Inhibitory Effect of Phosphonium-Based Ionic Liquids on Coal Oxidation

To develop a chemical inhibitor that can efficiently suppress coal oxidation, nine tetraalkylphosphonium-based ionic liquids (ILs) and one imidazolium-based IL [1-allyl-3-methylimidazolium chloride ([AMIm]Cl)] were examined as additives. These ILs were used to treat and investigate the inhibitory effect on the oxidation activity and the structure of lignite coal. Characterization using thermogravimetric analysis showed that phosphonium-based ILs are able to inhibit coal oxidation up to 400 degrees C with the tributylethylphosphonium diethylphosphate ([P-4,P-4,P-4,P-2][DEP]) found to be the most effective. In contrast to the tetraalkylphosphonium-based ILs, inhibition using [AMIm]Cl was only found to be effective at temperatures below 250 degrees C, indicating that the tetraallcylphosphonium-based ILs may be more suitable for the future application of suppressing coal spontaneous combustion over a wide range of temperatures. Fourier transform infrared spectroscopic data showed that the various functional groups change in the coal following IL treatment, which are a decrease in the minerals and hydrogen bonds in all treated coals, while decreased aliphatic hydrocarbon and increased carbonyl bonds only appeared in some samples. During the oxidation of coal, the decomposition of aliphatic hydrocarbon groups is inhibited and the formation of carbonyl groups is delayed, so that the evolved gas concentration decreased, as shown by the temperature-programmed oxidation-mass spectrometry results. The deployment of the [P-4,P-4,P-4,P-2][ DEP] and tributylmethylphosphonium methylsulfate Its as additives also show good inhibitory effect on coal oxidation over the temperature range studied, and a relatively stronger interaction between [P-4,P-4,P-4,P-2] [DEP] and coal is demonstrated by the additive model.

Selective Palladium-Catalysed Aerobic Oxidation of Alcohols

Palladium has a significant track record as a catalyst for a range of oxidation reactions and it has been explored for the selective oxidation of alcohols for many years. This chapter focuses on the two main types of aerobic Pd catalysts: heterogeneous and ligand-modulated systems. In the case of heterogeneous systems, the mechanistic understanding of these systems and the use of in situ and operando techniques to obtain this knowledge are discussed. The current state-of-the-art is also summarized in terms of catalytic performance and substrate scope for heterogeneous Pd-based catalysts. In terms of ligand-modulated systems, leading examples of molecular Pd(ii) catalysts which undergo direct O2 coupled turnover are highlighted. The catalyst performance for such catalysts is exemplified and mechanistic understanding for these molecular systems is discussed.

A Highly Efficient Palladium(II)/Polyoxometalate Catalyst System for Aerobic Oxidation of Alcohols

A simple catalyst system composed of Pd(OAc)2, phosphomolybdic acid and tetrabutylammonium acetate oxidises a range of alcohols efficiently, with turnover numbers (TONs) of up to 10 000.

Quantum yield measurements for the photocatalytic oxidation of Acid Orange 7 (AO7) and reduction of 2,6-dichloroindophenol (DCIP) on transparent TiO2 films of various thickness

This work comprises the photoactivity assessment of transparent sol–gel TiO2 coatings of various thickness using two test systems. The initial rates of both photocatalytic reactions, namely the oxidative bleaching of Acid Orange 7 (AO7) and the reductive bleaching of 2,6-dichlorindophenol (DCIP) increase linearly with increasing titania film thickness as well as with increasing absorbed light flux. The latter work revealed quantum yields (QY) of 0.19% and 92% for the AO7 and DCIP test system, respectively. The low QY for the AO7 oxidation is due to the combination of a slow irreversible reduction of oxygen and also for the oxidation of AO7, thus favouring the high efficiency for electron–hole recombination that is typical for aqueous organic pollutants. In contrast, the very high QY for the photocatalysed reduction of DCIP is due to the presence of a vast excess of glycerol which traps the photogenerated holes efficiently and so allow time for the slower reduction of dye to take place. Furthermore, the oxidation of glycerol results in the generation of highly reducing R-hydroxyalkyl radicals that are able to also reduce DCIP. As a consequence of this ‘current doubling’ effect, the observed QY (92%) is much higher than the apparent theoretical value of 50%.

