass spectrometry is particularly suited for the analysis of complex, natural wax ester mixtures R₁-CO₂-R₂. Reduction of the mixture with deuterium provides species that are separble (through mass spectrometry) based on the number of original double bonds. Chemical ionization with isobutane produces high yields of protonated molecular ions and very little further fragmentation. These ions are separated by the first mass filter and then dissociated through collisions with argon. The positively charged dissociation products are almost exclusively the protonated acid ions (R₁-CO₂ H₂)⁺ that can then be separated by the second mass filter before detection and quantitation. The technique overcomes many of the obstacles previously faced during wax ester analysis. Results from this method are compared with those obtained by previous work, and the isomer composition of a new wax ester oil, orange roughy oil, is given. *** DIRECT SUPPORT *** A03O2445 00003     

Differential scanning calorimetry index for estimating level of saturation in transesterified wax esters

Differential scanning calorimetry (DSC) thermograms of fatty esters can give valuable information on melting characteristics and heats-of-fusion enthalpy (ΔH). A series of jojoba liquid wax esters was constructed by transesterifying native jojoba oil with 5–50% completely hydrogenated jojoba wax esters. This series, when subjected to a standardized DSC tempering method with heating/cooling cycles, exhibited an excellent correlation for level of saturation based on area changes in endothermic ΔH. Endothermic events were recorded for native (ΔH_A) and completely hydrogenated (ΔH_C) jojoba wax esters. A third endotherm, ΔH_B, was observed when they were transesterified. Based on a multiple regression program, the best fit (R²=0.98) using ΔH data was: % saturation=16.847–0.162 (ΔH_A)+0.209 (ΔH_B)+0.600 (ΔH_C). Standard errors for predictions were approximately 1.045 at 0% saturation, 0.770 at 25% saturation, and 1.158 at 50% saturation. Endothermic events A, B, and C each represent the respective diunsaturated, mounounsaturated, and saturated contents of wax esters in the transesterified blends. This was verified by measuring the dropping points for both the native and completely hydrogenated wax esters. These findings provide an index which can predict the degree of saturation in transesterified wax ester blends and serves as a research tool in process and product developments. Presented at the 1995 AOCS Meeting, May 7–11, 1995, San Antonio, Texas. Retired.     

Analysis of sterol esters by capillary gas chromatography-electron impact and chemical lonization-mass spectrometry

Synthetic mixtures of C₄₀ to C₄₇ sterol esters in groups of 7 esters were effectively separated and analyzed by capillary gas chromatography-mass spectrometry. Ammonia chemical ionization of all 20 sterol esters analyzed at a source block temperature of 120 C yielded (M+NH₄)⁺ and (M+H-RCO₂H)⁺ ions of high abundance or as base peak, thereby indirectly indicating the molecular weights of the ester and the sterol and acid moieties. Ammonia CI spectra of all esters containing a Δ⁵-sterol moiety exhibited in addition to the above 2 ions an M+NH₄-RCO₂ H fragment. At a source block temperature of 150 C, M+H-RCO₂ H fragment was the base peak for all esters, and there was little or no indication of an (M+NH₄)⁺ adduct ion. Protonated molecules were not observed for any esters analyzed by methane or isobutane CI. Molecular ions of 3–14% intensity were obtained for only 3 of the esters analyzed by electron impact; they contained a Δ⁷-bond in the sterol nucleus, and the acid moiety was either saturated normal or branched chain or contained a single double bond. The base peak was a function of both the acid and sterol moieties of the sterol ester. The esters containing both saturated straight chain acid and saturated sterol moieties exhibited a base peak at m/z 215. The Δ⁵-sterol esters with saturated branched or straight chain acid moieties exhibited base peaks at M-RCO₂ H. Other ions also were of diagnostic value.     

