The partial oxidation of C4–C6 alkanes to maleic anhydride, 2-methyl maleic anhydride, and acetic acid over MoVO catalysts

Alkanes such as iso-butane, n-pentane, and cyclohexane have been converted effectively to maleic anhydride, 2-methyl maleic anhydride, and acetic acid over MoVO catalysts below 330 °C. In order to explore the possible reaction pathways, the oxidation of iso-butene, cyclohexene, 2-methyl-1-propanol, tert-butanol, and 2-methylacrylic acid were examined over the catalysts. In iso-butene oxidation, acetic acid and 2-methyl maleic anhydride were detected but not maleic anhydride. In cyclohexene oxidation, benzene and phenol were detected as major products but it was not the case in cyclohexane oxidation. The results of our investigation indicate that the oxidation pathway of iso-butane is different from that of iso-butene, 2-methyl-1-propanol, tert-butanol, and 2-methylacrylic acid, whereas the oxidation pathway of cyclohexane is different from that of cyclohexene.     

Tannin sensitivity in larvae ofMalacosoma disstria (Lepidoptera): Roles of the peritrophic envelope and midgut oxidation

Final-instarMalacosoma disstria fed artificial diets containing tannic acid develop lethal pupal deformities. We examined some of the factors potentially underlying tannin sensitivity in this species, including the permeability of the peritrophic envelope to tannic acid and the chemical fate of tannic acid in the gut. Tannic acid does not penetrate the peritrophic envelope ofM. disstria, demonstrating that the containment of tannic acid within the endoperitrophic space is not sufficient to protect an insect herbivore from the adverse effects of ingested tannins. Ingested tannic acid undergoes extensive chemical modification in the midgut. Only 19–21 % of the high molecular weight components of the tannic acid ingested was recovered in the frass. Of two possible chemical fates of ingested tannic acid, oxidation is the predominant chemical transformation, whereas little hydrolysis occurs. Measurements of gut redox parameters showed that conditions in the midgut favor the oxidation of phenols. However, similar conditions occur in the midguts ofOrgyia leucostigma, in which no oxidation occurs. Therefore, oxidizing gut redox conditions do not necessarily lead to polyphenol oxidation in lepidopteran larvae. We conclude that the sensitivity ofM. disstria to ingested tannins is a consequence of their oxidation in the midgut.     

Facile and not facile reactions for the production of maleic and phthalic anhydrides with vanadium mixed oxides based catalysts

Vanadium is a key element in the formulation of catalysts for the production of anhydrides by selective vapor oxidation with molecular oxygen. A study of the oxidations ofo-xylene,n-butane and benzene on V-P, V-Mo and V-Ti mixed oxides, the commercial catalysts for the synthesis of anhydrides, was carried out. The oxidation ofo-xylene on the three catalysts was the most facile reaction leading to high yields in phthalic anhydride; on the contrary in the oxidation ofn-butane only V-P mixed oxide was active and selective. V-P mixed oxide is active and selective in the oxidation of all the feedstocks and can be identified as the most polyfunctional catalyst. V-Mo is active and selective in botho-xylene and benzene oxidation and V-Ti only ino-xylene oxidation. Moreover the lesser selectivity in phthalic anhydride observed with V-P and V-Mo mixed oxides has been attributed to parallel oxidation reactions to the formation of phthalic anhydride, evidenced by a higher amount of phthalide.     

Deracemisation of Mandelic Acid to Optically Pure Non‐Natural L‐Phenylglycine via a Redox‐Neutral Biocatalytic Cascade

A biocatalytic redox‐neutral reaction cascade was designed for the deracemisation of racemic mandelic acid to yield optically pure L ‐phenylglycine employing three enzymes. The cascade consisted of three steps: a racemisation, an enantioselective oxidation and a stereoselective reductive amination. The enantioselective oxidation of D ‐mandelic acid to the corresponding oxo acid was coupled with the stereoselective reductive amination of the latter; thus the oxidation as well as the reduction reactions were performed simultaneously. The formal hydrogen abstracted in the first step – the oxidation – was consumed in the reductive amination allowing a redox‐neutral cascade due to a cascade‐internal cofactor recycling. The enantiomers of the starting material were interconverted by a racemase (mandelate racemase) ensuring that in theory 100% of the starting material can be transformed. Using this set‐up racemic mandelic acid was transformed to optically pure L ‐phenylglycine (ee >97%) at 94% conversion without the requirement of any additional redox reagents in stoichiometric amounts.     

