3.2.3. Hydroformylation 2467 3.2.4. Dimerization 2468 3.2.5. Oxidative Cleavage and Ozonolysis 2469 3.2.6. Metathesis 2470 4. Terpenes 2472 4.1. Pinene 2472 4.1.1. Isomerization: R-Pinene 2472 4.1.2. Epoxidation of R-Pinene 2475 4.1.3. Isomerization of R-Pinene Oxide 2477 4.1.4. Hydration of R-Pinene: R-Terpineol 2478 4.1.5. Dehydroisomerization 2479 4.2. Limonene 2480 4.2.1. Isomerization 2480 4.2.2. Epoxidation: Limonene Oxide 2480 4.2.3. Isomerization of Limonene Oxide 2481 4.2.4. Dehydroisomerization of Limonene and Terpenes To Produce Cymene 2481

Chemical Routes for the Transformation of Biomass into Chemicals

Iron Catalysis in Organic Synthesis

Antioxidant activity has been assessed in many ways. The limitation of many newer methods is the frequent lack of an actual substrate in the procedure. The combination of all approaches with the many test methods available explains the large variety of ways in which results of antioxidant testing are reported. The measurement of antioxidant activities, especially of antioxidants that are mixtures, multifunctional or are acting in complex multiphase systems, cannot be evaluated satisfactorily by a simple antioxidant test without due regard to the many variables influencing the results. Several test procedures may be required to evaluate such antioxidant activities. A general method of reporting antioxidant activity independent of the test procedure is proposed.

http://ucce.ucdavis.edu/files/datastore/608-46.pdf

Methods for testing antioxidant activity

Sonochemistry is the use of ultrasound to enhance or alter chemical reactions. Sonochemistry in the true sense of the term occurs when ultrasound induces “true” chemical effects on the reaction system, such as forming free radicals which accelerate the reaction. However, ultrasound may have other mechanical effects on the reaction, such as increasing the surface area between the reactants, accelerating dissolution, and/or renewing the surface of a solid reactant or catalyst. This comprehensive review summarizes several topics of study in the sonochemical literature, including bubble dynamics, factors affecting cavitation, the effects of ultrasound on a variety of chemical systems, modeling of kinetic and mass-transfer effects, the methods used to produce ultrasound, proposed cavitation reactors, and the problems of scaleup. The objective of this paper is to present a critical review of information available in the literature so as to facilitate and inspire future research in the field of sonochemistry.

Sonochemistry: Science and Engineering

Deep-fat frying produces desirable or undesirable flavor compounds and changes the flavor stability and quality of the oil by hydrolysis, oxidation, and polymerization. Tocopherols, essential amino acids, and fatty acids in foods are degraded during deep-fat frying. The reactions in deep-fat frying depend on factors such as replenishment of fresh oil, frying conditions, original quality of frying oil, food materials, type of fryer, antioxidants, and oxygen concentration. High frying temperature, the number of fryings, the contents of free fatty acids, polyvalent metals, and unsaturated fatty acids of oil decrease the oxidative stability and flavor quality of oil. Antioxidant decreases the frying oil oxidation, but the effectiveness of antioxidant decreases with high frying temperature. Lignan compounds in sesame oil are effective antioxidants in deep-fat frying.

https://onlinelibrary.wiley.com:443/doi/pdf/10.1111/j.1750-3841.2007.00352.x

Chemistry of deep-fat frying oils

This paper reviews our studies of fatty acid hydroperoxides, their secondary products and mechanisms for their formation in the context of some of their possible biological consequences. The uneven distribution of isomeric hydroperoxides in oxidized linolenate and photosensitized oxidized linoleate is related to the formation of hydroperoxy cyclic peroxides. Interest in the hydroperoxy mono-and bi-cycloendoperoxides from oxidized linolenate stems from their structural relationship to the prostaglandins. However, the biological activity of hydroperoxy cyclic peroxides formed by autoxidation has not yet been reported. Thermal decomposition studies of secondary lipid oxidation products show they are important precursors of volatile compounds. An acid-acetalation decomposition procedure establishes that 5-membered hydroperoxy cyclic peroxides and 1,3-dihydroperoxides are important precursors of malonaldehyde. This approach provides a more specific test than the thiobarbituric acid (TBA) color reaction to evaluate lipid oxidation products as sources of malonaldehyde and its biological effects due to crosslinking. A better understanding is needed of the biological effects of a multitude of lipid oxidation decomposition products other than malonaldehyde.