Analysis of the polyethylene glycol glucosides and FA esters thereof by atmospheric-pressure ionization MS

Polyethylene glycol (PEG) glucosides (PEGG) and the PEGG esters of lauric acid were analyzed by atmospheric-pressure ionization MS (API-MS) with electrospray ionization. Straightforward mass characterization of the complex mixtures could be achieved without prior chromatographic separation. The constituents were identified on the basis of quasi-molecular ions. Individual components could be observed as protonated molecular ions [M+H]⁺ and/or as their NH₄ ⁺, Na⁺, or K⁺ adducts in positive ion mode. The mass spectrometric investigation showed that mixtures of PEGG consisted of monoglucoside, diglucoside, polyglucoside, and free PEG. The esterification product is a mixture of two types of nonionic surfactants: PEG-laurates and PEGG-laurates. The reasons for distortion of the quasi-molecular ion intensities and the stabilization of adduct ions were discussed. The rapid and highly sensitive API-MS analysis technique proposed here is well suited for direct characterization of complex mixtures and suitable for development as a routine analytical method.     

Physico‐chemical properties of wax esters synthesised from corresponding alcohols using hydrobromic acid and hydrogen peroxide action

Symmetrical wax esters were prepared directly from the C₁₄–C₂₂ alcohols using HBr and H₂O₂. Conversion of alcohol up to 98% was obtained. Physical properties such as melting point, refractive index, viscosity and specific gravity were determined for these wax esters at different temperatures. The physical properties of the synthetic wax esters were compared with those of some commercial samples of wax esters. The physical properties of the wax esters can be manipulated by starting with commercially available mixtures of alcohols.     

Application of selective ion monitoring to the analysis of molecular species of vegetable oil triacylglycerols separated by open-tubular column GLC on a methylphenylsilicone phase at high temperature

Analyses of the molecular species of authentic triacylglycerols and of soybean triacylglycerols, which were separated on a fused silica open-tubular column coated with a methylphenylsilicone gum stationary phase, were carried out by selective ion monitoring mass spectrometry. It was determined that peak assignments could be made by selecting certain characteristic ions with the same retention time on the SIM profile, that is, three ions of the type RCO⁺ corresponding to the fatty acyl residues (R₁CO⁺, R₂CO⁺ and R₃CO⁺) and the corresponding three M-acyl ions ([M-OCOR₁]⁺, [M-OCOR₂]⁺ and [M-OCOR₃]⁺ instead of the molecular ion. The yield of [RCO-1]⁺ and [RCO-2]⁺ and relating these to the unsaturated fatty acyl residues is inconvenient for an exact peak assignment. The SIM method was further applied to the peak assignment of the triacylglycerols from palm, cottonseed and safflower oils and certain new fatty acid combinations are proposed.     

Molecular analysis of intact preen waxes of Calidris canutus (Aves: Scolopacidae) by gas chromatography/mass spectrometry

The intact preen wax esters of the red knot Calidris canutus were studied with gas chromatography/mass spectrometry (GC/MS) and GC/MS/MS. In this latter technique, transitions from the molecular ion to fragment ions representing the fatty acid moiety of the wax esters were measured, providing additional resolution to the analysis of wax esters. The C₂₁−C₃₂ wax esters are composed of complex mixtures of hundreds of individual isomers. The odd carbon-numbered wax esters are predominantly composed of even carbon-numbered n-alcohols (C₁₄, C₁₆, and C₁₈) esterified predominantly with odd carbon-numbered 2-methyl fatty acids (C₇, C₉, C₁₁, and C₁₃), resulting in relatively simple distributions. The even carbon-numbered wax esters show a far more complex distribution due to a number of factors: (i) Their n-alcohol moieties are not dominated by even carbon-numbered n-alcohol moieties are not dominated by even carbon-numbered n-alcohols esterified with odd carbon-numbered 2-methyl fatty acids, but odd and even carbon-numbered n-alcohols participate in approximately equal amounts; (ii) odd carbon-numbered methyl-branched alcohols participate abundantly in these wax ester clusters; and (iii) with increasing molecular weight, various isomers of the 2,6-, 2,8-, and 2,10-dimethyl branched fatty acids also participate in the even carbon-numbered wax esters. The data demonstrate that there is a clear biosynthetic control on the wax ester composition although the reasons for the complex chemistry of the waxes are not yet understood.     