Inhibition of lipid peroxidation by anthocyanins,anthocyanidins and their phenolic degradation products

Food components that delay or prevent biomolecule oxidation may be relevant in shelf life extension as well as disease prevention. Anthocyanins are a potentially important group of compounds, but they are prone to degradation both in vitro and in vivo, producing simple phenols. In this study, eight structurally related (poly)phenols [anthocyan(id)ins and phenolic acids] were examined for their ability to inhibit lipid oxidation at physiologically relevant concentrations (100–1000 nM) using the Cu²⁺‐mediated low‐density lipoprotein oxidation model. Interaction between each (poly)phenol and Cu²⁺ ions was also investigated. (Poly)phenols with an ortho‐dihydroxy group arrangement, i.e. cyanidin‐3‐glucoside, cyanidin and protocatechuic acid, were the most effective within their class, extending the lag phase to oxidation by 137, 255 and 402%, respectively (at 1000 nM). At the same concentration, trihydroxy‐substituted compounds (delphinidin and gallic acid) were of intermediate efficacy, extending the lag phase by 175 and 38%, respectively. Compounds with the 4'‐hydroxy‐3',5'‐methoxy arrangement (i.e. malvidin‐3‐glucoside and malvidin) were the least effective (3 and 58% extension, respectively), while syringic acid (4‐hydroxy‐3,5‐dihydroxy benzoic acid) was pro‐oxidant (lag phase shortened by 31%). (Poly)phenols with the ortho‐dihydroxy arrangement chelated Cu²⁺ ions, which in part explains their greater efficacy over the other (poly)phenols in this model oxidation system. However, differences in their hydrogen‐donating properties and their partitioning between lipid and hydrophilic phases are also relevant in explaining these structure‐activity relationships.     

Antioxidant activities of selected oriental herb extracts

Antioxidant activities of methanol extracts of 180 Oriental herbs were studied by determining the peroxide values of linoleic acid during storage at 50°C. Among the herb extracts tested, 44 species showed strong antioxidant activities on the oxidation of linoleic acid. The antioxidative effects of these 44 selected herb extracts were studied further in a methyl linoleate system during storage for 35 d. Among the 44 species tested, 11 species had particularly high antioxidative effects. The effects of type of extraction solvent (methanol, petroleum ether and ethyl acetate) on the antioxidant activities of the 11 species were studied. Antioxidant activities of most herb extracts were greatly dependent on the extraction solvent used; however, some of the extracts showed strong antioxidant activities regardless of the solvents used for the extraction. Among the 11 herbs selected, based on the antioxidant activity of their methanol extracts, two (i.e.,Psoralea corylifolia L. andSorphora angustifolia Sieb. & Zucc.) were selected for further study in lard held at 75°C for 7 d. The methanol extracts ofP. corylifolia L. andS. angustifolia Sieb. & Zucc. greatly decreased the peroxide formation of lard during storage. Treatment with 0.20% methanolic extract ofP. corylifolia L. exhibited significantly stronger antioxidant effect on the oxidation of lard than treatment with 0.02% butylated hydroxyanisole (P<0.05).     

Soybean lipoxygenase is active on nonaqueous media at low moisture: a constraint to xerophilic fungi and aflatoxins?