Char oxidation of torrefied biomass at high temperatures and high heating rates

The char oxidation of a torrefied biomass and its parent material was carried out in an isothermal plug flow reactor (IPFR), which is able to rapidly heat the biomass particles to a maximum temperature of 1400 °C at a heating rate of 104 °C/s, similar to the real conditions found in power plant furnaces. During each char oxidation test, the residues of biomass particles were collected and analyzed to determine the weight loss based on the ash tracer method. According to the experimental results, it can be concluded that chars produced from a torrefied biomass are less reactive than the ones produced, under the same conditions, from its raw material. The apparent kinetics of the torrefied biomass and its parent material are determined by minimizing the difference between the modeled and the experimental results. The predicted weight loss during char oxidation, using the determined kinetics, agrees well with experimental results

Arene cis-Diol Dehydrogenase-Catalysed Regio- and Stereoselective Oxidation of Arene-, Cycloalkane- and Cycloalkene-cis-diols to Yield Catechols and Chiral α-Ketols

Benzene cis-diol dehydrogenase and naphthalene cis-diol dehydrogenase enzymes, expressed in Pseudomonas putida wild-type and Escherichia coli recombinant strains, were used to investigate regioselectivity and stereoselectivity during dehydrogenations of arene, cyclic alkane and cyclic alkene vicinal cis-diols. The dehydrogenase-catalysed production of enantiopure cis-diols, α-ketols and catechols, using benzene cis-diol dehydrogenase and naphthalene cis-diol dehydrogenase, involved both kinetic resolution and asymmetric synthesis methods. The chemoenzymatic production and applications of catechol bioproducts in synthesis were investigated.

Mechanistic studies of the photocatalytic oxidation of microcystin-LR: An investigation of byproducts of the decomposition process

Microcystins (cyclic heptapeptides) are produced by a number of freshwater cyanobacteria and cause concern in potable water supplies due to their acute and chronic toxicity. The present study reports the structural characterization of the degradation products of the photocatalytic oxidation of microcystin-LR, so aiding the mechanistic understanding of this process. TiO₂ photocatalysis is a promising technology for removal of these toxins from drinking water. However, before it can be adopted in any practical application it is necessary to have a sufficient knowledge of degradation byproducts and their potential toxicity. Liquid chromatography-mass spectrometry analysis demonstrated that the major destruction pathway of microcystin appears to be initiated via three mechanisms: UV irradiation, hydroxyl radical attack, and oxidation. UV irradiation caused geometrical isomerization of microcystin converting the (4E), (6E) of the Adda configuration to (4E), 6(Z) or 4(Z), 6(E). Hydroxyl radical attack on the conjugated diene structure of Adda moiety produced dihyroxylated products. Further oxidation cleaved the hydroxylated 4-5 and/or 6-7 bond of Adda to form aldehyde or ketone peptide residues, which then were oxidized into the corresponding carboxylic acids. Photocatalysis also hydrolyzed the peptide bond on the ring structure of microcystin to form linear structures although this appeared to be a minor pathway.

Mechanistic and toxicity studies of the photocatalytic oxidation of microcystin-LR

Cyanobacterial toxins present in drinking water sources pose a considerable threat to human health. Conventional water treatment systems have proven unreliable for the removal of these toxins and hence new techniques have been investigated. Previous work has shown that TiO₂ photocatalysis effectively destroys microcystin-LR in aqueous solutions, however, a variety of by-products were generated. In this paper, we report a mechanistic study of the photocatalytic destruction of microcystin-LR. In particular, the toxicity by-products of the process have been studied using both brine shrimp and protein phosphatase bioassays. 

Hydrogen peroxide enhanced photocatalytic oxidation of microcystin-lR using titanium dioxide

Cyanobacterial toxins present in drinking water sources pose a considerable threat to human health. Conventional water treatment systems have proven unreliable for the removal of these toxins and hence new techniques have been investigated. Previous work has shown that TiO₂ photocatalysis effectively destroys microcystin-LR in aqueous solutions, however non-toxic by-products were detected. It has been shown that photocatalytic reactions are enhanced by utilisation of alternative electron acceptors. We report here enhanced photocatalytic degradation of microcystin-LR following the addition of hydrogen peroxide to the system. It was also found that hydrogen peroxide with UV illumination alone was capable of decomposing microcystin-LR although at a much slower rate than found for TiO₂. No HPLC detectable by-products were found when the TiO₂/UV/H₂O₂ system was used indicating that this method is more effective than TiO₂/UV alone. Results however indicated that only 18% mineralisation occurred with the TiO₂/UV/H₂O₂ system and hence undetectable by-products must still be present. At higher concentrations hydrogen peroxide was found to compete with microcystin-LR for surface sites on the catalyst but at lower peroxide concentrations this competitive adsorption was not observed. Toxicity studies showed that both in the presence and absence of H₂O₂ the microcystin solutions were detoxified. These findings suggest that hydrogen peroxide greatly enhances the photocatalytic oxidation of microcystin-LR.