Identification of steroids by chemical ionization mass spectrometry

Chemical ionization (CI) mass spectra of various natural and synthetic steroids have been studied using methane, isobutane, ammonia, trideuterioammonia and hydroxy anion as reagent gases. The CI spectra of steroids give simple and well characterized ions, which provide information about molecular weight as well as functionalities in the molecules. Trideuterioammonia exchanges rapidly with active hydrogens (e.g., OH, SH, COOH, NH₂) in steroid molecules in the CI reaction and thus provides a convenient means of active hydrogen determination by mass spectrometry. Application of various CI processes to the analysis of steroids and conjugates have been made. Low levels of hydroxycholesterols in biological samples and in cholesterol autoxidation products were identified by the 4 ion patterns, [M+NH₄]⁺, [M−OH+NH₃]⁺, [M−OH]⁺ and [M−H₂ O−OH]⁺, in ammonia CI. The position of hydroxy functions in the cholesterol side chain can be identified from the methane CI of hydroxycholesterol trimethylsilyl (TMS) derivatives. Sterol carboxylic esters can be identified as the ammonium adduct ion of the intact molecule, [M+NH₄]⁺, in ammonia CI. Isobutane and hydroxy anion CI spectra of the steroid esters give abundant ion fragments of both steroids and carboxylic acid moieties. Identification of free bile acids and steroid glycosides without derivatization is also feasible with the CI process when ammonia is used as reagent gas.     

Fast atom bombardment and tandem mass spectrometry of phosphatidylserine and phosphatidylcholine

Fast atom bombardment (FAB) desorption of phosphatidylserine and various phosphatidylcholines produces a limited number of very informative negative ions. Especially significant is the formation of (M-H)⁻ ions for phosphatidylserine, a compound which does not yield informative high mass ions by other ionization methods. Phosphatidylcholines of not yield (M-H)⁻ ions but instead produce three characteristic high mass ions, (M-CH ₃ ⁺ _⁻, [M-HN(CH₃) ₃ ⁺ ]⁻ and [M-HN(CH_{3 3} ⁺ -C₂H₂]⁻. Both classes of lipids also yield anions attributed to the carboxylate components of these complex lipids. FAB desorption in combination with collisional activation allows for characterization of fragmentation and determination of structural features. Collisional activation of the carboxylate anion fragments from the complex lipids is especially informative. Structural characterization of the fatty acid chain can be achieved as the released saturated carboxylate anions undergo a highly specific 1,4-elimination of H₂, which results in the losses of the elements of CH₄, C₂H₆, C₃H₈...in a fashion entirely consistent with the chemistry of carboxylate anions desorbed from free fatty acids. These C_nH_2n+2 losses begin at the alkyl terminus and progress along the entire alkyl chain. Modified fatty acids undergo a similar fragmentation; however, the modification affects the series of C_nH_2n+2 losses in a manner which permits determining the type of modification and its location on the fatty acid chain.     

Enzyme hydrolysis of babassu oil in a membrane bioreactor

This work deals with the enzymatic hydrolysis of babassu oil by immobilized lipase in a membrane bioreactor using unmixed aqueous and lipid streams. The experimental work was carried out in a flat plate membrane module with two different membranes: hydrophobic (nylon) and hydrophilic [mixed cellulose esters (MCE)], with different nominal pore sizes ranging from 0.10 to 0.65 μm. Candida cylindracea lipase was adsorbed on the membrane surface area, and the reactor was operated in batch mode. The initial enzymatic rate increased from 80 to 150 μmol H⁺/min when the organic phase velocity increased from 1.0×10⁻³ to 3.0×10⁻³ m/s, indicating that mass transfer in that phase was the process-limiting step. Calcium ions had a marked effect on immobilized lipase activity, increasing around twofold the lipolytic activity. Long-term experimental runs showed that the immobilized lipase remained stable for at least 8 d. The values for immobilized protein and maximal productivities observed for 0.45 μm membranes were: 1.01 g/m² and 193 μmol H⁺/m²·s for MCE membrane and 0.78 g/m² and 220 μmol H⁺/m²·s for nylon membrane. The productivities obtained are among the highest values reported in the technical literature.     

