Lipase-catalyzed synthesis of lesquerolic acid wax and diol esters and their properties

Lesquerolic acid was and α,Ω-diol esters were synthesized via immobilizedRhizomucor miehei lipase-(Lipozyme) catalyzed esterification of lesquerolic acid and alcoholysis of lesquerella oil. For each wax ester synthesis, when alcohol substrate was present at a slight (ca. 20%) stoichiometric excess and water content was kept low, over 94% of the hydroxy acyl groups were esterified. The extent of reaction and the ratio of monoester to diester produced for α,Ω-diol reactions was controlled by the solubility of diol in the medium. This latter quantity increased as alcoholysis proceeded due to the formation of partial glycerides and monoesters, which increased the polarity of the medium. Alcoholysis reactions were significantly slower when the medium diol content was above saturation. As the diol chainlength increased, diol solubilization decreased, the ratio of monoester to diester decreased, and the extent of hydrolysis increased. Alcoholysis reactions involving either fatty alcohols or diols suffered from acyl migration, which lowered the purity of lesquerolic acid esters. Several lesquerolic acid esters, synthesized on a preparative scale and purified via column chromatography, were evaluated for their properties: density, viscosity, and melting point. Potential applications for lesquerolic acid esters are discussed.     

Determination of unsaturated fatty acid composition by high-resolution nuclear magnetic resonance spectroscopy

High-resolution nuclear magnetic resonance (NMR) spectroscopy provides useful data for analyzing fatty acid compositions of edible vegetable oils. Quantitation of each fatty acid was carried out by evaluation of particular peaks. According to the ¹H NMR method, terminal methyl protons, divinyl protons, and allyl protons are useful to calculate linolenic acid, linoleic acid, and oleic acid, respectively. The ω-2 carbon, divinyl carbon, and allylic carbons were used for calculation of these acids by the ¹³C NMR method. Compositional results obtained by NMR coincided well with those of the conventional gas chromatography (GC) method. Results from ¹³C NMR were in better agreement with those from GC than were the results obtained by the ¹H NMR method.     

Determination of unsaturated fatty acid composition by high-resolution nuclear magnetic resonance spectroscopy

High-resolution nuclear magnetic resonance (NMR) spectroscopy provides useful data for analyzing fatty acid compositions of edible vegetable oils. Quantitation of each fatty acid was carried out by evaluation of particular peaks. According to the ¹H NMR method, terminal methyl protons, divinyl protons, and allyl protons are useful to calculate linolenic acid, linoleic acid, and oleic acid, respectively. The ω-2 carbon, divinyl carbon, and allylic carbons were used for calculation of these acids by the ¹³C NMR method. Compositional results obtained by NMR coincided well with those of the conventional gas chromatography (GC) method. Results from ¹³C NMR were in better agreement with those from GC than were the results obtained by the ¹H NMR method.     

Proton NMR studies on concentrated aqueous sulfuric acid solutions and Nafion-H

Sulfuric acid containing limited amounts of water, H₂SO_4.nH₂O with 0.23≤n≤4, has been studied by ¹H broad-line NMR at 4 K and MAS NMR at room temperature. The broad-line NMR spectra indicate the formation of H₃O⁺ and HSO₄ ^- ions. H₂SO_4.2H₂O is correctly written as H₃O⁺HSO₄ ^-.H₂O. The results are compared with the Nafion- H/water system. This revised version was published online in July 2006 with corrections to the Cover Date.     

The peroxidic species generated by ozonolysis of oleic acid or methyl oleate in a carboxylic acid medium

The ozonolysis of oleic acid or methyl oleate in a carboxylic acid medium produces three major peroxidic species as well as aldehyde. These peroxidic compounds have been identified as 1-acyloxyalkyl-1-hydroperoxides, 1,2,4-trioxolanes, and bis(1-acyloxy-1-alkyl) peroxides. The bis(1-acyloxy-1-alkyl) peroxides have not been reported previously as oleic acid or methyl oleate ozonolysis products. A¹H nuclear magnetic resonance examination of the ozonization products of oleic acid or methyl oleate in carboxylic acids, as well as methanol and iso-octane, led to the identification of the peroxidic compounds and aldehyde.     

Niobium oxide acidity studied by proton broad-line NMR at 4 K and MAS NMR at room temperature

The quantitative study of the Brønsted acidity of niobic acid (Nb₂O₅·xH₂O) using broad-line¹H NMR at 4 K has been performed by interacting niobic acid, pretreated at 573 K under vacuum, with water molecules. The number of oxyprotonated species (H₃O⁺ and H₂O...HO species formed, unreacted acidic OH groups or excess H₂O molecules) deduced from the simulations of the broad-line¹H NMR spectra shows a continuous increase in the number of H₃O⁺ species with adsorbed water molecules. This increase may be due to a classical dilution effect or to a synergistic interaction between Brønsted and Lewis acid sites. These results are compared with those of some HY zeolites with or without framework defects.     