Previous workers have reported that certain products of the lipoxygenase pathway are detrimental either to the development and growth of Aspergillus species or to aflatoxin production by these organisms. Since Aspergillus often thrives on “dry” stored grains, depending on the level of the relative humidity, we sought to determine if lipoxygenase could catalyze the oxidation of linoleic acid on these “dry” substrates equilibrated at various relative humidities. A desiccated model system, previously adjusted to pH 7.5, was composed of soybean extract, linoleic acid, and cellulose carrier. The model system was incubated for up to 24 h at four relative humidities ranging between 52 and 95% to determine the extent of oxidation catalyzed by lipoxygenase, compared with heat-inactivated controls. Oxidation in the active samples was much greater than in the controls at all relative humidities, and oxidation was principally enzymatic as demonstrated by chiral analysis of the linoleate hydroperoxides formed. The main product was 13S-hydroperoxy-9Z,11E-octadecadienoic acid, accompanied by a significant percentage of 9S-hydroperoxy-10E,12Z-octadecadienoic acid. Since the products became more racemic with time of incubation, autoxidation appeared to be initiated by the lipoxygenase reaction in dry media. Additionally, the biological relevance of lipoxygenase activity was tested under these xerophilic conditions. Thus, enzyme-active and heat-inactivated defatted soy flour amended either with or without 3.5% by weight linoleic acid was inoculated with fungal spores and incubated at 95% relative humidity. Although fungal growth occurred on all treatments, samples inoculated with Aspergillus parasiticus showed significantly less aflatoxin in the enzyme-active samples, compared to inactivated flour. Addition of linoleic acid had little effect, possibly because the defatted soy flour was found to contain 1.7% residual linoleic acid as glyceride lipid.     

A New Strategy for the Preparation of Terephthalic Acid by the Aerobic Oxidation of p‐Xylene using N‐Hydroxyphthalimide as a Catalyst

A new methodology for the production of terephthalic acid ( 3 ) by the aerobic oxidation of p‐xylene ( 1 ) using a combined catalytic system of N‐hydroxyphthalimide (NHPI)/Co(OAc) ₂/Mn(OAc) ₂was developed. The oxidation of 1 under a dioxygen atmosphere in the presence of a catalytic amount of NHPI/NHPI(OAc) ₂/Mn(OAc) ₂at 100 °C for 14 h afforded terephthalic acid in 82% yield. Removal of Mn(OAc) ₂ from the catalytic system resulted in considerable reduction in the yield of 3 . When the oxidation of 1 was carried out under a pressure of air (30 atm) at 150 °C, the reaction was completed within 3 h to give 3 in 84% yield. The oxidation of p‐toluic acid ( 2 ), which can be prepared by the oxidation of 1 using the NHPI/NHPI(OAc) ₂ system at room temperature, by the NHPI/NHPI(OAc) ₂/Mn(OAc) ₂system under pressure of air (30 atm) at 150 °C gave 3 in 95% yield. N‐Acetoxyphthalimide (NAPI) was found to require a lower catalyst loading than NHPI, but oxidation with NAPI was slower. Thus, the oxidation of 1 catalyzed by NAPI (5 mol %)/Co(OAc) ₂ (0.5 mol %)/Mn(OAc) ₂ (0.5 mol %) under a dioxygen atmosphere (1 atm) in acetic acid at 100 °C gave 3 in 80% yield.     

Chlorophyll breakdown by gamma irradiation in a model system containing linoleic acid

The possible breakdown of chlorophyll by irradiation was investigated. Chlorophyll b standard (3 ppm) was added to a methanol solution containing 1% linoleic acid. Irradiation up to 20 kGy was performed with or without N₂-bubbling, and nonirradiated control was also prepared. Residual chlorophyll b content was analyzed by HPLC and UV-visible spectra after irradiation, and color was measured during 6 h of light exposure (3,300 lux, light intensity) to induce photooxidation. The added chlorophyll b was destroyed by irradiation at 20 kGy with or without N₂-bubbling. With N₂-bubbling the oil sample did not develop lipid oxidation during irradiation, and irradiated samples did not develop photooxidation during storage under light. Without N₂-bubbling, irradiated oil samples had higher PV than nonirradiated samples. The Hunter color a-value of oil increased and the b-value decreased with irradiation at 20 kGy. UV-visible spectra also supported the break-down of chlorophyll b in solution by irradiation. Irradiation at 2.5 kGy or above destroved all added chlorophyll b. The results indicate that irradiation technology could be applied to reduce or eliminate the residual chlorophyll in oil processing without developing lipid oxidation during the irradiation process, which would prolong the shelf life of oil products by protecting them from photooxidation during display.     