Preparation, separation, and confirmation of the eight geometrical cis/trans conjugated linoleic acid isomers 8,10-through 11,13–18∶2

Conjugated linoleic acid (CLA) mixtures were isomerized with p-toluenesulfinic acid or I₂ catalyst. The resultant mixtures of the eight cis/trans geometric isomers of 8,10-, 9,11-, 10,12-, and 11,13-octadecadienoic (18∶2) acid methyl esters were separated by silver ion-high-performance liquid chromatography (Ag⁺-HPLC) and gas chromatography (GC). Ag⁺-HPLC allowed the separation of all positional CLA isomers and geometric cis/trans CLA isomers except 10,12–18∶2. However, one of the 8,10 isomers (8cis, 10trans-18∶2) coeluted with the 9trans,11cis18∶2 isomer. There were differences in the elution order of the pairs of geometric CLA isomers resolved by Ag⁺-HPLC. For the 8,10 and 9,11 CLA isomers, cis,trans eluted before trans,cis, whereas the opposite elution pattern was observed for the 11,13–18∶2 geometric isomers (trans,cis before cis,trans). All eight cis/trans CLA isomers were separated by GC on long polar capillary columns only when their relative concentrations were about equal. Large differences in the relative concentration of the CLA isomers found in natural products obscured the resolution and identification of a number of minor CLA isomers. In such cases, GC-mass spectrometry of the dimethyloxazoline derivatives was used to identify and confirm coeluting CLA isomers. For the same positional isomer, the cis,trans consistently eluted before the trans,cis CLA isomers by GC. High resolution mass spectrometry (MS) selected ion recording (SIR) of the molecular ions of the 18∶1 18∶2, and 18∶3 fatty acid methyl esters served as an independent and highly sensitive method to confirm CLA methyl ester peak assignments in GC chromatograms obtained from food samples by flame-ionization detection. The high-resolution MS data were used to correct for the nonselectivity of the flame-ionization detector.     

The electrochemical hydrogenation of edible oils in a solid polymer electrolyte reactor. I. Reactor design and operation

A new electrochemical method has been devised and tested for the moderate temperature/atmospheric pressure hydrogenation of edible oils, fatty acids, and fatty acid methyl esters. The method employed a solid polymer electrolyte (SPE) reactor, similar to that used in H₂/O₂ fuel cells, with water as the source of hydrogen. The key component of the reactor was a membrane-electrode-assembly, composed of a RuO₂ powder anode and either a Pt-black or Pd-black powder cathode that were hot-pressed as thin films onto the opposing surfaces of a Nafion cation-exchange membrane. During reactor operation at a constant applied current, water was back-fed to the RuO₂ anode, where it was oxidized electrochemically to O₂ and H⁺. Protons migrated through the Nafion membrane under the influence of the applied electric field and contacted the Pt or Pd cathode, where they were reduced to atomic and molecular hydrogen. Oil was circulated past the back side of the cathode and unsaturated triglycerides reacted with the electrogenerated hydrogen species. The SPE reactor was operated successfully at a constant applied current density of 0.10 A/cm² and a temperature between 50 and 80°C with soybean, canola, and cottonseed oils and with mixtures of fatty acids and fatty acid methyl esters. Reaction products with iodine values in the range of 60–105 were characterized by a higher stearic acid content and a lower percentage of trans isomers than those produced in a traditional hydrogenation process.     

The mass spectrometry of iso and anteiso monoenoic fatty acids

The normal, iso, and anteiso Δ⁸- and Δ⁹-17:1 fatty acid methyl esters were synthesized and their electron impact-induced fragmentation was studied by mass spectrometry. The mass spectra of the preterminal branched monoenoic fatty acid methyl esters present characteristic fragment ions, now understood to be indicative of the position of the methyl group. These fragment ions are in the iso compound m/e 227 [M-55]⁺, m/e 195 [M-87]⁺, and m/e 177 [M-105]⁺, while in the anteiso compound these fragments are shifted by 14 mass units to m/e 213, m/e 181, and m/e 163. The 15-D-iso Δ⁸- and Δ⁹-17:1 methyl esters were synthesized because the characteristic fragment ions in the methyl branched compounds indicated a key role of the tertiary hydrogen atom in the rearrangement process. A fragmentation mechanism consisting of a double bond migration triggered by the tertiary hydrogen and an allylic cleavage assuming a displacement mechanism is proposed.     