Detoxification of microcystins (cyanobacterial hepatotoxins) using TiO2 photocatalytic oxidation

TiO₂ photocatalysis has been used to destroy microcystin-LR in aqueous solution. The destruction of this toxin was monitored by HPLC, and the disappearance was accompanied by the appearance of seven UV detectable compounds. Spectral analysis revealed that some of these compounds retained spectra similar to the parent compound suggesting that the Adda moiety, thought to be responsible for the characteristic spectrum, remained intact whereas the spectra of some of the other products was more radically altered. Six of the seven observed reaction products did not appear to undergo further degradation during prolonged photocatalysis (100 min). The degree to which microcystin-LR was mineralized by photocatalytic oxidation was determined. Results indicated that less than 10% mineralization occurred. Mass spectral analysis of the photocatalyzed microcystin-LR allowed tentative characterization of the reaction process and products. Reduction in toxicity due to the photocatalytic oxidation was evaluated using an invertebrate bioassay, which demonstrated that the disappearance of microcystin-LR was paralleled by a reduction in toxicity. These findings suggest that photocatalytic destruction of microcystins may be a suitable method for the removal of these potentially hazardous compounds from drinking water.

Cationic palladium(II) complexes as catalysts for the oxidation of terminal olefins to methyl ketones using hydrogen peroxide.

Ligated Pd(II) complexes have been studied for the catalytic oxidation of terminal olefins to their corresponding methyl ketones. The method uses aqueous hydrogen peroxide as the terminal oxidant; a sustainable and readily accessible oxidant. The choice of ligand, counterion and solvent all have a significant effect on catalytic performance and we were able to develop systems which perform well for these challenging oxidations.

Toluene dioxygenase-catalysed oxidation route to angular cis-monohydrodiols and other bioproducts from bacterial metabolism of 1,2-dihydrobenzocyclobutene and derivatives

A mutant strain (UV4) of the soil bacterium Pseudomonas putida, containing toluene dioxygenase, has been used in the metabolic oxidation of 1,2-dihydrobenzocyclobutene 12 dagger and the related substrates 1,2-dihydrobenzocyclobuten-1-ol 13 and biphenylene 33. Stable angular cis-monohydrodiol metabolites (1R,2S)-bicyclo[4.2.0]octa-3,5-diene-1,2 7, (1S,2S,8S)-bicyclo[4.2.0]octa-3,5-diene-1,2,8-triol 8 and biphenylene-cis-1,8b-diol 9, isolated from each of these substrates, have been structurally and stereochemically assigned. The structure, enantiopurity and absolute configuration of the other cis-diol metabolites, (2R,3S)-bicyclo[4.2.0]octa-1(6),4-diene-2,3-diol 14 and cis-1,2-dihydroxy-1,2-dihydrobenzocyclobutene 16, and the benzylic oxidation bioproducts, 1,2-dihydrobenzocyclobuten-1-ol 13, 1,2-dihydrobenzocyclobuten-1-one 15 and 2-hydroxy-1,2-dihydrobenzocyclobuten-1-one 17, obtained from 1,2-dihydrobenzocyclobutene and 1,2-dihydrobenzocyclobuten-1-ol, have been determined with the aid of chiral stationary-phase HPLC, NMR and CD spectroscopy, and stereochemical correlation. X-Ray crystallographic methods have been used in the determination of absolute configuration of the di-camphanates 27 (from diol 7) and 32 (from diol 9), and the di-MTPA ester 29 (from diol 14) of the corresponding cis-diol metabolites. The metabolic sequence involved in the formation of bioproducts derived from 1,2-dihydrobenzocyclobutene 12 has been investigated.

Oxidation of N-(4-methoxybenzyl)-2-pyrrolidinones to N-(4-methoxybenzoyl)-2-pyrrolidinones. Rapid entry to optically active Aniracetam analogues.

Oxidation of readily available N-(4-methoxybenzyl)-5-alkylpyrrolidin-2-ones to the corresponding N-(4-methoxybenzoyl)-5-alkylpyrrolidin-2-ones gives direct access to enantiomerically pure 5-alkyl analogues of the cognition activating agent Aniracetam. Copyright (C) 1996 Elsevier Science Ltd

BACTERIAL OXIDATION OF BENZOCYCLOALKENES TO YIELD MONOL, DIOL AND TRIOL METABOLITES

Benzylic monooxygenation of benzocycloalkenes, 2-4, by enzymes in intact cultures of Pseudomonas putida UV4 yielded exclusively the [R] enantiomers, 6-8, and the derived ketones 10-12; by contrast, biotransformation of benzocyclobutene, 1, yielded both monooxygenation (5 and 9), dioxygenation (13, 14 and 15), and trioxygenation (16) products.