A revision of the mechanism of o-xylene oxidation to phthalic anhydride with V/Ti/O catalysts, and the role of the promoter Cs

This paper describes the effect of Cs oxide, a promoter of an anatase-supported 7 wt.% V₂O₅ catalyst for the oxidation of o-xylene to phthalic anhydride. The effect of Cs was investigated in relation to the reaction network at 320 °C, i.e., under conditions of incomplete o-xylene conversion. It was found that at this temperature the catalytic performance was affected by a surface-saturation effect. However, Cs had the role of favoring the desorption of intermediates and keeping a cleaner and more oxidizing catalyst surface, so accelerating the conversion of the reactant and the consecutive oxidations occurring upon the reaction intermediates finally leading to phthalic anhydride. This de-saturation derived from the enhancement of the V re-oxidation rate, which is one main effect of Cs in V/Ti/O catalysts. Besides the route of o-xylene oxidation to the main reaction intermediate o-tolualdehyde, a parallel reaction pathway included the direct oxidation of o-xylene to phthalaldehyde; the latter was one intermediate in the formation of phthalide, via intramolecular condensation, and of phthalic acid.     

The efficient liquid‐phase oxidation of aromatic hydrocarbons by molecular oxygen in the presence of MnCO3

BACKGROUND: The liquid‐phase catalytic oxidation of aromatic hydrocarbons by molecular oxygen is a commercially important process. We consider the MnCO₃‐promoted oxidation of toluene to produce benzaldehyde and benzoic acid. In this investigation, toluene was oxidized with 25.0% conversion and 80.8% selectivity with respect to benzoic acid in the presence of MnCO₃ under 1.0 MPa of oxygen at 190 °C for 2 h. RESULTS: Moreover, the oxidation of other aromatic hydrocarbons, such as ethylbenzene, p‐xylene, m‐xylene, o‐xylene, and p‐chlorotoluene, were also efficiently promoted by MnCO₃. CONCLUSION: It is concluded that an efficient oxidation of aromatic hydrocarbons can be achieved in the presence of MnCO₃ under solvent‐free conditions. The catalytically active species are high‐valence Mn generated via the action of MnCO₃ with oxygen. Copyright © 2007 Society of Chemical Industry     

Oxidation of acylglycerols and phosphoglycerides by soybean lipoxygenase

Lipoxygenase (EC 1.13.11.12) catalyzes the incorporation of oxygen into polyunsaturated fatty acids, resulting in the formation of their corresponding hydroperoxides. The ability of a commercial preparation of soybean (Glycine max L. Merr.) lipoxygenase to catalyze the oxidation of acylglycerols and phosphoglycerides was investigated. The oxidation rate of trilinolein increased nearly 100% when 5 mM deoxycholate was added to the reaction medium. With further increases in the concentration of deoxycholate, the oxidation rate decreased slightly. The pH profile of trilinolein oxidation was bell-shaped. The rate of oxidation was maximal at pH 8, and it decreased to near zero at pH 5 and pH 11. Even under optimal conditions, the rate of trilinolein oxidation was only 3% of that of linoleic acid, and analysis of time course data showed that, at most, 15% of available linoleate was oxidized. In contrast to the slow rate of trilinolein oxidation, tested phosphoglycerides and diacylglycerols were oxidized at moderate rates. The rate of phosphoglyceride oxidation depended upon the structure of the polar head group and varied between 7–28% of the rate of linoleic acid oxidation. Diacylglycerols reacted at a rate that was 40% of that of linoleic acid. Analysis of the time course of 1,3-dilinolein oxidation showed that as much as 67% of the available linoleate could be converted to the corresponding hydroperoxide. Analyses by high-performance liquid chromatography revealed that more than 20% of the 1,3-dilinolein was converted to unidentified products that are not hydroperoxides.     