Incorporation of oxygen-18 into secondary alcohols of grasshopperMelanoplus sanguinipes

Incorporation of¹⁸O₂ and H₂ ¹⁸O into the secondary alcohol moiety of wax esters in the grasshopperMelanoplus sanguinipes was determined by mass spectrometry. Results of this study show that oxygen-18 from¹⁸O₂ was incorporated into the secondary alcohol, whereas no incorporation of oxygen-18 from H₂ ¹⁸O was detected. The data suggest that the reaction, which hydroxylates n-alkanes at or near the center of the carbon chain, involves a mixed function oxidase type enzyme.     

Synthesis of borosilicalite-1 with more than four boron per unit cell from fluoride containing media

More than four boron per unit cell has been introduced into the framework of silicalite-1, using fluorine containing media. The initial gels were of composition 9MF–xH₃BO₃–10SiO₂–1.25TPABr–330 H₂O with M = NH₄, Na, K and Cs and x = 0.1–10. The syntheses were carried out in hydrothermal conditions at 170°C. The amount of incorporated TPA⁺ ions remains quasi constant (3.5–3.8/u.c.) up to 4 B/u.c., while it decreases with increasing boron content. The amount of tetrahedral B/u.c. can be as high as 8 in presence of K⁺ or Cs⁺ ions in the as-synthesized samples. It is observed that the preferential countercations to framework negative charges related to the presence of tetrahedral boron, [SiOB]⁻, are TPA⁺, K⁺ and Cs⁺ ions. It is interpreted, that the −4.0 ppm versus BF₃.OEt₂ NMR line stems from tetrahedral framework boron, while the −2.9 ppm NMR line represents both extraframework and/or tetracoordinated deformed framework boron in the structure.     

Effect of potassium ion on the stability and release rate of hydrogen peroxide encapsulated in silica hydrogels

Hydrogen peroxide (H₂O₂) is encapsulated in silica hydrogels using sol‐gel method and the effects of the K⁺ : Na⁺ ion ratio on gelation time, hydrogel structure, stability, and release rate of H₂O₂ were investigated. As the amount of K⁺ ions increased relative to the amount of Na⁺ ions at the same pH, the gel structure became less compact and the pore diameter increased. Hydrogen peroxide retention values up to 90 and 80% were observed at the end of 7 and 20 days, respectively, in the presence of K⁺ ions at low pH values when the initial H₂O₂ concentration was 19.9 wt %. Release rate of hydrogen peroxide decreased with decreasing pH for the two K⁺ : Na⁺ ion ratios studied. This work presents an environmentally friendly, low cost, and easy to scale up method to increase the stability of high initial concentrations of H₂O₂ at room temperature and customize the release rate. © 2016 American Institute of Chemical Engineers AIChE J, 63: 409–417, 2017     

Kinetics of Ion Formation in the Volumetric Reaction of Methane with Air

The formation of ions in the volumetric reaction of methane and hydrogen with air is analyzed. In methane–air mixtures, the highest concentrations are observed for NO⁺, NO₃ ^–, CO₃ ^–, CO₄ ^–, OH^–, and NO₂ ^– ions. In hydrogen–air mixtures, maximum concentrations are characteristic for NO⁺, OH^–, H₃O⁺, O^–, and O₂ ^– ions. In both rich and lean mixtures after ignition there is a long time interval during which the ion concentrations are far from equilibrium. The duration of this interval and the ion concentrations in it depend on the initial parameters of the mixture and the air–fuel ratio. Key words: volumetric reaction of methane with air, ion-molecular reactions, kinetics, ions.     

Adsorption and Diffusion of VO2+ and VO2 + across Cation Membrane for All‐Vanadium Redox Flow Battery

A method based on a selectivity coefficient and the Nernst‐Planck equation is proposed to determine diffusion coefficients of vanadium ions across a cation exchange membrane in VO²⁺/H⁺ and VO₂ ⁺/H⁺ systems. This simplified method can be applied to high concentrations of vanadium ions. Three cation exchange membranes were studied. The logarithmic value of the selectivity coefficient was linearly dependent on the molar fraction of vanadium ions in solution. The diffusion coefficient of vanadium ions decreased with decreasing water content. The membrane with the lowest diffusion coefficient was selected as a battery separator and showed the lowest capacity loss of the studied membranes.