Lipid oxidation: Mechanisms, products and biological significance

Eight different vegetable oils obtained commercially were analyzed for volatiles by capillary gas chromatography (GC). Volatiles generated in a GC static headspace sampler at 180 C were injected automatically onto a chemically bonded capillary column. Only a small number of GC peaks of low intensity were observed in the fresh samples, which varied in peroxide values from 0.2 to 3. Several major peaks were evident in the oils aged eight and 16 days at 60 C with peroxide values ranging from 16 to 65. Thirty-four GC peaks were identified on the basis of relative retention time of reference compounds and on the basis of gas chromatography-mass spectrometry (GC-MS). Volatile compounds identified were those expected from the autoxidation of principal unsaturated fatty acid components of each vegetable oil tested. The relative concentrations of volatile components increased with the level of oxidation as determined by peroxide value.

Capillary gas chromatographic analyses of headspace volatiles from vegetable oils

Three samples each of soybean, sunflower and low erucic acid rapeseed (LEAR) oils were evaluated for flavor and oxidative stability. The commercially refined and bleached oils were deodorized under identical conditions. No significant differences were noted in initial flavor quality. After storage at 25°C or 60°C in the dark, soybean oils—with or without citric acid—were more stable than either sunflower or LEAR oils. However, in the presence of citric acid, soybean oils were significantly less stable to light exposure than either LEAR or sunflower oils. In contrast, in the absence of citric acid, soybean oils were significantly more light stable than LEAR oils. In either the presence or absence of citric acid, sunflower oil was significantly more stable to light than soybean oil. Analyses by static headspace gas chromatography showed no significant differences in formation of total volatile compounds between soybean and LEAR oils. However, both oils developed significantly less total volatiles than the sunflower oils. Each oil type varied in flavor and oxidative stability depending on the oxidation method (light vs dark storage, absence vs presence of citric acid, 100°C vs 60°C).

Flavor and oxidative stability of soybean, sunflower and low erucic acid rapeseed oils

β-Carotene was added to soybean salad oils to study its effect in inhibiting flavor deterioration due to light exposure. Flavor evaluations indicated that (a) when oils treated with citric acid were exposed to light (7535 lux) for 8 to 16 hr, oils containing 5 to 10 ppm β-carotene showed improved flavor stability compared to oils containing 0 to 1 ppm β-carotene; and (b) when oils were not treated with citric acid, only oils containing 20 ppm β-carotene were more stable to light. Capillary gas chromatographic analysis showed that the addition of 1 to 20 ppm of β-carotene significantly decreased formation of 2-heptenal and 2,4-decadienal in the absence or presence of citric acid. Determination of peroxide values showed the same trends as gas chromatographic analyses of volatiles. In the presence of 15 and 20 ppm β-carotene, some off-flavors, as well as poor ratings for color quality, were reported by panelists. Therefore, flavor deterioration initiated by light can be inhibited effectively in soybean oil, without affecting color quality, by addition of β-carotene at concentrations from 5 to 10 ppm to oils treated with citric acid.

Effects of β-carotene on light stability of soybean oil

To develop new knowledge on undesirable flavors affecting the quality of foods containing polyunsaturated lipids, we investigated the volatiles in soybean oil oxidized at different conditions by three capillary gas chromatographic methods: (a) direct injection (5 min heating at 180 C); (b) static headspace (20 min heating at 180 C, pressurizing for one min), and (c) dynamic headspace (purging 15 min at 180 C onto a porous polymer trap, desorbing from trap for five min). A fused silica column was used with bonded polymethyl and phenyl siloxane phase. At peroxide values between 2 and 10, the major volatile products found in soybean oil by the three methods were pentane, hexanal, 2-heptenal, 2,4-heptadienal and 2,4-decadienal. The intensities of each volatile compound varied with the analytical methods used.

E. N. Frankel

Papers

Lipid oxidation: Mechanisms, products and biological significance

Capillary gas chromatographic analyses of headspace volatiles from vegetable oils

Flavor and oxidative stability of soybean, sunflower and low erucic acid rapeseed oils

Effects of β-carotene on light stability of soybean oil

Comparison of gas chromatographic methods for volatile lipid oxidation compounds in soybean oil