Environmentally friendly liquid phase oxidation: enhanced selectivity in the aerial oxidation of alkyl aromatics,epoxidations and the Baeyer–Villiger oxidation using novel silica supported transition metal ions

Active transition metal species (Co, Cu, Cr, Ni or Mn) supported on a chemically modified silica gel are used as heterogeneous catalysts in a range of liquid phase oxidation reactions: alkyl aromatic side chain oxidations, epoxidations of alkenes and Baeyer–Villiger oxidations of linear ketones to esters and cyclic ketones to lactones. The catalyst employs metal centres bound to the silica surface via a hydrophobic spacer chain and is thus chemically robust and has a relatively high loading for a supported reagent (c 0.4 mmol g⁻¹). The Cr version of the catalyst promotes the oxidation of ethylbenzene to acetophenone in a solvent‐free system at a rate of 5.5% h⁻¹ (>370 turnover h⁻¹). It is also active for the oxidation of p‐chlorotoluene and p‐xylene to p‐chlorobenzoic acid and p‐toluic acid respectively. Cyclohexene is converted to its oxide at room temperature at a rate of c 28% h⁻¹ (c 12 turnover h⁻¹) using either the Ni or Cu versions of the catalyst. The room temperature Baeyer–Villiger oxidation of cyclohexanone is achieved at a rate of 44% h⁻¹ (49 turnover h⁻¹) using the Ni‐containing catalyst. The same material also promotes the Baeyer–Villiger oxidation of linear aliphatic ketones and aromatic side chains. All the above systems use either air or molecular oxygen as the oxidant rather than peroxides or peracids. © 1999 Society of Chemical Industry     

Electrooxidation of Aqueous p-Methoxyphenol on Lead Oxide Electrodes

Oxidation of p-methoxyphenol (pmp) in aqueous solution on bismuth-doped lead oxide was studied, and the effects of the initial pmp concentration, applied potential and hydrodynamic conditions upon the oxidation rate were identified. Under all conditions studied, the concentration decay of pmp during electrooxidation follows first—order reaction kinetics. Through analysis of rotating ring-disc currents, the faradaic efficiencies for oxidation at various concentrations of pmp in solution were determined. Using u.v.—vis. and H¹RMN spectroscopy for solution analysis, it is shown that partial oxidation of pmp occurs in chloride-free aqueous solutions. The principal products were p-benzoquinone and maleic acid, with low production of CO₂ up to 1000 C dm^–3 charge. Mineralization to CO₂ was considerably improved upon addition of chloride ions to the solution. In situ FTIR spectra of the electrode surface during electrolysis indicated that the presence of chloride ions enhances the mineralization of pmp by reaction of benzoquinone with anodically generated hypochlorite.     

Manganese Dioxide and N‐Hydroxyphthalimide. An Effective Catalytic System for Oxidation of Nitrotoluenes with Molecular Oxygen

The inexpensive manganese dioxide has been proven to be an efficient auxiliary for oxidizing N‐hydroxyphthalimide (NHPI) to form the phthalimide N‐oxyl radical via reduction and reoxidation. The combination of manganese dioxide and NHPI could catalyze effectively the oxidation of nitrotulenes by molecular oxygen. Thus, the oxidation of p‐nitrotoluene with molecular oxygen (0.4 M Pa) in the presence of manganese dioxide (10 mol %) and NHPI (10 mol %) in acetic acid at 110 °C for 4 h proceeded with 97 % conversion, and gave p‐nitrotoluene in 89 % isolated yield.     

Advanced oxidation with ozone of 1,3,6‐naphthalenetrisulfonic acid in aqueous solution

The kinetics of oxidation with ozone of 1,3,6‐naphthalenetrisulfonic acid was analysed by studying the influence of different experimental parameters such as the concentration of tert‐butyl alcohol (2‐methyl‐2‐propanol), initial concentration of the acid, pH, and temperature. The rate constant of the direct reaction at 25 °C was calculated (k_D = 6.72 M ^?1s^?1). The constant of the free radical reaction was determined with the competitive kinetics method, using sodium 4‐chlorobenzoate as reference compound, obtaining a value of k_OH = 3.7 × 10⁹ M ^?1s^?1. It was demonstrated that even at very acid pH values, 80% of the 1,3,6‐naphthalenetrisulfonic acid was degraded by free radical reactions, so that the ozonation of this acid may be considered an advanced oxidation process. © 2002 Society of Chemical Industry     