Solid-state NMR and FT-IR investigation of 12-tungstophosphoric acid on TiO2

The chemical and dynamic nature of the tungstophosphoric acid (TPA) species adsorbed on pressed, extruded, and powdered TiO₂ support was studied by ³¹P and ¹H solid-state NMR spectroscopy and diffuse reflectance FT-IR. From ³¹P NMR and FT-IR results the TPA appeared to be present in at least five forms on the titania surface: a bulk salt phase, two weakly bound intact Keggin species, a range of partially fragmented clusters such as the 11-“defect” Keggin ion, and a range of species formed by high or complete fragmentation of the Keggin ion. The relative amount of these species varied depending on the form of the support. Adsorption was incomplete on extruded titania resulting in bulk salt formation. There was almost complete adsorption on pressed titania pellets, yielding predominantly fragmented Keggin units, along with a small amount of bulk salt. However, complete adsorption (and fragmentation) without bulk salt formation was attained by impregnation of powdered TiO₂. The acidic nature of the catalysts and the degree of TPA dispersion were investigated by solid-state ¹H high-speed MAS-NMR. Pure TPA salt yielded resonances at about 6.5 ppm. The catalysts yielded acidic proton resonances at about 7–8 and 10–11.5 ppm. The broad resonance observed at 7–8 ppm is due to a dispersion of acidic sites on the surface. The intensity of the acidic resonance at around 11 ppm increased with adsorption effectiveness and could, therefore, be related to the formation of hydroxonium ions upon fragmentation of adsorbed Keggin ions. This revised version was published online in July 2006 with corrections to the Cover Date.     

Off-line coupling of high-performance liquid chromatography and 1H nuclear magnetic resonance for the identification of filbertone in hazelnut oil

A new procedure is presented for off-line coupling of high-performance liquid chromatography and proton nuclear magnetic resonance spectroscopy (¹H NMR) in hazelnut oil analysis. The optimization of some parameters affecting both the liquid chromatography preseparation step and the effective multiple-solvent suppression required for the NMR study enabled us to determine the presence in a hazelnut oil of (E)-5-methyl-hept-2-en-4-one (filbertone), a marker previously proposed to detect the adulteration of olive oil with hazelnut oil. The described procedure requires the filtration of the oil prior to its introduction into the chromatographic system and combines the advantages of providing sufficient sensitivity and selectivity with simple methodology and reduced sample handling.     

Synthesis of triglyceride estolides from lesquerella and castor oils

Triglyceride (TG) estolides were synthesized from the hydroxy moieties of lesquerella and castor oils with oleic acid. Complete esterification of the hydroxy oils was possible when a slight excess of oleic acid was employed (1 to 1.5 mole equivalents). The estolides could be formed in the absence of catalyst at 175 to 250°C under vacuum or a nitrogen atmosphere. The optimal reaction conditions were found to be under vacuum at 200°C for 12 h for lesquerella and 24 h for castor oil. The lesquerella esterification reaction was completed in half the time of the for castor and with lower equivalents of oleic acid due to the difunctional hydroxy nature of lesquerella TG compared to the trifunctional nature of castor TG. Interesterification or dehydration of the resulting estolides to conjugated FA was not a significant side reaction, with only a slight amount of dehydration occurring at the highest temperature studied, 250°C. Use of a mineral-or Lewis-acid catalyst increased the rate of TG-estolide formation at 75°C but resulted in the formation of a dark oil, and the reaction did not go to completion in 24 h. Estolide numbers (i.e., degree of estolide formation) for the reaction and characterization of the products were made by ¹H NMR and ¹³C NMR. The decrease in the hydroxy methine signal at 3.55 ppm was used to quantify the degree of esterification by comparing this integral to the integral of the alpha methylene protons on the glycerine at 4.28 and 4.13 ppm.     

Identification of cyclopentenyl fatty acids by 1H and 13C nuclear magnetic resonance

Gorlic, chaulmoogric and hydnocarpic fatty acids, specific to the seed oil of the genus Hydnocarpus sp. (Flacourtiaceae), are determined only with difficulty by gas chromatography. These fatty acids were isolated in their methyl ester form by a combination of different chromatographic techniques (thin-layer chromatography/Ag⁺ and high-pressure liquid chromatography). The proton and carbon nuclear magnetic resonance analysis of these fatty acid methyl esters showed some characteristic signals of the cyclopentenyl ring. The presence of these signals in the proton and/or carbon nuclear magnetic resonance spectrum of an oil thus will allow us to confirm the presence of these cyclopentenyl fatty acids in lipids.     

Solid-state characterization of polyethylene reactor powders and their structural changes upon annealing

Polyethylene reactor powders prepared under different conditions were characterized using transmission electron microscopy, ¹H nuclear magnetic resonance and X-ray diffraction techniques. The molecular weight of the polyethylene reactor powders was around 1 × 10⁵. A unique domain morphology, quite different from the usual melt- or solution-crystallized lamellar structure, was observed, independent of polymerization temperature (T_poly). Annealing of reactor powders caused the aggregation of these crystalline domains, due to the significant molecular motion of the amorphous chains, before melting. The critical temperature was 20 °C higher than each T_poly, and corresponded to the temperature at the active catalyst site producing the chain growth. The morphologies of powders prepared at the lower T_poly contained smaller crystals that exhibited a constrained monoclinic form. In contrast, only usual orthorhombic crystals of larger size were found within the powder prepared at the higher T_poly. These results suggest that the competitive processes of chain propagation and crystal growth upon polymerization may lead to unique variations of the crystalline and amorphous phases, but with similar intermediate components in the phase that connects them.     

Heterogenization of 12-tungstophosphoric acid on stabilized zeolite Y

Topics in Catalysis - 12-tungstophosphoric acid (PW12) has been supported on dealuminated zeolite Y, containing a secondary pore system with the predominant pore radii of 15 Å. The interaction...     

Sequence analysis of poly(ethylene/1,4-cyclohexanedimethylene terephthalate) copolymer using H and C NMR

The triad-level sequence analysis of poly(ethylene/1,4-cyclohexanedimethylene terephthalate) copolymer was reported in a solvent system of o-chlorophenol/deuterated chloroform mixture (50/50 v/v) at 80 °C using 600 MHz ¹H NMR. The well-resolved alcoholic CH₂ proton peak of the glycol units was observed, which made the detailed sequence analysis possible. The peaks of the cis- and trans-forms of the 1,4-cyclohexanedimethylene glycol units were split into the triad sequence in the chain and could be assigned by a comparison of the spectra with those of homopolymers and by an additional two-dimensional heteronuclear multiple bond correlation observation. The triad sequence distributions centered on 1,4-cyclohexanedimethylene glycol units were determined, which was independent of the cis- and trans-forms of the units and controlled according to Bernoullian statistics.     

Effects of Green Liquor (GL) and Sodium Carbonate (SC) Pretreatment on Structural Characteristics of Wheat Stem Lignin

The content and structure of lignin have been considered as important factors that affect both pretreatment and enzymatic hydrolysis of lignocellulosic biomass. In this work, wheat stems (WS) were pretreated using mild alkali including green liquor (GL) and sodium carbonate (SC). The results indicate that GL pretreatment exhibits better delignification selectivity and higher enzymatic digestibility than SC pretreatment. Analysis of ¹H–¹³C HSQC NMR and FTIR on cellulolytic enzyme lignin (CEL) preparations isolated from untreated and pretreated WS also proves that a certain amount of lignin degrades which leads to a decrease of β-O-4′ linkages. Under mild alkaline conditions, more guaiacyl units in lignin are removed than syringyl units, which results in a higher condensation degree and S/G ratio of CELs isolated from GL- and SC-pretreated stems. Compared with p-coumarate structures, ferulates in lignin are more stable under mild alkaline conditions.     

The effect of fatty acid composition on the acrylation kinetics of epoxidized triacylglycerols

Epoxidized oils, epoxidized triacylglycerols, and epoxidized fatty acid methyl esters were made by reaction with performic acid formed in situ. The extent of epoxidation was ca. 95% for all of the epoxidized samples, as determined by ¹H nuclear magnetic resonance. The epoxidized samples were reacted with an excess of acrylic acid for different reaction times. The acrylation reaction was found to have a first-order dependence on the epoxide concentration for all oils, pure triacylglycerols, and fatty acid methyl esters. However, the rate constant of acrylation was found to depend on the composition of the epoxidized material. The acrylation rate constant for 9,10-epoxystearic acid was 96 L²/(mol²·min). The rate constant of acrylation for the epoxides on 9,10,12,13-diepoxystearic acid was 60 L²/(mol²·min). The acrylation rate constant for the epoxides on 9,10,12,13,15,16-triepoxystearic acid was 50 L²/(mol²·min). Thus, the rate constant of acrylation increased as the number of epoxides per fotty acid decreased. Multiple epoxides per fatty acid decrease the reactivity of the epoxides because of steric hindrance effects, and the oxonium ion, formed as an intermediate during the epoxyacrylic acid reaction, is stabilized by local epoxide groups. These results were used to derive an acrylation kinetic model that predicts rate constants from fatty acid distributions in the oil. The predictions of the model closely match the experimentally determined rate constants.     