Oxidation of p-methoxyphenol on SnO2–Sb2O5 electrodes: Effects of electrode potential and concentration on the mineralization efficiency

The oxidation of p-methoxyphenol in aqueous solution on antimony-doped tin oxide has been studied, and the effects of applied potential and initial PMP concentration upon the oxidation rate have been identified. The concentration decay of PMP during its electrooxidation follows first-order reaction kinetics. Analysis solution during electrolysis using UV–Vis spectroscopy revealed that under some experimental conditions partial oxidation of PMP occurs. The principal products were p-benzoquinone and aliphatic (maleic and oxalic) acids. The Faradaic efficiencies for oxidation at different applied potentials were determined from the UV–Vis spectra obtained. It is shown that production of CO₂ was very low at potentials below 2.3 V with respect to the saturated calomel electrode, and that at more positive potentials mineralization to CO₂ decreased as the concentration of PMP in solution increased.     

Application of NOX storage/release materials based on alkali-earth oxides supported on Al2O3 for high-temperature diesel soot oxidation

Alkali-earth oxides and nitrates supported on alumina were studied as model systems for NO_X storage/release. Their impact on the high-temperature soot oxidation has been investigated. The stability of surface nitrates and temperature of NO_X release increase parallel to the basicity of the cation. The presence of soot decreases the temperature of NO_X release. The storage capacity depends on the several factors, such as basicity, dispersion of the cation, and pre-treating conditions. Adsorption of NO with O₂ at 200 °C leads to the formation of surface nitrates that mainly exist as ionic nitrates. Stored nitrates contribute to the soot oxidation and assist to lower the temperature of soot oxidation up to almost 100 °C. In the presence of only NO_X storage material the efficiency of NO_X utilization is, however, quite low, around 30%. Therefore, the presence of an oxidation catalyst is essential to increase the efficiency of NO_X utilization for soot oxidation up to 140% and selectivity towards CO₂. A combination of oxidation catalyst with NO_X storage materials enables to lower the temperature of soot oxidation more than 100 °C for the Sr- and Ca-based systems.     

Bioleaching of acid‐consuming low‐grade nickel ore with elemental sulfur addition and subsequent acid generation

The bioleaching of a nickel concentrate and an acid‐consuming nickel ore was studied using a co‐culture of Acidithiobacillus ferrooxidans and A. thiooxidans, as well as a thermophilic enrichment culture, VS2. The VS2 was dominated by a Sulfolobus species related to Sulfolobus metallicus. Nickel concentrate was readily solubilized with A. ferrooxidans and the VS2, resulting in nickel yields of 56% and 100%, respectively. Low‐grade nickel ore required 350 g H₂SO₄ kg^?1 ore for maintaining the pH of the leaching solution below 3. To overcome the high acid demand, biological elemental sulfur oxidation was combined with the ore leaching. Leaching of a 2% (wt/vol) nickel ore with a co‐culture of A. thiooxidans and A. ferrooxidans resulted in nickel yield of up to 86% with acid supplementation of 290 g H₂SO₄ kg^?1 ore. When coupled with biological sulfur oxidation, an 86% nickel recovery was achieved with 0.5% (wt/vol) ore concentration without further sulfuric acid addition. The VS2 oxidized sulfur at a rate of 0.063 g L^?1 d^?1 and the simultaneous nickel ore leaching resulted in 100% nickel yield. In summary, the potential of using elemental sulfur addition and subsequent biological acid generation to maintain the low pH during bioleaching of an acid‐consuming nickel ore was demonstrated. Copyright © 2005 Society of Chemical Industry     

KMnO4/guanidinium-based sulfonic acid: as an efficient Brønsted acid organocatalyst for the selective oxidation of organic compounds

KMnO₄/guanidinium-based sulfonic acid as a green organocatalytic oxidative system can be used effectively for the selective oxidation of organic compounds in n-hexane as a nonpolar and inert solvent at room temperature in good yields. The use of this approach is described for the oxidation of alkyl arenes, alcohols, and sulfides.