NMR investigation of the miscibility of new antiplasticizers in densely cross-linked epoxy-amine resins

The behaviour of antiplasticized epoxy-amine networks was investigated by variable-temperature determinations of ¹H NMR free induction decays. Up to 50 °C, all antiplasticized resins exhibited a solid-like behaviour. At higher temperatures, resins containing the less polar additives were shown to be phase-separated, in contrast to systems containing polar additives. The temperature dependence of the phase composition of the resins, as detected by NMR, supports the conclusions previously deduced from the dynamic mechanical analysis (DMA) study: non- or slightly-polar antiplasticizer molecules are sharply phase-separated in highly cross-linked epoxy-amine networks cured extensively. The resulting morphology mainly consists in nano-scale aggregates of additives entrapped within the polymer matrix.     

Effect of time on the hydration and temperature-induced phase separation in aqueous polymer solutions. H NMR study

Dehydration during temperature-induced phase separation in D₂O solutions of poly(vinyl methyl ether) (PVME), poly(N-isopropylmethacrylamide) (PIPMAm) and poly(N-isopropylacrylamide) (PIPAAm) was followed from time dependences of NMR spin-spin relaxation times T₂ of HDO. Both the time characterizing the exclusion of the water from mesoglobules (manifested by the increase in T₂ values) and the induction period which precedes the increase in T₂ values, increased in the order PVME < PIPMAm < PIPAAm. For D₂O solutions of PIPMAm/PVME (or PIPMAm/PIPAAm) mixtures a direct connection between the state of the mesoglobules (hydrated or dehydrated) formed by the component with lower LCST (PVME, PIPAAm) and the temperatures of the phase transition of the PIPMAm component was established by NMR spectroscopy.     

Study on relationship between the concentration of hydrocarbon groups in heavy oils and their structural parameter from H NMR spectra

More than 60 heavy oils samples, belonging to the hydrogen adding tail oil, catalytic oil slurry, catalytic heavy oil slurry and catalytic heavy tar waxy oil, which taken from different processing units in Nanjing Refinery, are analysed by ¹H NMR and column chromatography. The analytical data of the heavy oils by two methods are compared and correlated, while good relationships between the specific area proton's percentage in ¹H NMR spectra and the contents of paraffinic and alicyclic hydrocarbons ((P+N)%), aromatic hydrocarbons (A%) are found. Our ¹H NMR method in calculating the amount of (P+N) and A in heavy oils proved fast, convenient and reliable.     

Brønsted acidity of amorphous silica–aluminas studied by 1H NMR

¹H broad-line (4 K) and MAS (room temperature) NMR have been used to study the acid strength of two amorphous silica–aluminas interacting or not with adsorbed water. The study is more difficult than for zeolites, because the acidic SiO(H)Al bridges are reversibly destroyed by dehydration. However, an acidity coefficient value (H₃O⁺ concentration per Brønsted acid site when one water molecule interacts with each Brønsted site) of 0.34±10%; has been determined. This value is equal to that obtained for H-faujasite and H-mordenite samples with Si/Al ratios high enough for maximum acid strength.     

The strong interaction between poly(vinyl chloride) and a new eco-friendly plasticizer: A combined experiment and calculation study

Hydrogenation has been proved to be an efficient way to remove the toxicity of phthalate plasticizer. However, other influences of this hydrogenation are still unknown. Here we chose di-2-ethylhexyl phthalate (DOP) and di(2-ethylhexyl) cyclohexane-1,2-dicarboxylate (DEHHP) to study the influence on interaction with poly(vinyl chloride) (PVC). By combining experiment and calculation, we found the interaction was stronger in PVC/DEHHP than in PVC/DOP. Low-Field ¹H NMR results showed that PVC chains could restrict much more DEHHP molecules than DOP. FTIR results showed that the interaction exists in form of hydrogen bonding complex, and it was stronger in PVC/DEHHP than in PVC/DOP system. Combined with FTIR results, theoretical calculation results revealed the three-center hydrogen bonded structure of the complex. Both the proportion and the binding energy of pre-complex in DEHHP are much larger than in DOP. Here, the hydrogenation-induced change of interaction was elucidated systematically and could be generalized to other phthalate plasticizers.